Sustainability in the Textile and Apparel Industries: Sourcing Natural Raw Materials (Sustainable Textiles: Production, Processing, Manufacturing & Chemistry) 303038540X, 9783030385408

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Sustainable Textiles: Production, Processing, Manufacturing & Chemistry

Subramanian Senthilkannan Muthu Miguel Angel Gardetti Editors

Sustainability in the Textile and Apparel Industries Sourcing Natural Raw Materials

Sustainable Textiles: Production, Processing, Manufacturing & Chemistry

Series editor Subramanian Senthilkannan Muthu, Head of Sustainability, SgT and API, Kowloon, Hong Kong

More information about this series at http://www.springer.com/series/16490

Subramanian Senthilkannan Muthu Miguel Angel Gardetti Editors

Sustainability in the Textile and Apparel Industries Sourcing Natural Raw Materials

Editors Subramanian Senthilkannan Muthu Head of Sustainability SgT and API Kowloon, Hong Kong

Miguel Angel Gardetti Centro de Estudios para el Lujo Sustentable Buenos Aires, Argentina

ISSN 2662-7108     ISSN 2662-7116 (electronic) Sustainable Textiles: Production, Processing, Manufacturing & Chemistry ISBN 978-3-030-38540-8    ISBN 978-3-030-38541-5 (eBook) https://doi.org/10.1007/978-3-030-38541-5 © Springer Nature Switzerland AG 2020 This work is subject to copyright. All rights are reserved by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland

Preface

Textiles and clothing industry impacts have been analyzed by many authors and organizations, and there are many publications in the literature, but even then, there are a lot of topics not covered in the scientific literature. Sustainability in the textile and apparel industries is an important and ongoing topic. There are a lot of new fibers, yarns, fabrics, finishes, chemicals, strategies, designs, technologies, and so on to address the sustainability in the textile sector. This book set comprises of five volumes which aim to address sustainability in the textile and apparel industries under many wide topics, and this volume deals with the natural raw materials for textile sourcing and gives a comprehensive outlook on various sustainable raw materials from natural origin for raw material sourcing. As anyone can imagine, sourcing is the vital and first step in apparel production, whereas the choice of sustainable raw materials plays a crucial role in deciding the fate of the product in terms of sustainability. There is a generic division of raw materials, namely, natural and man-made ones. To begin with, the work titled “The Effects of Ecological and Sustainable Chemical Surface Modification Methods on the Properties of Lignocellulose-Based Fibers” developed by Emine Dilara Koçak and Merdan Nigar analyzes the physical, mechanical, and morphological properties of fibers, comparing chemical methods for the fibrillation of lignocellulose-based fibers (bananas, Agave Americana, sisal, raffia, artichoke, etc.) with ecological methods (ultrasonic, microwave, plasma methods) and enzymes. The following chapter, “Sustainable Plant-Based Natural Fibers,” written by Seyda Eyupoglu, explores sustainability in plant-based natural fibers (cotton, bamboo, flax, hemp, kenaf, sisal, jute, ramie, abaca, banana, pineapple, coconut, and okra fiber). It describes the structure, production process, production and application areas, potentials and limitations of the fibers, and the importance of sustainable agriculture and ecology. Subsequently, Marisa Gabriel, Miguel Angel Gardetti, and Ivan Cote-Maniére, in “Coyoyo Silk: A Potential Sustainable Luxury Fiber,” present mounting a silk, v

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Preface

explore the whole process of obtaining and processing the fiber, and analyze ­artisans’ hardships to maintain this local and cultural legacy alive and the potential of this material as sustainable luxury. Moving on to the next chapter, “Hemp Fiber as a Sustainable Raw Material Source for Textile Industry: Can We Use Its Potential for More Eco-friendly Production?,” the authors, Görkem Gedik and Ozan Avinc, present sustainable and biodegradable hemp fiber as an alternative to cotton- and petroleum-based synthetic fibers, exploring common and special uses and possible future innovative alternatives of hemp fibers for technical textile production. Finally, Fatma Filiz Yıldırım, Ozan Avinc, Arzu Yavas, and Gökcin Sevgisunar, in their chapter “Sustainable Antifungal and Antibacterial Textiles Using Natural Resources,” describe antimicrobial activity (antifungal and antibacterial activities) on textile products imparted by natural dyes and natural resources and their application methods to textile materials, exploring antimicrobial properties of different plant extracts and animal extracts and their characteristics, uses, and potentials. Kowloon, Hong Kong  Subramanian Senthilkannan Muthu Buenos Aires, Argentina  Miguel Angel Gardetti

Contents

The Effects of Ecological and Sustainable Chemical Surface Modification Methods on the Properties of Lignocellulose-Based Fibers ����������������������������������������������������������������������    1 Emine Dilara Koçak and Merdan Nigar Sustainable Plant-Based Natural Fibers��������������������������������������������������������   27 Seyda Eyupoglu Coyoyo Silk: A Potential Sustainable Luxury Fiber������������������������������������   49 Marisa Gabriel, Miguel Angel Gardetti, and Ivan Cote-Maniére Hemp Fiber as a Sustainable Raw Material Source for Textile Industry: Can We Use Its Potential for More Eco-Friendly Production?��������������������������������������������������������������   87 Görkem Gedik and Ozan Avinc Sustainable Antifungal and Antibacterial Textiles Using Natural Resources ��������������������������������������������������������������������������������  111 Fatma Filiz Yıldırım, Ozan Avinc, Arzu Yavas, and Gökcin Sevgisunar Index������������������������������������������������������������������������������������������������������������������  181

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The Effects of Ecological and Sustainable Chemical Surface Modification Methods on the Properties of Lignocellulose-Based Fibers Emine Dilara Koçak and Merdan Nigar

Abstract  Ecological and sustainable production has attracted great attention recently because of the rapid consumption of natural resources and increase in environmental problems due to synthetic production activities globally. Therefore, natural-­based materials find their place in production activity progressively. The United Nations Food and Agriculture Organization and the Common Fund for Commodities (CFC) evince strict regulations for governments in order to clear harmful chemical reactions and environment in line with the genuine environmental awareness that is envisaged by the use of plant-based materials. Identification of the use of agricultural waste and legislations by governments will lead to the use of natural materials in this direction. Lignocellulose-based fibers are used in the production of green composites because of easy shaping, low price, and variety of raw materials, and they can be considered as suitable candidates for sustainable production in the generations to come. Surface modifications of lignocellulose-based fibers are made by using chemical and enzyme-based agents on the surface of the fibers. This process increases the functional properties of the fibers and enables fibers to be used in the industrial scale. Chemical surface modifications are carried out by conventional methods as well as ecological methods such as ultrasonic energy, microwave energy, and plasma technique. In this chapter, chemical methods for the fibrillation of lignocellulose-based fibers (bananas, Agave americana, sisal, raffia, artichoke, etc.) are compared with ecological methods (ultrasonic, microwave, and plasma methods) and enzymes in terms of physical, mechanical, and morphological properties of fibers. Thus, it can be concluded that ecological methods improve the properties of the fibers and help to reduce the chemical waste, water, and energy consumption. E. D. Koçak (*) Marmara University, Faculty of Technology, Department of Textile Engineering, Istanbul, Turkey e-mail: [email protected] M. Nigar Istanbul Commerce University, Faculty of Architecture and Design, Istanbul, Turkey e-mail: [email protected] © Springer Nature Switzerland AG 2020 S. S. Muthu, M. A. Gardetti (eds.), Sustainability in the Textile and Apparel Industries, Sustainable Textiles: Production, Processing, Manufacturing & Chemistry, https://doi.org/10.1007/978-3-030-38541-5_1

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Keywords  Lignocellulosic fibers · Sustainability · Ecological · Ultrasonic energy · Microwave energy

1  Introduction Environmental sustainability is now becoming a global trend, and large companies and municipalities are taking steps for creating a cleaner environment, thus; materials science has to draw a sustainable path as a result of increasing environmental concerns as of the end of the twentieth century. This roadmap is “green material, green chemistry” approaches to produce sustainable, renewable, and environmentally friendly materials. Green chemistry has announced to the world under the name of 12 rules that chemical processes are based on processes that reduce and completely eliminate the use of harmful substances [1]. Other branches of the industry have begun to use the 12 rules adopted by green chemistry. With this approach, the US Department of Energy aims to obtain at least 10% of all chemicals by 2020, and at least 50% by 2050 of plant resources [2]. The society is confident in products with a “green conceptual design”, which leads to higher selection/consumption of products by customers. Plant-based natural fibers used in the production of green materials have been utilized quite a lot in all branches of the industry, especially in the production of green composites and textile garment production, and alternative fiber approaches to cotton has become a trend. The use of adjectives such as green, bio, renewable, and sustainable has increased with the increase of alternative natural materials. In fact, the concept of sustainability, which is a trend topic, has given the name green to all materials that match all the given tariff. Materials from renewable sources have been offering an incredible growth curve over the last two decades, and sustainable materials have become billions of dollars in the industry. Among the green materials, green composites are one of the fastest-growing branches. In the textile industry, water, energy, and time consumption are quite high. Alternative energy sources and new processes with different environmental approaches are being searched for sustainability. In the textile industry, 35–40 L of water is consumed in the factory to produce a T-shirt. In fact, from field to production, this T-shirt consumes 2700 L of water. This is called virtual water [3]. In some processes in the textile sector such as bleaching, fleece, rinsing, dyeing, and washing of final products, high volumes of water are used. In order to prevent this, ultrasonic energy, microwave energy method, plasma method, and ozone-free dyeing methods could be used as alternative environmental friendly methods. It is clear that water will be more important than oil in the future. Increased global warming and depletion of usable water resources will lead to wars for water in the future. However, with increasing industrialization and growing population in Turkey, it is estimated that country may face water shortages by 2030. Sustainable use of existing water resources is very important. An important condition for sustainability of water is to maintain and manage the water resources in an efficient manner. Water footprint is a concept that has become popular recently. Water footprint is the most important element for sustainable water management. Water footprint consists of

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blue, green, and gray water. Blue water is the footprint of surface and groundwater. Green water footprint is the amount of rain. The gray water footprint is the amount of contaminated freshwater. With the water footprints and green chemistry approach, time, energy, chemical, and water-saving processes will be inevitable to use in order to protect our future from an environmental hazard. Studies are conducted to expand the area of lignocellulosic fibers usage in the industry. To make lignocellulosic fibers a suitable reinforcing material with adequate bonding characteristics for general use, various modification methods, including conventional, ultrasonic energy, and microwave energy treatment, are used to improve interfacial compatibility. In this chapter, studies are carried out to improve the hydrophilic characteristic of lignocellulosic fibers by means of chemical processes. The studies are based on cleaning those impurities affecting the mechanical, chemical, and physical characteristics of the fibers.

2  Fibers Over the past few decades, the growing desire for low-cost, lightweight materials has resulted in significant interest in polymer materials. During this time, polymers have emerged as viable alternatives to some conventional materials such as metals due to their inherent properties such as ease of manufacture, structural control, efficiency, availability, less physical work, and cost reduction. As a matter of fact, due to their superior properties, polymers have replaced many conventional materials for many applications and are currently playing an important role in the economy of many countries. Depending on their origin, polymers are generally divided into two types: natural and synthetic [1–5].

Natural Fibers Different types of natural fibers are used all over the world. These natural fibers have been used in a number of applications in our daily lives. Among these fibers, plant-based fibers are frequently used in a variety of applications and are of high commercial importance. Natural fibers include those produced by plants, animals, and geological processes and are biodegradable over time. Natural fibers can be classified by origin. Natural fibers generally contain cellulose, hemicellulose, beeswax, or lignin. Examples of these fibers are cotton, hemp, jute, flax, ramie, sisal, and bagasse (Fig. 1). Pure alpha-cellulose fiber has superior heat resistance (260 °C) compared to wood (200 °C). The cellulose fiber for automotive use is a cost of about 1.4–2.0 USD/kg. However, the cost of glass fiber is about 2 USD/kg [6]. Natural fibers are used in paper and textile (fabric) production. Wood fiber, which is distinguished from vegetable fibers, is obtained from wood. Animal fibers are largely composed of certain proteins. Examples include silkworm silk, spider silk, catgut, wool,

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Fig. 1  Different natural fibers [1–5]

marine silk and cashmere wool, mohair and angora, sheepskin, rabbit, mink, fox, and beaver. Asbestos is the only mineral fiber that occurs naturally. The use of natural fibers as reinforcing fibers in various polymer matrices (natural  =  synthetic) provides a number of benefits, including environmental benefits. Natural fiber-reinforced composites have recently been found in commercial applications such as deck surfaces, door components, windows, sports facilities, packaging, automotive industry, and furniture.

Synthetic Fibers Synthetic fibers generally consist of synthetic materials such as petrochemicals, but some types of synthetic fibers are produced from natural cellulose including rayon, modal, and lyocell. Cellulose-based fibers are of two types, namely, regenerated or pure cellulose such as from the cupro-ammonium process and modified cellulose such as the cellulose acetates. The intrinsic mechanical properties of both reinforcement materials give rise to unique structural materials in terms of toughness and strength. Fiber composites are widely used in sectors such as transportation, sporting goods, and wind power (Fig. 2). Although carbon-fiber composites are about one-­ fifth of the weight of steel, they can have at least as much hardness and strength as steel depending on the degree and orientation of the fiber. In addition, the carbon fiber exhibits good creep resistance and good compatibility with the epoxy matrix. However, the main disadvantages of carbon fiber composites for industrial use are highly susceptible to stress concentration and impact damage caused by the brittleness of carbon fiber. To overcome these problems, hybridization is performed. In this process, a softer and lower-priced fiber is added to the structure in certain proportions to improve the mechanical properties. Hybrid composites normally contain

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Fig. 2  Different types of fibers use to composites

US Dollars / kg fibers Sisal Ramie Kenaf Jute Hemp Flax Coon Coir Bamboo Abaca E -Glass 0

0.5

1

1.5

2

2.5

3

3.5

US Dollars Fig. 3  Cost per weight comparison between glass and natural fibers

a high modulus and expensive fibers such as graphite or carbon fiber. The second fiber is generally a low modulus and inexpensive fiber such as Kevlar, PE, or Basalt; thus, the mechanical properties of both reinforcement materials result in unique materials in terms of toughness and strength. Glass fiber could also be a suitable candidate for the manufacturing of hybrid composites of this type. It has good toughness properties as well as lower price and better interfacial adhesion to the matrix [7]. Different kinds of natural fibers such as sisal, banana, flax, jute, kenaf, and Agave americana offer a number of advantages over synthetic fibers due to their renewable nature. The advantages of these natural fibers could be summarized as low cost, biodegradability, recyclability, acceptable specific strength, ease of separation, low density, high toughness, good thermal properties, reduced tool wear, nonirritation to the skin, and enhanced energy recovery. İn addition to these, natural fibers are very cheap and promising in comparison to traditional synthetic fibers. Figure 3 shows the cost comparison between glass and natural fibers [8–12].

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3  Fiber Modifications The bonding of hydrophilic natural fibers to polymers leads to heterogeneous systems with low properties due to the lack of adhesion between the fibers and the matrix. They are hydrophilic fibers and therefore show poor resistance to moisture. In order to eliminate the problems associated with high water absorption, the fibers are treated with hydrophobic aliphatic and cyclic structures. These structures contain reactive functional groups which can be linked to reactive groups in the matrix polymer. Therefore, the treatment of the fibers to achieve high tack properties is a critical step in the development of composite structures. The treatment of the fiber may be bleaching, grafting of monomers, acetylation, etc. [13]. Some chemical methods are used to improve and optimize the weak interface between fiber and matrix in natural fiber-reinforced composites. In fiber modification, friction breaking stress can be increased by roughening the fiber surface, additional materials having bonding properties may be used, chemical vapor may be used, or bonding methods may be tried by increasing bond strength. In addition, physical methods such as corona and plasma can be applied [14]. By alternating the matrix polymer as well as fiber modification, the interface resistance can be improved. The basic interface modification methods between fiber and matrix to improve the efficiency of the interface in the production of natural fiber-reinforced composites are discussed in detail in the following text.

Alkali Treatment Treatment with alkali process is one of the most commonly used methods in natural fiber processes. Natural fibers show polar structure due to their hydroxyl groups. Some of these substances on the surface of cellulose fibers are removed by alkali treatment, and many cellulose ends are formed on the surface of the fiber which are open and can interact with the polymer. Alkali treatment increases the free energy on the fiber surface and furthermore roughens the fiber surface [15]. Alkali treatment reduces the degree of polymerization of cellulose and determines the amounts of lignin and hemicellulose extracted from the fiber by affecting cellulose fibers [16, 17]. In some studies, it has been shown that alkali treatment increases tensile strength and modulus of flax fiber-reinforced composite, removes pectin from fibers [18], creates a rough surface of jute fibers, and increases interface resistance between jute and polypropylene [19]. The 5% NaOH treatment improves the mechanical properties of jute fiber-reinforced epoxy and polyester composites, according to some studies. However, the modification treatment with silica binder along with alkali treatment increases the interfacial resistance of the composite structures that results in an important improvement [20].

Fiber → −OH + NaOH Fiber − O − Na + H 2 O

The effectiveness of the alkali treatment may vary depending on the concentration, type, processing time, and temperature of the solution. Modification using a 5%

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NaOH solution has been found to help the sisal-reinforced composite gain higher tensile strength than the treatment using 10% NaOH solution [21–23]. Excessive removal of lignin weakens the fiber. Therefore, the alkali treatment improves the mechanical properties of the composite only when applied under optimum conditions.

Acetic Acid Treatment The acetylation process can be defined as a reaction in which an acetyl functional group (CH3COO–) is introduced into an organic compound. Acetylation of natural fibers is an esterylation method that causes plasticization of cellulosic fibers. The reaction involves the formation of acetic acid (CH3COOH) as a by-product which must be removed from the lignocellulosic material before the fiber is used. Chemical modification with acetic anhydride (CH3–C (=O) –OC (=O) –CH3) replaces the polymer hydroxyl groups of the cell wall with acetyl groups. Thus, they become hydrophobic by changing the properties of the polymers. The reaction of acetic acid with fiber is shown in [16]. Fiber – OH + CH 3 – C ( = O ) – O – C ( = O ) – CH 3 → Fiber – OCOCH 3 + CH 3 COOH

4  Surface Treatments with Enzymes Nowadays, enzymes can be used in all stages of the pretreatment and finishing processes of textile products obtained from cellulose, protein, and synthetic-based fibers. Enzyme proteins function catalytically in most reactions in organisms. In parallel with the developments in the field of biotechnology, the use of natural products in industrial applications is increasing [24]. In recent years, rapid progress has been made on the effects of enzymes on textile fibers [25, 26]. Pectinase enzymes affect pectin with polysaccharide structure in the structure of plant-derived fibers. Bacillus sp. DT7 from soil can be used to obtain the pectinase enzyme [27]. The performance of the hydrophilicity applied to the fibers positively affects the dyeing up and finishing processes. Cotton, flax, ramie, marijuana, and hemp fibers can be hydrophilized with pectinase enzyme and combinations with other enzymes (lipase, protease, cellulase, etc.) [28, 29].

5  Methods Used in Surface Treatments Intensive research is being carried out on nontraditional alternative surface treatment techniques such as radiofrequency, microwave energy, infrared heating, and ultrasound energy use. These methods are an alternative to conventional methods in terms of shorter processing times and better product quality [30, 31].

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6  Ultrasonic Energy Ultrasonic energy in textile industry is a method used in wet applications (dyeing and bleaching) to save the amount of chemical materials, water, time, and energy. It speeds the physical and chemical reactions during the dyeing process at low temperatures when used instead of the conventional method, and optimizes the usage of heat energy. Having better washing fastness and color strength properties of the materials dyed with ultrasonic method and having low dyeing duration, temperature of dyeing bath, and need of electrodes and dyes make it an environmental dyeing method. Ultrasonic energy leads to the formation of cavitation bubbles in the liquid and induces physical and chemical effects between solid-liquid and liquid-liquid by the inherent production of shock waves. As a result, increase in fiber swelling in liquid, decrease in temperature of the glass transition point, increase in diffusion coefficient of dyeing molecules, increase in coefficient of the rate of fiber/dye, and dyeing molecules movement to the surface occur [32, 33].

7  Microwave Energy Microwaves are the high-frequency radio waves between 30 and 30.000 MHz in the infrared spectrum. Using the energy of microwaves provides ease of use in textile industry by heating quickly and economically in drying, dyeing, and printing. The product should have a dielectric loss for applying microwave method, and electric charges should occur in the material when applying a variable electromagnetic area. Therefore, structures in aqueous environments or containing water are suitable for heating with microwave, while water molecules create the dipolar electrical charge [34, 35]. Because of accelerating chemical processes, especially having energy saving in reactions and having short process durations, the microwave energy method can be described as an environmental friendly method. The material gets heated from inside to outside in this method; hence, the macromolecules of the material conduct the heat to each other in a short period. Because of those advantageous properties, the process durations, usage of the chemicals, energy, and water can be reduced in this method [36, 37].

8  Surface Treatment of Agave americana Fibers Agave americana L. known the native name which is patience herb in Turkey belongs to Liliaceae family. Agave americana L. resembles cactus is a succulent plant [38]. Also, Agave americana L. in the West Mediterranean Region is endemic in Turkey (Fig. 4).

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Fig. 4  Agave americana L. plant and fibers

Agave americana L. is commonly found in Africa which has a hot and dry climate. Afterward, Agave americana started to spread in North Africa, Arabian Peninsula, China, and the Mediterranean Region [39]. The Turkish name of this plant is “sarisabir,” which means a “yellow sword.” The pedicle may grow up to 150 cm. Pipe-like yellow flowers grow on the pedicle. As the flowers of the plant “sarisabir” are infertile, its reproduction is realized through the separation of the young buds from the plant. The plants usually have 12–16 leaves. Its life is around 12 years. When the plant is at the age of 4, it is considered to be grown. The leaf size of a 4-year-old plant is approximately 60–90 cm [40, 41].

Fibers The surface treatment was applied to Agave americana L. with pectinase enzyme by using conventional and ultrasonic methods. The conditions of the two methods are given in Table 1. At the ultrasonic method, Branson B2200B E4 (220 V and 205 W) which has 20 kHz frequency was used. At the conventional method, Polimat HT Sample Dyeing Machine (Tip A11612N-Emsey) was used. The spectrophotometer measurement of the raw and enzyme-implemented materials for their respective wavelengths of 400–700 nm has been performed in every 10 nm and whiteness levels of the fabrics have been defined in accordance to the Berger Whiteness Index Formula with the help of the % remission values of the fabrics. The tensile strength of the Agave americana L. fibers applied to pretreatment according to conventional method increased with the increase in the quantity of pectinase enzyme concentration and application time. At the ultrasonic method, the tensile strength increased with the increase in the concentration and decrease in the application time (Figs. 5 and 6). It was observed from the tensile strength values,

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Table 1  The conditions of the surface treatment [41] Solution (chemicals) Nonionic cellulose enzyme pH 5

Producer/ Concentration Temperature Rinsed process supplier (g/L) (°C) (25 °C, 10 min, pH 7) Dry process 1 50 Distilled water At room Indiblue temperature E7 – Denge chemistry

Fig. 5  The tensile strength of the samples treated by using conventional method [41]

Tensile Strength, gf

Conventional method time: 20, 40 min and ultrasonic energy method time: 5, 10 min

120 100 80 60 40 20 0

Conventional Method

Untreated

Pectinase Pectinase enzyme 1% enzyme 3% Time

omin

40min.

Ultrasonic Energy Method Tensile Strength gf

Fig. 6  The tensile strength of the samples treated by using ultrasonic energy [41]

20 min.

100 80 60 40 20 0 Untreated

0min

Pectinase enzyme 1% Time 5 min.

Pectinase enzyme 3%

10min.

ultrasonic energy method is more effective. It was found that ultrasonic energy ­correlates between the macromolecules that belong to the cellulose chain with the help of pectinase enzyme. This correlation saves time, water, and energy. Figures 7 and 8 show that according to ultrasonic and conventional methods, the elongation of fibers increases with the increase in the concentration of pectinase enzyme. For the ultrasonic method, the fibers are exposed to less damage due to cavitation bubbles, and time saving was achieved owing to cavitation bubbles. When the results are evaluated, it has been observed that ultrasonic energy is an innovative and ecological method providing time, water, and energy conservation and minimizes the tensile strength loss of the Agave americana L fibers. This method does not induce any harm to the fibers [41, 42].

Fig. 7  The elongation values of the samples treated by using conventional method [41]

Elongation %

The Effects of Ecological and Sustainable Chemical Surface Modification Methods…

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Conventional Method

9 8 7 6 5 4 3 2 1 0

Untreated

Pectinase enzyme 1%

Pectinase enzyme 3%

Time

omin

40min.

Ultrasonic Energy Method

10 Elongation %

Fig. 8  The elongation values of the samples by using ultrasonic method [41]

20 min.

8 6 4 2 0 Untreated

Pectinase enzyme 1%

Pectinase enzyme 3%

Time omin

5 min.

10min.

9  Surface Treatment of Sisal Fibers Sisal fiber, one of the most commonly used natural fibers, is used to produce carpets, ropes, mats, and other things and it is very easily cultivated (Fig. 9). Sisal fibers are obtained from sisal plant (Agave sisalana) which is widely grown in tropical regions such as Africa, the West Indies, and the Far East [44]. Sisal fibers have the second highest volume of production among natural fibers after cotton, and especially these fibers have been used as the raw material to reinforce composite production owing to its high strength, durability, renewability, biodegradability, and strain-to-failure. The composites reinforced with sisal fibers have been widely used in the internal covering area of cars, bus, and trucks due their mechanical properties [45, 46].

Fibers In this work, sisal fibers were washed with 1 g/L nonionic detergent (Orgafen N 130) via conventional and ultrasonic method (Table  2). For ultrasonic method, Branson B2200B E4 (220 V and 205 W) Marque Ultrasonic machine which has

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Fig. 9  Sisal fibers [43] Table 2  Washing methods [43] Conventional washing method Materials and equipment Wash bath: 1000 mL capacity stainless steel wash bath Detergents: (Orgafen N 130) nonionic detergent Washing parameters Bath ratio: 1/500 Washing temperature: 40 °C Detergents concentration: 1 g/L Washing time: 10, 30, 40 min

Ultrasonic washing methods Materials and equipment Wash bath: Branson 2200 ultrasonic washing bath Detergents: (Orgafen N 130) Nonionic detergent Washing parameters Bath ratio: 1 / 500 Washing temperature: 40 °C Detergents concentration: 1 g/L Washing time: 3, 5, 10, 15 min

20 kHz frequency is used. Determination of tenacity and elongation results was carried out on Instron 1011 equipment using ASTM 02256-97 standard. For all the ultrasonic washing, Branson 2200 ultrasonic bath was used. At 40 °C, 1 g/L detergent was added to deionized water and 100 mm length fibers were placed in the ultrasonic bath and washing were started with the appropriate (conventional 10, 30, 40 min and ultrasonic 3, 5, 10, 15 min) washing times. After the washing, all the samples were washed off with 1 L of deionized water and conditioned under 20 ± 2 °C and 65 ± 2 RH% 24 h before the tests started. When the tensile strength of untreated samples is compared with the tensile strength of samples washed via conventional and ultrasonic methods, the tensile strength values of untreated samples are higher than the tensile strength values of treated samples (Figs. 10, 11, 12, and 13). During the washing process, the liquids, waxes, and lignin are removed. As a result, the tensile strength of fibers decreases so that weight losses occur on the fiber surface. The optimum washing time is 30  min for conventional method. With an increase in the treatment time, it is observed that the tensile strength and elongation values decrease [43]. When the mechanical properties of samples that are washed via ultrasonic method are evaluated, the best results are obtained from the sample washed for 10 min. Also, the mechanical properties of samples washed via ultrasonic method decrease with an increase in the treatment time [43, 47, 48].

The Effects of Ecological and Sustainable Chemical Surface Modification Methods… Conventional method

Tensile strength gf

Fig. 10  The tensile strength values of samples washed via conventional method [43]

20 15 10 5 0 0 min

10 min

Elongation %

Untreated

Fig. 11  The % elongation values of sample washed via conventional method [43]

Tensile strength gf

40 min

Conventional method

10.0 8.0 6.0 4.0 2.0 0.0

0 min

10 min

30 min

40 min

Conventional Method

Ultrasonic method

20 15 10 5 0

0 min

3 min

Elongation %

Untreated

Fig. 13  The % elongation values of sample washed via ultrasonic method [43]

30 min

Conventional Method

Untreated

Fig. 12  The tensile strength values of samples washed via ultrasonic method [43]

13

12 10 8 6 4 2 0

5 min

10 min

15 min

Ultrasonic method

Ultrasonic method

0 min

3 min

Untreated

5 min

10 min

15 min

Ultrasonic Method

10  Surface Treatment of Kenaf Fibers Kenaf fibers are annual plant (Hibiscus cannabinus L.) and belong to Malveceae family. It grows on warm climate zones of the world. Kenaf grows rapidly and reaches to 3 m. Kenaf is a stem fiber and fibers are obtained from the 34–38% of the stem. Chemical composition and photos of the kenaf fibers are given in Fig.  14. Kenaf fibers are processed by extrusion, molding, and nonwoven processes due to

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Fig. 14  Kenaf fibers [49]

their excellent tensile and flexural strength properties. Kenaf fibers are widely used in European automotive industry for sound insulation [43, 48–54]. Chemical surface treatments are required to increase the usage of the kenaf fibers in the industry.

Fibers Kenaf fibers were collected from South Africa (Fig. 14). Their overall lengths were between 30 and 60 mm. The kenaf fibers were washed with water to remove the adhering dirt (20 °C distilled water for 30 min). They were dried in an oven at 70 °C for 4  h. After treatments, they were conditioned for 48  h prior to testing under 20 ± 2 °C and 65 ± 2%RH conditions. Kenaf fibers were exposed to three processes: Tables 3, 4 and 5 show the properties of the conventional, ultrasonic, and microwave processes, respectively. Conventional process was applied in laboratory condition. Branson B2200B E4 (220 V and 205 W) ultrasonic bath was used for the ultrasonic method with 20 kHz frequencies. Microwave method was performed by using Kenwood Mw 440 at a frequency of 2.45 GHz. The microwave oven was set to medium-low (M-L) power of 350 W. The samples were placed in a sealed glass vessel and treated by the microwave energy according to the experimental design. According to the tensile strength results, tensile strength of the kenaf fiber increased after all chemical treatments by using all methods. Better results were obtained by using alternative ecological methods (ultrasonic and microwave methods) than conventional method (Figs. 15 and 16). NaOH treatment is a conventional mercerization process which removes the part of lignin and hemicellulose and helps the fiber getting wet easily [55]. Alkali treatments also affect the cellulose fibrils and decrease the polymerization degree of the cellulose and affect the quantity of the lignin and hemicelluloses removed from the fiber [56]. Therefore, amorphous zones of the fibers increase and so elongation properties of the kenaf fibers increase [18].

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15

Table 3  Conventional processes applied to kenaf fibers [49] Conventional process Chemicals Method 1 Sodium hydroxide Method 2 Acetic acid

Producer-­ Temp. code Concent. (°C) Merck 5 g/L 23 (106462) Merck 100% 30 (109944)

Rinsing process Time (25 °C, 10 min, Drying process (min) pH 7) 30 Distilled water At room temperature 40 Distilled water At room temperature

Table 4  Ultrasonic energy processes applied to kenaf fibers [49] Ultrasonic process Chemicals Method 1 Sodium hydroxide Method 2 Acetic acid

Producer-­ Temp. code Concent. (°C) Merck 5 g/L 23 (106462) Merck 100% 30 (109944)

Time (min) 30 20

Rinsing process (25 °C, 10 min, Drying pH 7) process Distilled water At room temperature Distilled water At room temperature

Table 5  Microwave processes applied to kenaf fibers [49] Microwave process Chemicals Method 1 Sodium hydroxide Method 4 Acetic acid

Producer-­ code Concent. Temp. Merck 5 g/L M-L (106462) Merck 100% M-L (109944)

Rinsing process Time (25 °C, 10 min, Drying process (min) pH 7) 7 Distilled water At room temperature 7 Distilled water At room temperature

Tensile strength, cN

14 12 10 8 6 4 2 0

Untreated

Conventional

Ultrasonic

Microwave

Chemical Treatments (NaOH)

Fig. 15  Tensile strength properties of the NaOH-treated kenaf fibers [49]

Application of acetic acid (CH3COOH) to the cellulosic fibers is known as acetylation or esterification method. Tensile strength and elongation properties of the acetylated kenaf fibers are higher than the NaOH. Acetylated fibers interact with hydroxyl groups situated on the cell wall; thus, they become effective between

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Elongation, %

2 1.5 1 0.5 0 Untreated

Conventional

Ultrasonic

Microwave

Chemical Treatments (NaOH)

Fig. 16  Elongation properties of the NaOH-treated kenaf fibers [49]

Tensile strength cN

20 16 12 8 4 0 Untreated

Ultrasonic Conventional Chemical treatments (Acetic acid)

Microwave

Fig. 17  Tensile strength of the acetic acid-treated kenaf fibers [49]

Elongation, %

3 2 1 0

Untreated

Conventional

Ultrasonic

Microwave

Chemical treatments (Acetic acid)

Fig. 18  Elongation properties of the acetic acid-treated kenaf fibers [49]

cross-linked lignin and cellulose. After acetylation, fibrillary structure increases and also amorphous structure increases due to the changes that occur on cell wall. Therefore, elongation properties of the kenaf fiber increase (Figs. 17 and 18).

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17

Mechanical properties of the treated kenaf fibers were higher when ecological processes were used (ultrasonic and microwave). By using ultrasonic process, microbubbles produced by ultrasonic energy carry chemicals into the kenaf fibers. Chemicals are carried into the kenaf fibers in the form of wave of the ultrasonic energy. Thus, molecules of the chemical substances are carried in a short time without harming the fiber morphology. As a result, molecular chains of the kenaf fibers are not damaged, and tensile strength and elongation properties of the fibers are higher than conventional process. The highest mechanical properties were obtained by using microwave energy treatment process. Microwave energy system creates high frequency and dielectric heating system, and molecular structures of kenaf fibers move side by side because of the electric field created by the microwave energy. Hence, heating of a material by using microwave energy is more economic than conventional process. Mechanical properties of the fibers are not affected negatively due to the short reaction time. Even, better wrinkle recovery resistance and tensile strength results were obtained by using microwave energy than conventional process on the esterification of the cotton fibers [57].

11  Surface Treatment of Luffa Fibers This fiber is quite common in the mid-south of America as well. As for Turkey, it grows well in the areas of the Mediterranean climate [58]. The luffa cylindrical fibers are a subtropical plant of the cucurbitaceous family, which produces a fruit with a fibrous vascular system. Their size varies in relation to the areas they grow, ranging from 15 cm to 1 m, or even more than 1 m in certain kinds [49]. Special uses of some of the fibers include wide use of luffa cylindrical as scouring pads during bathing, for the manufacture of palm sole, inner soles for filters, leather straps, and filters for automobiles (Fig. 19) [58–61].

Fig. 19  Luffa fibers [58]

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E. D. Koçak and M. Nigar

Luffa fibers were obtained from the Mediterranean Region of Turkey. Its fruit has a fibrous vascular system that forms a natural mat when dried. Their overall lengths were between 400 and 600 mm. The Luffa fibers were washed with water to remove the adhering dirt for 30 min at 20 °C distilled water. They were dried in an oven 6 h at 70 °C. After drying, they were conditioned for 48 h prior to testing under ±20 °C and 65 ± 2 RH% condition. Luffa fibers have been treated using three methods such as conventional methods, ultrasonic methods, and microwave methods that are listed in Tables 6, 7, and 8, respectively. In addition to this, two kinds of chemical processes were applied for each of the three methods. In, ultrasonic method Branson B2200B E4 was carried out at (220 V and 205 W) ultrasonic bath with 20 kHz frequencies. Microwave method with a Galanz/WP800T was carried out at a frequency of 2.45 GHz. The microwave oven had a maximal power of 800 W with six discrete settings. The mixtures were placed in a sealed glass vessel and treated by the microwave according to the experimental design.

Table 6  Conventional methods applied to luffa cylindrical fibers [58, 61] Conventional Solution Producer/ Temp. methods (chemicals) supplier Concent. (°C) Method 1 Formic acid Merck 99% 20 (100263) Method 2 Acetic acid Merck 100% 40 (109944)

Rinsed process Time (25 °C, 10 min, Dry process (min) pH 7) 40 Distilled water At room temperature 40 Distilled water At room temperature

Table 7  Ultrasonic energy methods applied to luffa cylindrical fibers [58, 61] Ultrasonic Solution Producer/ Temp. methods (chemicals) supplier Concent. (°C) Method 1 Formic acid Merck 99% 20 (100263) Method 2 Acetic acid Merck 100% 25 (109944)

Rinsed process Time (25 °C, 10 min, Dry process (min) pH 7) 40 Distilled water At room temperature 20 Distilled water At room temperature

Table 8  Microwave methods applied to luffa cylindrical fibers [58, 61] Microwave Solution methods (chemicals) Method 1 Formic acid Method 2

Acetic acid

Producer/ Temp. supplier Concent. (°C) Merck 99% 20 (100263) Merck 100% 25 (109944)

Time (min) 40 40

Rinsed process (25 °C, 10 min, pH 7) Dry process Distilled water At room temperature Distilled water At room temperature

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Tensile Strenght (cN/tex)

2.5 2

1.5 1

0.5 0

Untrated

Conventional

Untrated

Ultrasonic

Methods Formic Acid

Microwave

Acetic Acid

3.5

Elongation (%)

3 2.5 2 1.5 1 0.5 0 Untrated Untrated

Conventional Methods Formic Acid

Ultrasonic

Microwave

Acetic Acid

Fig. 20  Comparing mechanical properties of the luffa fibers [58, 61]

Luffa fibers were examined in terms of mechanical characteristics using different chemical methods and two different processes. By comparing our experimental results to bibliographical data obtained with luffa fibers, we can observe that mechanical properties of the ultrasonic method values were improved [58, 61] (Fig. 20). It shows that the chemical treatments (acetylation and formlyatin used) reduce the mechanical properties due to removing of waxes, gums, etc. In contrast acetylation and formlyatin that performed using ultrasonic and microwave methods have resulted in increases mechanical properties. This results from the fact that the energy of the cavitation increases the reaction of fibers with the acids [61, 62]. Microwave method, increases mechanical properties owing to microwave irradiation that played a positive role in biomass digestion [58].

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SEM micrographs of untreated luffa cylindrical fibers, which are presented in Figs. 21, 22, 23, and 24, show SEM photographs of fibers treated with formic acid and acetic acid by ultrasonic, microwave, and conventional processes. The conventional processes carried out on flax fibers with formic acid is known to disclose micro fibers better than those treatments carried out with NaOH. It is also known that it reveals themacro fibers on the surface of luffa cylindrical fibers. Following the treatment with formic acid and acetic acid by means of microwave, the outer layers of parenchyma cells have been removed to expose the inner fibers [58, 61–63].

Fig. 21  Untreated luffa fiber [58]

Fig. 22  Treated luffa fiber with acetic acid by ultrasonic energy process [58]

The Effects of Ecological and Sustainable Chemical Surface Modification Methods… Fig. 23  Treated luffa fiber with acetic acid by microwave process [58]

Fig. 24  Treated luffa fiber with formic acid microwave process [58]

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12  Conclusions The three surface modification techniques on natural fibers have been compared. This technique varies in terms of chemicals, enzymes, and treatment durations. The advantages of using ultrasonic and microwave energy treatment methods can be summarized as follows: All the mechanical properties of the fiber were obtained by using ultrasonic and microwave processes. The reason for the ultrasonic and microwave processes to be successful is the strength achieved by sonication and microwave energy. 1. Ultrasonic energy used in surface treatment improved the tensile strength and elongation properties of the fibers. It induced in the fibers and molecular s­ tructure of the affected fibers with cavitation. By using ultrasonic process, microbubbles caused by ultrasonic energy are carrying chemicals into the fibers. 2. Chemicals are carried into the fibers in the form of wave of the ultrasonic energy. Thus, molecules of the chemical substances are carried in a short time without harming the fiber morphology. As a result, molecular chains of the fibers are not damaged, and tensile strength and elongation properties of the fibers are higher than conventional process. 3. In enzyme applications with the ultrasonic energy method, the surface modifications with higher tensile strength and elongation properties were more effective in conventional methods. An increase in ultrasonic energy treatment duration had a positive effect on the mechanical properties for all the fibers. 4. All the mechanical properties of the fibers were improved by using microwave energy treatment process. Microwave energy system creates high frequency and dielectric heating system. Molecular structures of the fibers  is  affected  positively  because of the rapid energy transfer with electric field created by the microwave energy. During this movement, spectacular heat is created by the friction. This heating  of the  fiber  structures  starts  at  every point  simultaneously,  thus uniformity heating effect occurs rapidly and selectively.

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Sustainable Plant-Based Natural Fibers Seyda Eyupoglu

Abstract  Since prehistoric ages, the most important equipment has been clothes after the nutritional requirement for humans; therefore, the history of textile fibers dates back to B.C. 9000 years. In these years, flax was harvested in Mesopotamia, cotton was cultivated in the Indus River region, silk was obtained from domesticated silkworm in North Chine, and wool was originated in West Asia. The nature-­ based textile fibers have been important due to its widespread in nature and technical appropriateness for many centuries. However, textile science has searched for new fibers which can substitute the natural fibers due to difficulties in obtaining natural fibers such as cost, need for improvement, desire to obtain products with higher qualities, fashion, and inability to meet the demands. By the twentieth century, cellulose acetate fiber, which is the first synthetic fiber, was produced. The discovery of cellulose acetate fiber followed the discovery of nylon 6.6, nylon 6, polyester, and polyacrylic fiber. However, natural fibers have been popular due to increasing demands at the present time. Furthermore, natural fibers have been used not only for clothing but also for technical applications such as composite materials, building materials, filtration, and insulation materials because of low price, sustainability, lightness, high strength properties, high insulation properties, and simple sourcing. The term “sustainability” is defined as how natural systems function, remain diverse, and produce everything it needs for the ecology to remain in balance. In other words, sustainability is to maintain productivity in agriculture and ecology despite obstacles. In textile science, natural fibers are known as the sustainable raw materials. For this purpose, in this chapter, plant-based natural fibers are investigated in all respects such as structure, production process, production areas, using areas, advantages, and limitations. First, the term sustainability is explained. After a brief summary of plant-based natural fibers, fiber properties of cotton, bamboo, flax, hemp, kenaf, sisal, jute, ramie, abaca, banana, pineapple, coconut, and okra are investigated. Furthermore, in sustainability, ecology is the most effective factor. The slightest damage in ecology affects the whole living population. This chapter focuses on sustainable agriculture and ecology. S. Eyupoglu (*) Department of Textile, Clothing, Footwear and Leather, Vocational School of Technical Sciences, Istanbul University - Cerrahpasa, Istanbul, Turkey e-mail: [email protected] © Springer Nature Switzerland AG 2020 S. S. Muthu, M. A. Gardetti (eds.), Sustainability in the Textile and Apparel Industries, Sustainable Textiles: Production, Processing, Manufacturing & Chemistry, https://doi.org/10.1007/978-3-030-38541-5_2

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Keywords  Plant-based natural fibers · Sustainability · Ecology · Production process

1  Introduction Worldwide, due to millions of tons of plastic wastes, global environmental concerns, such as decrease in polar ice caps, increasing global temperature, increasing sea levels, and fast depleting petroleum resources, have been observed in the environment. Above mention reasons cause to increase in demand of green and sustainable products. Many researchers have focused on the usage of plant-based natural fibers in many areas such as textiles, composites, and packing. Plant-based natural fibers have many advantages compared with synthetic fibers; these advantages include biodegradability, low density, high toughness, acceptable specific strength, reduced dermal and respiratory irritation, low cost, and less use of nonrenewable resources [1]. The fibers are manufactured in billions of tons around the world because they are abundant, inexpensive, and readily available. Plant-based natural fibers are mainly composed of cellulose, lignin, and hemicellulose components. Owing to these components, plant-based natural fibers are named as cellulosic or lignocellulosic fibers. Physical and mechanical properties of fibers depend on the fiber chemical composition (cellulose, hemicellulose, lignin, pectin, waxes, and water content), growing conditions (soil features, climate, and aging conditions), and extraction process. Among them, growing conditions are the most influent parameter affected by the mechanical properties of fibers. The main structure of plant cell walls comprises complex architecture of cellulose. It is a polymer of poly-b(1fi4)-D-glucose having a linear structure with a syndiotactic arrangement. The bundles are formed with the parallel arrangement of cellulose chains. Cellulosic macromolecules link with each other by hydrogen bonds [2].

2  What Is Sustainability? The origin of sustainability is based on a Latin word “subtenir” which means “protecting” or “supporting from below.” Sustainability means continuation of a situation or process over an unlimited duration. There are a variety of definitions about sustainability; however, sustainability is described as providing natural resource continuation in the simplest definition. Furthermore, it means that ecology and ecological application will continue the functions in the future. Sustainability is defined with regard to term as protecting productivity in spite of all drawbacks in agriculture and ecology. It is related to agriculture, forestry, fishery, agrology, and hydrology. Global warming, ecological environment, and population lead to sustainability which has become a significant subject. The ecological impact of sustainability is very important as ecology concerns the whole living population closely.

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Sustainable Plant-Based Natural Fibers

Global Warming  Whole humanity feels the climatic changes all over the world. Global warming and climatic changes are the most important subjects which are discussed by the world. The most important causes of global warming are economic and commercial factors. Sustainability is one of the factors needed due to the changes. Ecological Environment  The amount of carbon gas released to the atmosphere during the energy conversion process causes global warming and climatic changes. Released carbon gas induces concern all around the world. As a result, Kyoto Protocol, an international agreement, was signed. The Kyoto Protocol aimed to reduce carbon dioxide emissions, the presence of greenhouse gases, and emission of methane, nitrous oxide, hydrofluorocarbons, perfluorocarbons, and sulfur hexafluoride. Population  Increasing population leads to problems of sustainability due to necessity of increasing consumer products. Due to climatic changes, agricultural manufacture has decreased and sustainable problems have became [3].

3  Plant-Based Natural Fibers Plant-based natural fibers are classified based on their origins which are shown in Fig. 1. The chemical composition of plant fibers is complex and basically comprises a rigid, crystalline cellulose microfibril-reinforced amorphous lignin and hemicellulose matrix. Types of plant-based natural fibers are given below. Bast Fibers  Bast fibers are commonly obtained from the outer bark of plant stems. Jute, flax, abaca, and kenaf fibers are examples of bast fibers. Bast fibers are obtained with the retting process and are accomplished through biological or chemical degradation of cut plant stems. These fibers are long and high in strength; therefore, they are used in making yarn, fabric, rope, sack, reinforcement, etc.

Cellulose Based Natural Fibers

Bast

Seed

Leaf

Wood

Fruit

Jute

Sisal

Kapok

Coil

Flax

Banana

Cotton

Oil Palm

Hemp Ramie Kenaf

Abaca Henequen n Agave

Fig. 1  Classification of plant-based natural fibers [4]

Stalk

Grass

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Leaf Fibers  Leaf fibers are hard fibers which are extracted from leaf tissues by hand after retting process or mechanical extraction. They are commonly used in the manufacturing of ropes, fabrics, carpets, and mats because of high tensile strength. Sisal, caroa, and pineapple are examples of leaf fibers. Seed Fibers  Seed fibers are obtained from the pod or boll of some plant seeds. These lightweight and strong fibers are used in textile, water safety equipment, buildings, and mattress products because of their softness and buoyancy. Coir, cotton, kapok, and milkweed floss fibers are examples of seed fibers [4]. Stalk Fibers  These fibers are located in plant stalks and are obtained from plants such as sugarcane, corn, eggplant, sunflower, wood, and the straw of various grain crops such as barley, wheat, and rice. Pulp of these fibers has been used in paper and paperboard products. Grass and Other Fiber Crop Residue  The significant sources of grass fiber are ryegrass, elephant grass, switchgrass, and bamboo. Crop residues such as pulse seed coat, peanut shell, hazelnut husk, corn husk, and millet stover can be used as fiber reinforcements in cement-based composites. Wood and Specialty Fibers  Wood fibers are obtained from different types of trees. These fibers are classified into two subgroups, softwood and hardwood. Compared with hardwood fibers, softwood fibers are generally longer, and more fibers are obtained from softwood pulp. On the other hand, specialty cellulose fibers are industrially processed plant-based natural fibers with unique attributes such as bond enhancement and alkali resistance. Plant-based fibers, except for seed fibers, are obtained by manual mechanical separation or the use of a decorticator after the retting process. In mechanical separation, fiber strands or wood chips are grounded in three different ways: without steaming, with steaming, and chemical/steam pretreatment. In chemical separation, in order to remove lignin from strands and wood chips, chemicals and heat are used. In enzymatic separation, lignin from strands and wood chips are removed with enzymatic treatments. Qualities of natural fibers are strongly influenced by growing environment, maturity, age of plant, species, temperature, humidity, and quality of soil. The variations that lead to difference in mechanical and chemical properties can be attributed to different stages: growth, harvesting, fiber extraction, and storage. Table 1 shows the mechanical properties of plant-based natural fibers. Plant-based natural fibers consist of cellulose, hemicellulose, lignin, extractives, and ash. The amount of these ingredients varies according to fiber type, growth condition, dimension, age, location on plant, extraction, and processing method. Chemical composition of some plant-based natural fibers is given in Table 2. These natural fibers are very hydrophilic because of hemicelluloses and hydroxyl groups in cell walls [4]. Plants included fibers are renewable resources and can help with the solution to climate change. Over the life-cycle, these plants absorb more carbon dioxide. During the fiber production process, these plants generate mainly organic wastes and leaf residues that can be used to generate bioenergy, produce animal feed, fertilizer, and ecological housing material.

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Table 1  Characteristic values for the density, diameter, and mechanical properties of natural plant fibers [4] Fibers Flax Hemp Jute Kenaf Ramie Sisal Cotton Coir Banana Agave Abaca

Density (g/cm3) 1.5 1.47 1.3–1.49 0.75 1.55 1.45 1.5–1.6 1.15–1.46 1.350 1.36 1.5

Diameter (μm) 40–600 25–500 25–200 130 170 50–200 12–38 100–460 240–260 100–150 150–260

Tensile strength (MPa) 345–1500 690 393–800 930 400–938 468–700 287–800 131–220 550–556 154 980

Young’s modules (GPa) 27.6 70 13–26.5 53 61.4–128 9.4–22 5.5–12.6 4–6 3.5 2.9 41

Elongation at break (%) 2.7–3.2 1.6 1.16–1.5 1.6 1.2–3.8 3–7 7–8 15–40 4–7 16.4 1.1

Table 2  Chemical ingredients of plant-based natural fibers [4] Grouping Bast

Stalk Straw

Leaf

Seed Wood

Fiber Jute Hibiscus Banana trunk Banana Ramie Hemp Flax Sorghum Bagasse Wheat Rice Barley Sisal Banana Pineapple Corn stover Coir Coconut tissue Eucalyptus

Cellulose 33.4 28.0 31.48 60–65 68–85 68–70 64–69 27.0 32–48 33–38 28–36 31–45 38.2 25.65 70–82 38–40 36–43 31.05 41.57

Hemicellulose 22.7 25.0 14.98 6–8 13–16 15–20 16–24 25.0 19–24 26–32 23–28 27–38 26.0 17.04 18.0 28.0 0.15–0.25 19.22 32.56

Lignin 28.0 22.7 15.07 5–10 0.5–0.7 10 2–8 11.0 23–32 17–19 12–14 14–19 26 24.84 5–12 7–21 41–45 29.7 25.4

Extractives – – 4.46 – – – – – – – – – – 9.84 – – – 1.74 8.2

Ash – – 8.65 4.7 – – – – 1.5–5 6.8 14–20 2–7 – 7.02 0.7–0.9 3.6–7 2.7–10.2 8.39 0.22

4  Cotton Fibers Recently, natural cellulose fibers have received rising attention because of their biodegradability and renewable resources compared with synthetic fibers. Especially cotton fibers are significant textile materials owing to their more cost-efficient production and nearly universal product possibilities [5].

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Table 3  The world cotton production and consumption values Countries Indian China USA Pakistan Brazil Australia Turkey Uzbekistan Other Total

2013/2014 6.770 6.929 2.811 2.076 1.705 890 760 940 3.402 26.283

2014/2015 6.562 6.500 3.553 2.305 1.563 528 724 885 3.581 26.201

2015/2016 6.240 5.260 2.820 1.610 1.550 470 640 860 1.624 21.074

2016/2017 5.865 4.900 3.738 1.663 1.530 931 703 789 2.975 23.094

2017/2018 6.296 5.345 4.266 2.094 1.703 968 852 804 3.041 25.369

Cotton plants belong to the genus Gossypium in the mallow family Malvaceae. Cotton plants are broad-leaves plants and each of the seeds is covered with white or cream color hairs. These hairs can be classified as short and long hairs. Short hairs are called linter and long hairs are called fiber. Warm and moist climate is suitable for cotton plants. Furthermore, for optimum development, these plants need warm climatic conditions, enough sunlight, and plenty of moisture for 6–7 months. Cotton plants flower 80–90 days after seeds are planted. Fibers are cultivated as soon as possible in order to prevent deterioration of quality of fibers by light and moisture [6]. The world cotton production and consumption values are given in Table 3. Chemical structure of cotton fiber differs from growing condition of cotton plants, and ingredients of cotton fiber are given below: Cellulose Hemicellulose and pectin Protein and pigments Inorganic substrates

88–96% 4–6% 1.5–5% 1–1.2%

Physical structure of cotton fiber is as follows: Length  The length of cotton fiber is an inherited attribute and it varies with environmental conditions. The length of cotton fibers is 1–6.5 cm. Thickness  Thickness is the most significant property for cotton fiber after length, and it is an inherited attribute. The thickness of cotton fiber varies from 6 to 25 μm. In general, long cotton fibers are thinner than short cotton fibers. Tensile Strength  In general, the tensile strength of cotton fibers varies from 19 to 45 CN/tex. The tensile strength of the cotton fibers is proportional to the maturity degree of fibers. The maturity degree of fibers is related to the thickness of cellulose layer. The tensile strength of the cotton fibers increases 10–20% in wet conditions. Maturity Degree  Maturity degree is related to the thickness of secondary wall known as cellulosic wall. The maturity degree of fibers increases with the thickness of wall.

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Elongation and Elasticity  The elongation of cotton fibers varies from 5.6% to 6.8%. Resilience  Cotton fibers have the lowest resilience capacity. It is difficult to return to its former state after the fibers remain under pressure. For this reason, cotton fibers are very creased. Moisture Absorption  Cotton fibers include wax in the structure, and hence, cotton fibers are hydrophobic before pretreatment. After the alkali pretreatment, wax is removed and fibers gain hydrophilic properties. Cotton fibers that absorb 25–27% humidity have high dehumidification capacity. Color  Color of cotton fibers which is an inherited attribute is intrinsic to genus and it changes with regard to climatic conditions. Gloss  Cotton fibers are not high in gloss capacity because of physical structure. In order to increase gloss of fibers, mercerization process is applied. Chemical structure of cellulosic-based fibers varies with chemical structure of macromolecules, location of macromolecules in fibers, and foreign substance in fibers. The chemical properties of cotton fibers are as follows: Effects of Acids  Concentrated inorganic acids such as sulfuric and hydrochloric acid damage cotton fibers. Effects of Alkali  Cotton fiber is very resistant to alkali; however, it damages cotton fibers in high temperatures. In low temperatures, mercerization process is treated to cotton fibers and the cross section area of cotton fiber becomes round. As a result, tensile strength, dyeing absorption, and brightness of fibers increase. Bleaching Agents  In high temperatures, bleaching agents damage cotton fibers. Organic Solvents  Cotton fibers are resistant to a variety of organic solvents. Light and Atmospheric Conditions  The ultraviolet radiations transform cotton into oxycellulose and decrease the fiber tensile strength. Muff and Fungi  Cotton fibers are not resistant to muff and fungi because of cellulose structure. Effect of Heat  Cotton fibers have excellent resistance to degradation by heat. At 120 °C, fibers begin to turn yellow after hours and decompose at 150 °C. At 240 °C, oxidation begins and cotton fibers are damaged after a few minutes. Throughout the world, cotton fibers are commonly used to produce conventional textiles such as home textiles and clothes. Furthermore, cotton fibers are used in technical textiles such as hygienic pads, napkins, and medical textiles [7].

5  Bamboo Fibers Bamboo plants belong to taxonomic group of large woody grasses which is subfamily Bambusoideae and family Andropogoneae/Poaceae. Because of high photosynthesis ability, high growth rate, low density, and low cost, it stands out from other

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plant fibers. Bamboos involve 1250 species which live within 5 years, but flowering infrequently. Some species of bamboo may be 10 cm in height, but most of the species are 15–20 m in height. Generally, bamboo plants are cultivated in tropical climate. Asia and South America are major locations of bamboo cultivation. Germany, the USA, China, India, Bangladesh, Indonesia, and Thailand are the significant bamboo production countries [5, 8]. The major economic species of bamboo plants are given in the following: Dendrocalamus strictus  This species belongs to India. In India, 100 bamboo species are cultivated; however, 10 species are commercially exploited and used mostly for paper making and construction. Dendrocalamus asper  It is considered to be native to Thailand. This species grows in the natural forest. Thyrsostachys siamensis  The native of Thyrsostachys siamensis is Thailand. It is used for construction material in both rural and urban areas. Phyllostachys pubescens  It is originated from China. This species is cultivated for both poles and edible shoots throughout Southeast Asia. This species requires a climate with precipitation of 1200–1800 mm, mean annual temperature of 13–20 °C, and monthly mean minimum temperatures no lower than freezing. Phyllostachys bambusoides  It originated in China; however, it is commonly harvested in Japan since 1866. This genus is the most commercial after Phyllostachys pubescens. Like other cellulose-based fibers, bamboo fibers contain primary wall, secondary wall, and lumen layers. Every layer of these fibers has different properties such as different length, diameter, constituent composition, and lumen size. The chemical ingredients of bamboo fibers have been reported as 73.83% of cellulose, 12.49% of hemicellulose, 10.15% of lignin, 0.37% of pectin, and 3.16% of aqueous extract [8]. Bamboo fibers are accepted as technical fibers such as flax, hemp, jute, and ramie because of fiber morphology (usually with length 1.9  mm and width 15.3  μm). Furthermore, like bast fibers, bamboo fibers consist of cellulose, lignin, hemicellulose, and pectin. Bamboo fibers have high absorbency and hygroscopicity, high thermal insulation, good electrostatic, and ultraviolet-resistant properties. However, in order to produce high added value textile products, bamboo fibers are treated with chemical, mechanical, and biological modification. Chemical method is based on the mechanism that cellulosic fibrils and noncellulosic substances have different stability in alkaline solution. In chemical modification, bast fibers are soaked in aqueous alkaline solution, such as sodium hydroxide (NaOH), potassium hydroxide (KOH), and sodium carbonate (Na2CO3), and it is a rapid and efficient process compared with mechanical and biological modification process. However, biological and mechanical modification processes are ecological and sustainable. Most of the bamboo species have strong, light, and flexible woody stems. For these reasons, it is used as construction materials in Asian countries. In some African countries, bamboo is used for construction materials and fuel [9].

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The properties of bamboo fibers are as follows [8]: • Compared with cotton, bamboo fibers are softer. • Because of high microgaps and microholes, it has much better moisture absorption and ventilation. • The hydrophilic nature of bamboo fiber leads to poor interfacial bonding between the hydrophilic polymer and fiber. • The fiber is shiny with drapability and abrasion resistance. • Bamboo fibers also have good antibacterial properties. • These fibers have high dyeing ability. Bamboo absorbs the dye faster and shows the colors better. • Because of anti-ultraviolet nature, these fibers are used to produce summer clothing. • Bamboo fibers are a nonpolluting, environmentally friendly fibers. Applications of bamboo fibers are as follows: • Due to its versatile properties, bamboo fibers are used in the production of attires, towels, and bathrobes. • Due to its antibacterial nature, these fibers are used for making sanitary napkins, nurse wears, masks, and bandages. • Bamboo fibers can be used for decoration purposes. • UV-proof, antibiotic and bacteriostatic curtains, television covers, and wallpapers are prepared from bamboo fibers [10].

6  Flax Fiber Ramie, jute, hemp, kenaf, and flax fibers which are obtained from the cortical region of plants are bast fibers. Flax (Linum usitatissimum L.) is an annual plant, 18–36 inches tall, with small and thin leaves and blue flowers. It is known as the oldest bast fiber and an agricultural product used as food and fuel. Flax plant has been used in industry since renaissance period. Flax fiber obtained from the plant of linseed/flax plant (Linum usitatissimum L.) belongs to the category of bast fiber. According to the historical records, the earliest example of flax is needle-netted headpiece from Nahal Hemar Cave in Israel, 8500 years ago. Furthermore, it is known that Swiss Lake Dwellers used native flax to make clothes 5000–6000  years ago. It was also known that ancient Egyptians used flax as bed sheets, clothings, and shrouds for mummies [11]. Flax fibers are obtained from the stems of flax bast plant. Like other plant-based fibers, flax fibers are a cellulose polymer, but its structure is more crystalline. Due to crystalline structure, the fibers have high mechanical properties and high wrinkle capacity. At the macroscopic level, flax stem involves bark, phloem, xylem, and a central void. At the mesoscopic level, the cross-section of a bundle contains between 10 and 40 fibers bonded together by pectin. The microstructure of flax fibers is extremely complex because of the hierarchical organization. At the macroscopic

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scale, every fiber is made of concentric cell walls, which differ from each other in terms of thickness and arrangement. At the center of the fibers, lumen layer which is the concentric cylinders with a small open channel takes place. The outer cell wall is called the primary cell wall which is 0.2  μm thick. The primary cell wall is enclosed with a secondary cell wall which is responsible for the fiber mechanical properties. Each layer is composed of microfibrils of cellulose which run parallel to another and form a microfibrillar angle with the fiber direction. The angle is minimum in the secondary cell wall [12]. The chemical components of flax fiber vary from fiber to fiber. The main constituents of a flax fiber are cellulose, hemicellulose, wax, lignin, and pectin. Cellulose, hemicellulose, and lignin are basic components and affect the physical properties of fibers. Flax fibers consist of 70–85% cellulose, 2.5% lignin, 2% pectin, 18.5% hemicellulose, 1–2% oil and wax, and 1% inorganic agents [12]. Flax fibers are obtained with mechanical or retting process which causes to separate fibers from plant. In the mechanical process, flax bastes are pulverized and flax fibers are separated. However, pectin is not removed from the flax fiber and is obtained from short fibers. For these reasons, mechanical method is not commonly used. The retting process is carried out by converting the pectinase, which binds the fibers to each other, to water-soluble compounds by penetrating microorganisms into the plant body or enzymatic processes. Retting process can be performed with slack water, running water, hot water, chemical agents, or enzymes. The properties of flax fibers are as follows [11]: • The microscopic images of flax fibers show that the cross-section area of fibers changes with the length. The length of the fibers varies from 30 to 90 cm. • The shape of flax is polygonal and the color of fibers is yellowish-white. • The brightness of fibers increases with the removal of wax and lignin. • The average tensile strength of flax fiber is 6.5 g/denye and it is more durable than cotton. • The elongation varies from 1.8% to 2.2%. The density of fiber is 1.54 g/cm3 and moisture absorption is 12%. • Flax fibers are resistant to alkali and dilute acids; however, fibers are hydrolyzed with dilute acids at high temperature. • Compared with cotton fibers, flax fibers are more resistant to bleaching agents. • Flax fibers are resistant to organic solvents, hence, dry cleaning is suitable. • It has no good affinity for dyes. Direct and vat dyes are suitable for flax fiber. • Thermal conductivity coefficient of flax fibers is low. Applications of flax fibers are as follows [11]: • Flax fibers are used in clothing production due to high thermal insulation capacity. • The fibers are used to produce damasks, sheeting, and lace. • The fibers are also used as a raw material in high-quality paper industry for the use of printed banknotes, rolling paper for tea bags, and cigarette paper manufacture.

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• Flax fiber-reinforced composite applications expand rapidly. The binding materials range from thermoplastics such as polypropylene to thermoset resin such as polyester or polyurethane. Typical applications are automotive interior substrates, furniture, and other flax-fiber-based products [11].

7  Hemp Fibers Hemp plant is a species of the Cannabis sativa plant that is grown for industrial uses. It is one of the fastest-growing plants and first plants to be spun into usable fiber 10,000 years ago. Europe is the biggest producer of hemp because of the contribution of energy conservation. Furthermore, hemp is grown in Canada, the USA, France, Hungary, Belgium, Holland, Thailand, Austria, Italy, China, the Philippines, Russia, Mexico, Germany, West Indies, and India [13]. Hemp is an important crop whose production is environmentally friendly. The plant is an annual plant which grows from seed. It can be cultivated in a range of soil and the soil must be well-drained, rich in nitrogen, and nonacidic. In the growing stage, hemp plant does not need pesticides, herbicides, and fertilizers, so it can make an important contribution to a sustainable future [13]. Hemp fibers have a multicellular structure like other bast fibers. The fibers are located in the cortex tissue of the stem and encircle the core cambium and xylem layer. In the cortex, single fibers which are 20–50  mm length are held together through their middle lamella to form fiber bundles situated parallel to the longitudinal axis of the stem. The fibers are made up of primary and secondary single fibers. The primary fibers are formed during the early growth stage and are larger than secondary fibers. The wall thickness of primary and secondary fibers is 7–13 μm and 3–6 μm, respectively. In a mature hemp fiber, the cell walls surround a small lumen and consist of a middle lamella on the outside, a primary wall, and a secondary wall. The middle lamella contains pectin and lignin, and the primary cell wall consists of hemicellulose [14]. The main components of hemp fibers are 70–74% of cellulose, 17.9–22.4% of hemicellulose, 3.7–5.7% of lignin, and 0.9% of pectin. Cellulose, hemicellulose, and lignin are basic components which affect mechanical properties of fibers. Cellulose gains stiffness and strength to the fibers. The components vary from fiber to fiber. The invariability leads to invariable results in their physical and mechanical properties. Diameters and properties of natural fibers depend on source, age, retting, separating techniques, geographic origin, rainfall during growth, and constituents’ content. Many microscopic and macroscopic factors cause variability in the properties of hemp fibers. These factors are crystallinity, microfibril angle, crystal modification, fineness, porosity, and size and shape of lumen [15]. The properties of hemp fibers are as follows: • Hemp fiber includes 62–67% alpha-cellulose, 8–15% hemicellulose, 4% lignin, 5% ash, and 1% waxes. • Hemp fibers show a high tenacity.

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• The fibers are cost-effective. • The fibers have a high absorption capacity against IR and UV radiation. • The water and moisture absorption capacity of fibers is high. Furthermore, the fibers have high air permeability capacity. • The fibers are not conductive and provide natural low flammability. • Their good dyestuff uptake properties allow easy dyeing, but their natural colors show many varieties. • The fibers are anti-mildew and antibacterial. • The fibers are ideally suited for needle-punched nonwoven products. • Although there are favorable properties of hemp fibers, some disadvantages limit the uses of hemp. The hemp fabrics are characterized by a dry and harsh touch, high wrinkle tendency, low-dimensional stability, and breaking elongation [16]. Application of hemp fibers are as follows: • Hemp fibers have been used for centuries to make rope and canvas. Long hemp fibers can be spun and woven to make crisp, linen-like fabric used in clothing, home furnishing textile, and floor covering. • Hemp fibers are commonly used in automotive industry for reinforcement of door panels, passenger rear decks, pillars, and boot linings. • Hemp fibers are also used to produce pulp and paper. • The fibers have high thermal and acoustic insulation capacity; hence, they are used in the insulation industry. Nonwoven hemp mats provide excellent insulation capacity. • Recently, it has been found that hemp fibers remove cobalt (II) agents from the aqueous solutions, leading to their use as an alternative in Co (II) wastewater treatment [17].

8  Kenaf Fibers All around the world, plant-based natural fibers are produced in billions of tons every year. Kenaf fiber is one of the fibers which has cellulose-based structure. It is economically viable and eco-friendly. Kenaf has a short seedling stage of only 4 months and has a high carbon dioxide absorbance capacity. In kenaf cultivation, it does not need pest control while it absorbs chemical and heavy metals from soil in growth period. It also has a wider range of adaptation to climates and soils than any other fiber plant in commercial production. Compared with other plant-based natural fibers such as hemp, jute, sisal, and flax fibers, kenaf fibers have many advantages with regard to production, anatomical properties, stem processing, fiber quality, yield, and prices. Kenaf (Hibiscus cannabinus), which belongs to Malvaceae family, is an annual plant that grows to 1.5–3.5 m tall with a woody base. It is native to Africa and has been cultivated to produce ropes and for animal consumption for at least 4000 years. The fibers in kenaf are found in the bast (bark) and core (wood). The bark of the plant has long fibers, while short fibers are located in the core. The individual fibers are 2–6 mm long and about 6 μm thick.

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The yield and composition of these plants can be affected by cultivar, planting date, photosensitivity, length of the growing season, plant populations, and plant maturity. Fiber production can be carried out with mechanical, chemical, enzymatic, and water retting (separation). Kenaf plant is cultivated for fibers in India, Bangladesh, the USA, Indonesia, Malaysia, South Africa, Viet Nam, Thailand, southeast Europe, and Africa. Furthermore, in many developing countries such as India, Thailand, and Indonesia, the development of kenaf production is the source of promise in the future advancement of rural areas [18]. Kenaf plant consists of three types of fiber: bast, core, and pith. The “bast” refers to the outer part of the fiber and represents about 30% of the dry weight of the stalk. Core refers to the inner part of fiber which is white color and contributes around 70% of dry weight of the stalk. The pith contains parenchymatous cells, which are not typically prismatic but polygonal in shape [19]. The physical properties of the fiber vary depending on the location, source, age of plant, separating technique, and history of fibers. The macrofibril size and chemical contents of kenaf fiber are given in Table 4. Kenaf fibers consist of 60–80% cellulose, 5–20% lignin (pectin), and 20% moisture. The cell wall contains a hollow tube which includes three different layers such as primary cell wall, three secondary cell walls, and a lumen. Recently, fiber-reinforced composites have gained attention owing to improving many characteristic properties and replacing the conventional materials in various applications. Kenaf fibers have been commonly used in fiber-reinforced composites as reinforcement due to its rapid growth at different climatic conditions, low cost, lightness, eco-friendly, sustainability, and high strength. However, in producing composites with kenaf, interfacial adhesion between the fiber and matrix is low [20]. Vilay et al. suggested that chemical treatments increase interfacial adhesion between the fiber and matrix. Alkaline modification treatment based on sodium hydroxide (NaOH) is suitable for kenaf fibers [21]. The other challenge of producing fiber-reinforced composite with kenaf is that kenaf fibers have poor water resistance. Researchers indicated that water repellent treatment with silicate-based compounds can resolve water absorption problem of kenaf fibers.

Table 4  Macrofibril size and chemical content of kenaf stem

Bark Fibril length, L (mm) 2.22 Fibril width, W (μm) 17.34 L/W 128 Lumen diameter (μm) 7.5 Cell wall thickness (μm) 3.6 Cellulose (%) 69.2 Lignin (%) 2.8 Hemicellulose (%) 27.2 Ash content (%) 0.8

Core 0.75 19.23 39 32 1.5 32.1 25.21 41 1.8

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9  Sisal Fiber Sisal fiber which is extracted from the leaves of plants belonging to the agave family are one of the commonly used plant-based natural fibers. The sisal fibers are obtained from sisal plant, which is very easily cultivated and can be harvested from 2 years after planting. The plant is known as Agave sisalana, and its productive life can reach up to 12 years, producing from 180 to 240 leaves depending on the location, altitude, level of rainfall, and variety of plant. Fibers are obtained from leaves of plant which contains a number of long and straight fibers. The fibers are obtained by machine decortications in which the leaves are crushed between rollers and then mechanically scraped. Then, the fibers are washed and dried by mechanical or natural means. In the cultivation of Agave sisalana, pesticides and chemical fertilizers are not used. Brazil is the largest producer of sisal fibers. Sisal plant can be cultivated in the semiarid climate. Besides, sisal plant is also cultivated in Angola, Cuba, Indonesia, Mozambique, South Africa, Thailand, Mexico, China, Tanzania, Kenya, and Madagascar [22]. Sisal fiber is composed of 78% cellulose, 8% lignin, 10% hemicellulose, 2% waxes, and 1% ash by weight. The amount of ingredients is different in every fiber, and soil, climate, maturity of the plants, and retting affect the amount of ingredients. The length of sisal fiber is between 1 and 1.5 m and the diameter is about 100–300 μm. The processing methods used to extract sisal fibers are retting, scraping, and mechanical decortication method. In mechanical decortication method, the fiber yield is 2–4% lower than retting method. However, decoration is the most common method for extracting sisal fiber. In this method, the leaves are crushed between blunt knives and the pulps are removed from the fiber. Water is used to clean, and obtained sisal fibers are dried in the hot sun [23]. The sisal plant and its products have been used for centuries for natural and commercial production. Sisal has a wide variety of traditional applications such as twine, ropes, string, and yarn. Furthermore, sisal has good potential as reinforcement in polymer composites owing to low density. The use of sisal fiber as reinforcement gains attention in automotive and furniture industry [24]. The properties of sisal fibers are as follows: • The color of fibers is soft gray ash. • The length of fiber varies from 80 to 120  cm and the fiber thickness is 0.2– 0.4 mm in diameter. • Sisal fiber is a durable fiber with low maintenance and minimal wear and tear. • It is a sustainable and biodegradable fiber. • Sisal fibers are obtained from the outer leaf of the plant. • The fibers are antistatic. • The fibers absorb dyes easily and offer the largest range of dyed colors of all natural fibers. • Sisal has moderately high stiffness, durability, ability to stretch, and resistance to deterioration in saltwater. • The acoustic absorption coefficient of fibers is high, and sisal fiber-reinforced composites are used as acoustic absorption materials [25].

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Application of sisal fibers are as follows: From ancient times, sisal has been the leading material for agricultural textile material because of its high tensile strength, durability, affinity for dyes, and resistance to deterioration in saltwater. • Sisal fibers are used commonly in the shipping industry for mooring small craft, lashing, and handling cargo. • The fibers are used in paper production industry because of its high cellulose and hemicellulose content. • Sisal fiber-reinforced composites are used in automobile industry. • Sisal is used in carpets or in blends with wool and acrylic for a softer hand. • Other products developed from sisal fiber include spa products, cat scratching posts, lumbar support belts, rugs, slippers, clothes, and disc buffers. • Sisal fibers are basic material for various engineering applications in the electrical industry, automobiles, railways, building materials, geotextiles, defense, and packing industry because of the low density and high specific strength and modulus. • The fiber is also used for nonwoven matting, brushing, and roving. • Sisal waste products can be used for making biogas, pharmaceutical ingredients, and building materials [25].

10  Jute Fiber In fiber-reinforced composite, jute is the most commonly used natural fiber as reinforcement. Jute plant belongs to Tiliaceae family and its scientific name is corchorus. Jute fibers are obtained from bast of corchorus and fibers are mentioned as corchorus capsularis. It is one of the low-cost natural fibers and has the bast fiber with the maximum production volume. It is cultivated in the Mediterranean, but in the present days, Bangladesh, India, China, Nepal, Thailand, Indonesia, and Brazil provide the finest types of jute. The height of jute can reach 2–3.5 m and it is very brittle because of the high lignin content. Jute fiber is mainly composed of cellulose, hemicellulose, and lignin. It is classified under the bast fiber category. The color of jute fibers is generally off-white to brown owing to the presence of minerals [26]. The composition of jute fiber is not uniform. The condition of the soil, climate, maturity of the plants, retting, etc. lead to significant variations in the structure of the fibers. The average composition of jute fiber is 60% of cellulose, 22% of hemicellulose, 12% of lignin, 1% of nitrogenous matter, 1% of fatty and waxy matter, 1% of mineral matter, and 3% of miscellaneous. The main constituents which are cellulose, hemicellulose, and lignin affect the properties of jute. The rest gives very little influence to the fiber’s structure [27]. Jute fibers are eco-friendly, biodegradable, and recyclable materials. Jute fibers have high insulating capacity for both acoustic and thermal energies. The worldwide production of jute fibers is about 3.3 million tons, and they are used for various applications. Especially, bag industry is the biggest user of jute fiber. Jute bags have gained an advantage as being an eco-friendly option of nonbiodegradable poly bags [28].

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The properties of jute fiber are as follows: • • • • • • • • • • • •

Jute fiber is biodegradable and recyclable. In the cultivation of jute plants, low pesticide and fertilizer are needed. Jute fiber has a golden color; hence, it is called “Golden Fiber.” The fibers are 1–4 m long. The fiber is bast-based and the production is very easy and cheap. In terms of usage, global consumption, and production, the fiber is the second most important vegetable fiber after cotton. The fiber has high tensile strength and low elongation. The fabrics produced with jute yarn have high capability of breathing; therefore, jute is very suitable in agricultural commodity bulk packaging. Jute fibers have less resistance to UV light, acid, and moisture. Like all natural fibers, jute fibers possess higher acoustic insulation capacity. Mechanical properties of fibers are better as compared to other natural fibers. Furthermore, mechanical properties of these fibers can be developed with surface treatment such as alkali treatment. Jute fibers are used in green (eco-friendly) composite applications and in various applications like automotive, structures, toys, and furniture. Application of jute fibers are as follows:

• The long jute bast fibers are used in the production of geotextiles. Jute fiber mats have high moisture retention and promote seed germination. Furthermore, jute fiber mats can also be used below ground in the road and other types of constructions as natural separators between different materials. • The fibers are used as air filters. • Medium- and high-density mats can be used for oil-spill clean-up pillow. • Jute fibers are used as reinforcement in fiber-reinforced composites because of their high tensile strength, biodegradability, accommodable, etc. • The fibers have been used for sacking products such as coffee, cocoa, nuts, cereals, dried fruits, and vegetables for many years. • In sophisticated products like fashion fabrics, jute fibers are used with wool, nylon, rayon, acrylic, polyester, etc. • Especially in the eastern region, jute industry is one of the major industries. It meets all standards for “safe” packing. • Jute fibers are used to produce handbags, shopping bags, wallets, and casual bags [29, 30].

11  Ramie Fiber Ramie belongs to the Urticaceae family derived from the bast of Boehmeria nivea and Boehmeria tenacissima and is called as China grass (Boehmeria nivea (L.) Gaud.). Now, it is commonly cultivated in China and other Asian countries including the Philippines, India, South Korea, and Thailand. It is an enduring plant, which

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grows to maturity in 44–55  days in a hot and moist climate. Ramie fibers are obtained from the bark layer of stem. The separation of fibers includes scraping, pounding, heating, washing, and chemical actions. The chemical compositions of fiber are 73–74% cellulose, 13–15% hemicellulose, 0.6–1.5% lignin, and 1–5.5% pectin. Due to the pectinous nature of bark, removal of fibers from the bark is ­difficult. Ramie fiber is characterized by high tensile strength, high thermal conductivity, coolness, moisture absorption, and antibacterial function [31, 32]. Ramie is one of the strongest cellulose-based fibers. In wet conditions, it exhibits greater tensile strength. Ramie fiber is known especially for its ability to hold shape and reduce wrinkles. It can be blended with other fibers. Many properties such as absorbency, density, and microscopic appearance are similar to flax fibers. The fibers have high crystallinity [33, 34]. The properties of ramie fiber are as follows: • • • •

The fiber length ranges within 150–200 mm. Rami fibers exhibit high tensile strength, high luster, and brightness. The fibers have high resistance to heat, light, acid, and alkali. Because of the availability, renewability, low density, and price, ramie fibers are an ecological alternative to glass, carbon, and synthetic fibers [33]. Applications of ramie fibers are as follows:

• Ramie is blended with other textile fiber for its high tensile strength, absorbency, and dye-affinity. After blending, it is used in clothes, bags, napkins, handkerchiefs, home textiles, and medical textiles. • Ramie is often blended with cotton to produce knit sweaters. • Ramie is used in fishnets, canvas, upholstery fabric, straw hats, and fire hose [34].

12  Abaca Fiber Abaca fiber, which is obtained from the leaf of Musa species plant that belongs to banana family, is a strong natural fiber. The leaves are pointed, narrower, upright, and more tapering than banana leaves. The plant is also known as Manila hemp, binomial name Musa textilis, and cultivated in Philippines and East Indonesia. The plant grows to 4–6.7 m and averages about 3.7 m. The main chemical constituents of abaca fiber are 76.6% cellulose, 14.6% hemicellulose, 8.4% lignin, 0.3% pectin, and 0.1% wax. The abaca fiber is extracted from the stalk of the plant using either manual or mechanical process. Volcanic regions, such as the Philippines, and tropical climate are suitable for abaca cultivation. Abaca fibers are extracted from the leaf with manual or mechanical process. Decortication is an alternative method to extract abaca fibers [35]. In the literature, it has been reported that abaca fiber has a high tensile strength, is resistant to rotting, and has a specific flexural strength compared with glass fiber. It has been widely used as raw material for ropes, bags, and paper. In recent years, abaca fiber-reinforced composites have been frequently used in the automotive

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industry by manufacturers like Mercedes-Benz. Furthermore, it is reported that abaca fiber is the first natural fiber to meet stringent quality requirements for the exterior components of vehicles [36]. The properties of abaca fibers are as follows: • Abaca fibers are defined as biodegradable and sustainable fiber. Furthermore, abaca plant prevents erosion control and biodiversity rehabilitation. • Abaca is superior fiber with high tensile and folding strength and high porosity. • The fiber length can reach to 3 m. • It is resistant to saltwater decomposition. • The fiber possesses high elongation. • Owing to high lignin content, fibers are resistant to acids. • Abaca fibers are soluble in hot alkali, readily oxidized, and easily condensable with phenol. • The fibers have an excellent ability to dyeing. Application of abaca fibers are as follows: • Abaca fibers are resistant to saltwater. For this reason, the fibers have been commonly used to produce fishing nets. • The fibers are mainly used to manufacture tea bags. • The fibers produce high-quality paper, diaper, napkins, machinery filters, medical textiles, and electrical conduction cables. • Abaca fibers are used to manufacture home textiles such as curtains and furniture. • Ropes, marine cordage, and cord are produced from abaca fibers. • Nonwovens produced from abaca fibers are used as medical gas masks, gowns, and diapers. • Abaca fiber-reinforced composite has got significant and outstanding interest in the automobile industries due to low-cost availability, high flexural and tensile strength, good abrasion and acoustic resistance, relatively better resistance to mold, and high resistance to UV rays [37, 38].

13  Other Plant-Based Natural Fibers Banana Fiber Banana fiber obtained from the pseudo-stem of banana plant is a lignocellulosic fiber. It belongs to the Musaceae family. Approximately, every year, 70 million metric tons of bananas are cultivated in the tropical and subtropical regions of the world. The fibers are obtained from the bast of the plant and have good mechanical properties. The fibers consist of 9% lignin, 43.46% cellulose, and 38.54% hemicellulose. Banana fibers can be blended with other fibers to manufacture textile fabric. Banana fibers are used to produce home textiles, rope, and fiber-reinforced composites [39, 40].

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Pineapple Fiber The chemical composition of pineapple fiber is similar to flax and jute fiber (Table 5); however, the lignin content is more than flax and less than jute. Physical properties of pineapple fiber are given in Table 6. Pineapple fiber is white color, soft, and smooth and feels like silk. The mechanical properties are higher than cotton. The fibers can be used for triangular core linens in geotextiles, central reinforcement material for rubber conveyor belts, and core materials for belt and high-strength canvas. Furthermore, it can also be used in the papermaking industry, for reinforced plastic, roof materials, ropes, and fishing nets [41].

Coconut Fiber Coconut fiber is obtained from the husk of coconut plant which belongs to the palm family. In order to extract coconut fiber, coconut is left in hot seawater, and subsequently, the fibers are removed from the shell. The individual fiber cells are narrow and hollow with cellulose thick walls. The length of coconut fibers varies from 15 to 35 cm. Coconut fiber has high lignin and cellulose content. The fibers are light and gold-yellow or brown color. The plant is cultivated in Europe, Africa, Asia, America, and Australia. Coconut fiber is used to produce hawsers, ropes, cords, runners, mats, brooms, brushes, paintbrushes, stuffing for mattresses, and upholstered furniture [41].

Okra Fiber Okra, Abelmoschus esculentus, plant belongs to Malvaceae family. The plant is cultivated in subtropical and tropical regions all around the world. Okra fibers are obtained from the bast of the plant. The fibers contain 67.5% α-cellulose, 15.4% hemicellulose, 7.1% lignin, 3.4% pectin, 3.9% fatty and waxy matter, and 2.7% aqueous extract. The density of okra fiber is approximately 881.817  kg/m3. The fibers have high mechanical properties. For this reason, the fibers are used in composites as reinforcement [42]. Table 5  Chemical composition of pineapple fiber Constituent %

Cellulose 56–62

Hemicellulose 16–19

Pectin 2.0–2.5

Lignin 9.0–1.3

Water-soluble Fat and material wax 1–1.5 4–7

Ash 2–3

Table 6  Physical properties of pineapple fiber Length (mm) 3–8

Diameter (μm) 7–18

Fineness (tex) 2.5–4.0

Length (mm) 10–90

Strength (cN/dtex) 4.26

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Sun Hemp Fiber Sun hemp is a tropical and subtropical plant cultivated in many countries, especially in India, mainly for its high-quality fiber. In literature, there are various studies used sun hemp fibers as textile materials. The raw fiber has an acceptable tensile strength and thickness and is used as a textile material. In order to use sun hemp fiber in textile, it is necessary to apply pretreatment. After the pretreatment process, the fibers can be dyed and spun into yarn [11].

14  Conclusion In recent years, plant-based fibers have become an important class of textile fibers. These fibers are a sustainable and biodegradable alternative to synthetic fibers. Furthermore, they have relatively low density and are abundant in nature, and their tensile properties are comparable to synthetic fibers. Plant-based natural fibers consist of three major components which are cellulose, hemicellulose, and lignin. The amount of these ingredients in a fiber depends on plant age, origin, and fiber extraction method. Industrial uses of cellulose-based natural fibers gain attention from various manufacturing sectors. Various fields apart from textile industry where these fibers can be used are automotive industry, nonstructural composites, geotextiles, packaging industry, filters, furniture, structural composites, and medical industry. Cellulose-­ based natural fibers are competitive materials thanks to biodegradability, availability, recyclability, low prices, renewability, high mechanical properties, and low density. Cotton, flax, jute, ramie, bamboo, banana, pineapple, sisal, kenaf, coir, and hemp fibers are used in the production of textile materials. Furthermore, these fibers are commonly used as reinforcement in polymer matrix composites. The use of these fibers contributes to the decrease in environmental pollution.

References 1. Lee BH, Kim HS, Lee S, Kim HJ, Dorgan JR (2009) Bio-composites of kenaf fibers in polylactide: role of improved interfacial adhesion in the carding process. Compos Sci Technol 69(15–16):2573–2579 2. Hajeeth T, Gomathi T, Vijayalakshmi K, Sudha PN (2014) Synthesis and characterization of graft copolymerized acrylonitrile onto cellulose prepared from sisal fibre. Macromolecules 10(1):7–17 3. Güler R (2018) Determination of the relationship between sustainability, environmental risks and environmental accounting: a research in Erzurum. M.Sc. thesis, Bayburt University, Graduate School of Natural and Applied Science, Bayburt, Turkey 4. Onuaguluchi O, Banthia N (2016) Plant-based natural fibre reinforced cement composites: a review. Cem Concr Compos 68:96–108

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Coyoyo Silk: A Potential Sustainable Luxury Fiber Marisa Gabriel, Miguel Angel Gardetti, and Ivan Cote-Maniére

Abstract  Capitalism, new technologies, synthetic fibers improvement, accelerated growth, and the never-ending pursuit of efficient and low-cost models of production are not only destroying environment but also demolishing cultures, ancestral knowledge, and risking natural fibers. Ancastí, Catamarca, Argentina, is the home to a very special wild silk named coyoyo silk, which could be considered sustainable luxury, but it is actually unknown. This chapter aims at enriching and enlightening the fashion industry with sustainable raw material that is being left. Sustainable luxury means returning to the ancestral essence of luxury, respecting social and environmental issues; it becomes a way of empowering and strengthening local communities. Doña Pabla Quiroga is the last known craftswoman who works with coyoyo silk and maintains this ancestral knowledge alive by creating unique pieces and training women in her neighborhood. This chapter studies the origin of mount silk, the ancestral knowledge required to process it, the spinning and weaving processes, the potential of this material as sustainable raw material, and how it can turn into sustainable luxury. Through interviews and photographs, we will explore the whole process of obtaining and processing the fiber, and we will focus on problems and hardships artisans face to maintain this local and cultural legacy alive. Keywords  Sustainable luxury · Coyoyo silk · Craftsmanship · Cultural heritage · Ancestral knowledge · Fashion and textiles M. Gabriel (*) Sustainable Textile Center, Buenos Aires, Argentina e-mail: [email protected] M. A. Gardetti Center for Studies on Sustainable Luxury, Buenos Aires, Argentina e-mail: [email protected] I. Cote-Maniére SKEMA Business School, SKEMA Paris – La Défense Campus, Pôle Universitaire Léonard de Vinci (PULV), Courbevoie, France e-mail: [email protected] © Springer Nature Switzerland AG 2020 S. S. Muthu, M. A. Gardetti (eds.), Sustainability in the Textile and Apparel Industries, Sustainable Textiles: Production, Processing, Manufacturing & Chemistry, https://doi.org/10.1007/978-3-030-38541-5_3

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1  C  apitalism and Fashion Impoverishing Cultures: An Introduction to the Problematic The current fashion system is based on economic growth and the continuous need to change when nothing really changes at all. Globalization and capitalism within the fashion system are demolishing cultures and standardizing societies by selling the same products – fashionable – to everybody. The world is undergoing an environmental and social crisis, climate change, waste and pollution, and scarcity of resources, while inequities increase. The actual prevailing economic system is unsustainable. Moreover, we are losing cultures and human values such as ethics and diversity. The actual system of production not only sacrifices communities but also an ancestral knowledge that we should preserve as a natural cultural heritage. Under these circumstances, the fashion system can be considered destructive. People try to copy others and companies try to copy business models and clothes from big corporations and multinational brands. Trends in fashion are expressions of sociocultural tendencies that can be seen in architecture, streets, cities, and people or groups. While trends in the broad sense is a way of anticipating and knowing people, in developing countries, for example, companies instead of making local research, they look abroad. Moreover, they do not make any research at all, and they just copy bestselling items and sometimes try to produce locally, but most of all import goods. This model is devastating for the local textile industry and also impoverishes cultural and social levels. It tries to adapt the textile industry to functional models for other countries instead of valorizing the local industry. While fashion could be the way in which our clothes reflect and communicate our individual vision within society [4] under this logic, fashion is losing all kinds of individual vision. In fashion, we always hear the same voices, those from dominant countries and fast-­fashion companies which offer “brand” clothes for accessible prices, so that people can buy more. However, it is known that someone pays for these low prices, and at high rates. Fashion, instead of continuing to operate under this system of standardization, has the potential to communicate and promote ethics and awareness. Fashion should reflect different perspectives by empowering people and nourishing the whole system from diversity. “As a cultural process, fashion is a profoundly social experience that invites individual and collective bodies to assume certain identities and, at times, also to transgress limits and create new ones” [15, p. 1]. Under these premises, fashion is a way to express ourselves, show our values, and reveal who we are. Fashion is a way to communicate ourselves, and influence others. Through fashion, we construct, distinguish, and show who we are. “Corporeal decorations, accessories, jewelry, costume, and types of fabrics, for example, have been historically used by diverse social groups to distinguish themselves and visually express particular cultural identities” [13, p. 17]. Fashion has the potential to express sociocultural attributes of people, while it is a powerful tool to preserve and revalorize cultural practices that are being lost. Furthermore, when we add luxury to fashion,

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textiles, and apparel, the scope can be even more. While fashion brands try to sell products, the luxury sector instead transcends the creation of products. In this way, luxury has the potential to rescue and preserve ancestral cultures being lost. This chapter aims to contribute to cultural diversity and textile fibers. To begin, we describe luxury and analyze different attributes of luxury, as well as fashion and sustainability. Second, we show the whole process of obtaining and processing coyoyo silk, and its final products. To conclude, in order to enrich the natural fibers and enlighten the process of coyoyo silk, we compare coyoyo silk attributes to those of luxury and expose the possible potentials and difficulties of bringing it to light.

2  Attributes to Be Considered in Luxury As fashion, luxury is a much criticized industry for lack of transparency and fostering inequalities being only accessible for a few. The idea of luxury is relative and considerations of luxury may change through time and context. However, in its broader sense, luxury goods might contain high standards of creativity and concentrate on details, craftsmanship and precision, exclusivity, innovation, and high quality. Therefore, price ultimately should be a consequence of all these attributes. Democratization of luxury made it lose the magic and the myth behind the product. Luxury was associated to uniqueness and made people feel really special. As luxury is completely related to cultural and environmental circumstances, it is relative, it is a subjective notion, and it is a matter of personal attributes and context. Dana Thomas suggested even in the introduction to her book Deluxe: How Luxury Lost Its Luster that the democratization of luxury made it lose its magic. “The luxury industry has changed the way people dress. It has realigned our economic class system. It has changed the way we interact. It has become part of our social fabric. To achieve this, it has sacrificed its integrity, undermined its products, tarnished its history and hoodwinked its consumers. In order to make luxury ‘accessible,’ tycoons have stripped away all that has made it special” [17, p. 13]. There is something implicit that makes luxury unaffordable for common people. Luxury being affordable everywhere changes consumer perception and becomes something premium but ordinary. Turunen mentioned, “Luxury used to have clearer boundaries; it was something rare and unattainable, something to which only a small elite used to have access” [19, p. 5]. Same as in fashion, under this system, luxury is losing its deepest sense and value. Desire, in this sector, plays a crucial role. “The greater the inaccessibility  – whether actual or virtual – the greater desire” [9, p. 67]. When someone buys luxury items, usually, they dream of such items over time. Luxury houses not only sell exquisite products, but also the experience of buying this type of products. In order to attract and engage consumers luxury brands should consider: price, time, availability, sociocultural attributes, and both, at the luxury house or by the online shop it might set different obstacles to strain consumers desire. Prolonging the time between dreaming and acquiring or having something attracts luxury consumers.

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Compared to a fashion item, the luxury purchase is a much more considered decision. For instance, when buying fashion products, people go to the store or enter online, purchase the item, and start wearing it. However, when someone buys luxury, first they spend time, could be months, choosing and deciding. Luxury is truly connected with desire, emotions, and dreams. Kapferer and Bastein [9] set some aspects to qualify a product as luxury. The first aspect, the way to conceive a luxury product or service should be holistic, it becomes part of a multisensory experience. If it is a product, it should be together with a service, and if it is a service, it should have a little symbolical souvenir or object. The second aspect should be its relationship with the dream. Dreaming is part of human beings and luxury should be extremely related with dreams. By purchasing luxury, people do not try to fulfill needs or desire, they try to afford something they have previously dream on. Som and Blanckaert [16] suggests one of the aims of luxury sector is selling a dream, making people feel special, and give them the sense of belonging to a group of special people. Luxury is aspirational. Moreover, people who belong to this niche become faithful to an identity; a luxury product is not compared to others because it is already differentiated. “The luxury item is an object loaded with meaning, to which one becomes attached” [9, p. 25]. Luxury is the business of durable value. This value is represented by different attributes: excellence and quality, ancestral heritage, craftsmanship, scarcity, iniquity and exclusivity, beauty aesthetics, design, innovation – through creativity and invention – the art of telling stories, sensibility, tradition and values, the potential to satisfy dreams, and high price. Excellence and very high quality are the attributes that distinguished luxury over time. Also durability of luxury items should be highlighted, since people who purchase luxury usually make them last, and pass it along through generations. At the same time, old and traditional luxury houses have a strong historical value, based on its background, and the techniques they use in making the products. “Mostly small family businesses operated by high-quality artisans and craftspeople that had highly specialized areas of expertise for which they have obtained global reputation” [14, p. 68]. As mentioned before, there is a strong relationship between luxury and time. Democratization of luxury drives away time from luxury; however, time is important for the creation, production, and sale of luxurious items. Furthermore, time is vital in the process of creating the brand. The brand, in luxury, should have a strong relationship with time. It should set its basis attached to different past events that could give a sense of belonging, and there are different strategies to keep this reference to our legacy. “Heritage gives the brand prestige, which in the field of luxury fashion products evokes a symbolic content” [8, p. 15]. Heritage is strongly related to sensibility, traditions and values, and the technique under the creation of luxury products. This technique should be unique, and each product should be printed by this sense of uniqueness. Craftsmanship is very important in luxury since it is the way to differentiate. It should be precise, which does not mean perfect, because the signs of handmade add value and should be countable in luxury pieces.

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Together with creativity, innovation, and vision, these attributes are mixed and having a story to tell is the key to create the universe of luxury. Every luxury brand has its own story. Nowadays, it is crucial for luxury brands to invest on their websites, selling platforms, and on the online channel. Consumers are rapidly moving to e-commerce, and brands should be prepared. Specifically luxury brands should be able to tell the story and recreate the experience of entering to a luxury house boutique, at an online website. Users may keep a long time dreaming of a luxury product before they buy it. The experience of buying luxury pieces used to be in boutiques, or main houses of designers; now, the online experience should be as pleasant and capable of generating desire as it is entering for example a luxury flagshipstore. As mentioned before, there are various aspects which determine luxury depending on sociocultural standards. Nowadays, environmental and societal crises are important issues that redefine luxury. Environmental awareness, scarcity of resources, and social inequities are different aspects that are reframing luxury. Through the vision of sustainable business management, the luxury sector has the potential to salvage traditions, values, and most of all, transcend and impact positively on society and the environment.

3  Sustainability and Sustainable Luxury Sustainable development implies satisfying human needs, without compromising environment and future generations. It establishes a close relationship between people, economic development, and the environment. These three are the pillars of sustainability, and as sustainability is systemic, these attributes are influenced and modified by the other. This holistic approach reflects the organism as a whole, and can be applied on individuals, groups, companies, and the society. Sustainability makes us responsible as individuals: it leads people to rethink their relationship with others, their ways of consumption and production, and the way they inhabit the Earth. However, if sustainability stays attached to current systems and development models, it would not be achieved. “At this moment in time, almost everything being done in the name of sustainability entails attempts to reduce unsustainability. But reducing unsustainability, although critical, does not and will not create sustainability” [3, p. 54]. It is imperative to make disruptive innovations, and think really different the way in which business could be made. The luxury sector has the opportunity, potential and, even more, the responsibility to assume commitment to sustainability. To begin with, sustainable luxury is based on making business and luxury products while preserving and looking after people and the environment. This not only includes consumers but also artisans and traditions behind the product. It is characterized by a strong transforming character in the society and the environment, presenting very exquisite techniques and resources that ensure uniqueness, and very high prices. In this sense, introducing sustainability to the luxury sector is an opportunity to bring back its authentic conception. “Sustainable luxury is the concept

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returning to the essence of luxury with its traditional focus on thoughtful purchasing and artisanal manufacturing, to the beauty of quality materials and to respect for social and environmental issues” [7, p. 4]. Sustainable luxury presents the opportunity to support craftsmanship and discover talents and fibers that are being abandoned, helping with those communities and people that do exceptional art pieces but need the vision to scale in market and sell those products at high rates. At the same time, in a world full of inequities, companies in the luxury sector have the responsibility to influence and impact positively in society. “Luxury has a mission. It is to be part of a new sustainable development policy, which would give more nobility to this very profitable business. Luxury enjoys continuous growth, and the limit of the growth is not clear; it seems impossible to say where the end may be, so enormous are the market potentials” [16, p. 417]. As mentioned by Som and Blanckaert [16], sustainable luxury is a vehicle to preserve and promote traditions. “The skill sets mainly focused on their passion for excellent craftsmanship and creative design that had their signature differentiation” [16, p. 239]. Products conceived under these premises are pieces of art, and representations of different cultures, that enrich cultural heritage. Sustainable luxury would not only be the vehicle for greater respect for the environment and social development but also synonym for culture, art, and innovation of different nationalities, maintaining the legacy of local craftsmanship [5]. The relationship between artisans, designers, and brand managers is key in this type of entrepreneurship. Both designers and artisans should be able to expand their scope and transcend their way of creating. While designers are nourished and inspired by the power of artisans and ancestral techniques, designers or brand managers nourish and empower artisans ensuring a high-rate income for their creations. Furthermore, while brand gains from the artisanal craft specificity, technique, and responsibility, they should respect and support the artisanal communities making them fulfill different needs and overcome different situations. “Sustainable luxury is the return to the ancestral essence of luxury, i.e., a thoughtful purchase, artisan manufacture, beauty of materials in its broadest sense, and respect for social and environmental issues” [6, p. 4].

The Importance of Craftsmanship Crafts are part of the cultural skills passed through generations, and they are inherent to human beings as a way of expression. Crafts should be at the heart of a sustainable luxury company, generating value, and at the same time, preserving local ecosystems. Craftsmanship is the most valuable element in the production process of luxury garments. It should be capable of transforming something rustic in a product of splendor that reflects human trace. For people who create, crafts are a bridge to their own emotions and sensitiveness. Sustainable luxury presents the opportunity to show humility and respect for process and time.

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Empowering communities, particularly women in communities, is basic to enable and create alternatives for them to afford better living standards. “As women gain confidence, they begin to make decisions within the household that were formerly left to other family members” [11, p.137]. One of the main issues to take into consideration is that women have an important role in family and childhood. Generating an income for them is an important opportunity for the improvement of children’s lifestyles. Littrell and Dickson suggest, “Artisans, desperate for income, are vulnerably positioned for potential exploitation in the process of product commercialization” [10, p. 12]. Usually with the purpose of selling, artisans underestimate the value of their work, selling garments at the price that customers may set. Customers are often ordinary travelers or tourists who do not take into consideration the importance of craftsmanship. In the first place, artisans make great efforts to get raw materials, living in remote places, and traveling long distances to get them. Second, they have to make crafts and garments at home, and usually this process needs time, skills, and techniques and they do it along with other home duties. At last, they should travel to villages, or tourists’ points, to try to sell these items. It is essential to consider that usually they travel by foot, walking long distances, and sometimes together with babies or children whom they cannot leave alone. Under these circumstances, young women in the communities do not want to continue with the legacy. They try to abandon those places looking for new possibilities. Sustainable luxury has the chance to revalue cultural heritage, making local cultures known globally. At the same time, Internet is making possible to track artisanal craftsmanship and bring them to light. “The contemporary handmade economy is enabled by a different intersection of the local with the global in the form of the international marketing and distribution pathways enabled by the ‘long tail’ of the internet distribution” [12, p. 1]. Today, Internet enables users to meet artisans, giving the possibility of transparency and traceability by making visible the story and the people behind the product. As it happened in the old days of luxury, where the buyer met the artisan personally to buy the product, now new technologies make this process easy. It is essential to prevent the disappearance of traditions and to preserve cultures. Furthermore, it is necessary to bring communities to light and give them a voice, to respect them and learn from them. Nowadays, the global interest of people in crafts is increasing. “Contemporary craft economy at least helps us foreshadow some alternative social and economic imaginaries” [12, p. 143]. It is important to mention the possibilities business have to transform society by rescuing ancestral wisdom. However, increasing interest on crafts does not mean that people are conscious about the history behind the object and the importance of salvaging cultures; ensuring this should be the aim of sustainable luxury businesses. Catamarca, Argentina, is home to coyoyo silk. In line with this, is coyoyo silk an undiscovered sustainable luxury? Doña Pabla is the woman behind this tradition. She presents the ancestral knowledge hidden in Ancasti, coyoyo silk, the history, the process, and the materials needed to work with it.

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4  Coyoyo Silk There are about 300 varieties of butterflies with caterpillars spinning silk fibers found in China, Japan, India, Madagascar, Africa, and Central America. In Latin America, these buds were detected by archeology in Huachichocana III, Jujuy (7760 to 6720 BC) [1]. At that time, they were used only as ornaments and bells for those first inhabitants. Afterward, it was common for women to weave scarfs and make ponchos or other garments from the buds of coyoyo silk. Native coyoyo silk in Latin American countries is obtained from a butterfly that thrusts in bushes and spinal forest trees. (Figure 1 shows the butterfly of Coyoyo’s silk.) Locally, this butterfly is known by the name of Purucha or Pulucha. Technical Information [2] Butterfly family: Saturnidae Gender: Rothschildia Species: R. Schreiter However, when China’s silk became popular, local production of coyoyo silk decreased. Argentina had had quality production of coyoyo silk, but could not compete with Chinese silk. A similar problem was seen in México and Perú. The cost of Chinese and European silks ended up drowning some nascent industries that could have long enriched certain Andean regions. The Argentine archaeologist Nestor Kriscautzy observed that the coyoyo silk textile art was present in Catamarca, Argentina [2]. Coyoyo silk pieces were found in the east and south of the province. Nonetheless, 20 years later, this art is being lost, and Ancastí is the last place, at least known, where there is still a woman who knows the story and the technique to maintain alive this craftsmanship. Doña Pabla Quiroga was interviewed and the whole process has been registered for this chapter. Figure 2 presents Doña Pabla, the master of coyoyo silk.

Fig. 1  Butterfly of coyoyo silk

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Fig. 2  Doña Pabla

Doña Pabla lives in the monte1 of Ancastí (see Fig. 3), and her lands used to be full of coyoyos. She had, and still has, native trees and bushes where coyoyos rest. However, nowadays, the survival of these coyoyos is beyond her control. The main bushes that the bugs choose to feed themselves are tinajera and tala (Fig. 4 presents a tinajera). Doña Pabla is 83 years old and she lives with Don Agüerito, a 76-year-old man, who is a friend of the family. They live in the countryside of Ancastí, 9 kilometers away from the village. Thirty years ago, Don Agüerito went to live with Doña Pabla and her husband, who was her great pillar and passed away 2 years ago. Luckily, she has Don Agüerito. He is the one in charge of farming. He provides firewood and keeps their home warm and is the one who drives if they need to go somewhere. He is also the one who fetches cocoons for her and makes spinning and weaving tools (see in Fig. 5, a coyoyo in a branch of a bush). Every morning he herds cows and goats, and in the meantime looks up for coyoyos, sometimes finding ten; others, only six. Nevertheless, Doña Pabla always has raw material to work with. While he herds the cattle, she spins and waits for him for lunch. See Fig. 6, a coyoyo with the bug, or butterfly still inside, hanging from a tala branch; and see at Fig. 7, two coyoyos attached to a tinajera.

1  Monte: a nonurban and uncultivated land where there is vegetation. This vegetation can be formed by trees, bushes, shrubs, and herbs.

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Fig. 3  Monte, lands of Ancastí

Fig. 4  Tinajera bush

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Fig. 5  Coyoyo in Tinajera bush

Fig. 6  Coyoyo attached to a branch of a tala

It is important to highlight that the authors had to travel to Catamarca to gather the necessary information for this research. It took time to get to know Doña Pabla and Don Agüerito, build trust, and above all respect the people behind this wonderful technique. The atmosphere in this place is really peaceful and simple. In Fig. 8, the authors present the home of Doña Pabla and Don Agüerito. There is no telephone or Internet. In the kitchen of coyoyo’s silk, hot water is always ready in a kettle for very sweet mate, and many cans or cooking pots are hanging (see coyoyo’s silk kitchen in Figs. 9 and 10). The elements and tools used are made there by the same people, and they try to help and collaborate with other neighbors.

60 Fig. 7 Two coyoyos holding from a tinajera bush

Fig. 8  Doña Pabla’s home

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Coyoyo Silk: A Potential Sustainable Luxury Fiber Fig. 9  Coyoyo’s silk kitchen

Fig. 10  The kitchen from the outside

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Obtaining Coyoyo Silk In the first place, we should mention Coyoyo is the name given to the cocoon from where the silk is obtained. Doña Pabla suggests this name came from the Diaguitas, a group of indigenous people from the region. As mentioned above, they used coyoyos as ornaments, for example, in necklaces. According to Corcuera [1], it is a Latin American silk and came from México. Coyoyo silk is produced by a local wild silkworm species and is harvested after the moths have left the bud when the butterfly flies. Sometimes coyoyos are harvested before the butterfly flies, but Doña Pabla knows by its weight that there is a caterpillar still inside. So, she leaves cocoons hanging all together until butterflies come out, and only after that does she start the process of creation (see Figs. 11 and 12). In the hands of Pabla Quiroga, coyoyo silk turns into very special threads and knits that are part of the cultural legacy of the region. This technique evidences ancestral knowledge that passed through generations, and still today we can find them as cultural treasures, always sustained by women. The fiber is considered to be sustainable, natural, and renewable raw material. Sometimes silk is criticized for killing the worm, but in this case, coyoyo silk could be named cruelty-free.

Fig. 11 Recollected coyoyos before the butterfly flies

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Fig. 12 Recollected coyoyos

Although the whole process used to be simple, today it is getting more complex because the cocoon migrated deep into the countryside, and gatherers must walk for hours to find even fewer cocoons than in the past. Like all species, they mutate through time. For instance, today, they are no longer feeding from the same plants they used to. Also, civilization forced them to go deep into the countryside. At the same time, the worm is polyphagous, which means it feeds not only from one variety of plants but also on what it can find. As shown in previous figures, coyoyos are found in the countryside, and they are not easily seen. To begin with, during spring, summer, and autumn, it is very hard to reach them because of the bushes and leaves from the same trees. Doña Pabla Quiroga said that she usually waits for winter to harvest them, and in this season, she faces freezing climate conditions. Today, the practice of collecting and weaving is no longer seen in its place of origin, it is only Doña Pabla who keeps the technique alive. She mentions that in the past, men collected cocoons for women to weave. She learned it from her ­grandmother, and it used to be practiced by families. As mentioned above, she is the last, at least known, craftswoman who knows this wonderful technique. In the past years, she trained four women in the art of spinning and weaving this coyoyo silk. However, none of them really practices it. For these women, it is easier to spin wool, it is practical, simple, and cheaper; so, if they cannot see the value

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Fig. 13  Doña Pabla and Lili hand-spinning

and potential of this technique, they will forget about it, and leave it behind. Only one of the women who learned the technique still goes to visit Doña Pabla, and tries to practice and improve her technique (see Fig. 13, Doña Pabla and Lili handspinning coyoyo silk). It is impressive that all that is needed in the process of coyoyo silk is found in the same natural space. And every tool that is needed is made by men with wood and bones from the animals they eat. As presented later on this chapter, the whole process is made locally, at home, and artisanal. Doña Pabla knows that there exist sophisticated winding tools, which could make the process faster, but she cares about the silk and prefers to maintain the authentic technique she learned from her grandmother. She mentions that she is and should be very careful with this material, because after all the work done by silkworm, introducing it to a faster or mechanical process means not caring about the silk. She sticks to being soft and patient.

About the Caterpillar When this type of caterpillar was found, it fed from three species of native trees: the mulberry, the tinajera, and the ancoche. Nowadays, coyoyo is also found in tala and other native species from this region. Usually, the tree where they eat is where

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Fig. 14  Fleece of coyoyo silk

afterward they start creating the silk filament and begin to wrap themselves in it, shaping the cocoon. With this filament, the bug, in the first place, gets attached to the tree; second, it shapes the coyoyo and stays there until the butterfly breaks through and flies. Cocoons are collected by hand, and as mentioned above, one of the main problems today is that bugs modified their diet, and moths are no longer concentrated in small areas around one type of bushes. While the shape of the cocoon stays the same, its size varies, and its color can sometimes be differentiated according to the type of worm and the plants they eat. They are usually brownish and present the shiny characteristic of Chinese silk, but it is not as soft. These fibers can be perfectly dyed; they present good resistance, stability, and performance. However, threads of coyoyo silk are more alike to vicuña wool than to Chinese silk (see in Fig.  14, coyoyo’s silk fleece color and shininess). Once the butterfly leaves the cocoon, they are collected and hooked all together in wires, where the butterfly reproduces and new buds are generated. Doña Pabla says that in the past she used to have a small domestic production, but nowadays she cannot do it because the bugs have changed their diet.

Obtaining the Thread In the first place, Doña Pabla needs to make lejía, which is a homemade bleach from ashes and water. To make it, it is necessary to put water and big quantities of ash in a pan or can. Ashes should be of firewood, if another type of wood is used, it does

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not work in the same way; for example, with quebracho you never get this kind of natural bleach. Doña Pabla collects them from the home fireside and leaves them aside for her lejía production. As pan, or pot, she uses a can, where she introduces ashes and water and hangs it from a chord over the fire. After 30 minutes of boiling, the can is retired from the fire and set aside to cool (see Fig. 15, the whole process of making artisanal bleach, and in Fig. 16, the pot of bleach ready). When it cools down, the ashes sink to the bottom of the can, and it is necessary to strain it, separating the water on one side and leaving the ashes that are thrown to the ground. (see Fig.  17). This water obtained is named lejía, and it is with this domestic bleach that the coyoyos should be boiled. Previously, ten coyoyos are grouped within an old, thin, whitish sock or piece of cloth. It is important to choose a whitish, noncolored textile since if it is colored, silk will rapidly absorb it and it may lose its natural colors (see Figs. 18 and 19).

Fig. 15  Process of making Lejía Fig. 16  Lejía ready to strain

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Fig. 17 Straining Lejía

Fig. 18 Setting coyoyos inside an old sock

In each sock or piece of cloth, Doña Pabla introduces ten coyoyos. She takes a can where she pours half a can of lejía, the cloth with coyoyos and leaves it hanging above the fire to boil approximately 20 minutes. When this process is ready, coyoyos sink to the bottom of the can. It is important to see that when the ashes are not sufficient, and the bleach is not strong enough, the fiber does not soften and the process should be repeated (see Fig. 20, coyoyos boiling in lejía).

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Fig. 19 Coyoyos ready to be boiled

Fig. 20 Placing coyoyos to boil in Lejía

When coyoyos silk is softened in the bottom of the can (Fig.  21), they are removed from lejía (Fig. 22), washed with cold water (Fig. 23), and left to dry (Fig. 24). During this process, the fiber should not be exposed to direct sunlight as this would affect its quality. It is important not only to wait until they cooled down but also to wait until they get dry. To continue with the spinning, they should be still a little humid, but this does not means wet.

Coyoyo Silk: A Potential Sustainable Luxury Fiber Fig. 21 Boiling coyoyos

Fig. 22 Taking coyoyos from the can

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Fig. 23 Washing coyoyos

Fig. 24  Coyoyos ready to start the spinning process

When Coyoyos are ready to disassemble, Doña Pabla with her fingers starts the process of moving and pressing the fiber. She starts opening the small hole through which the butterflies come out. And inside the bud, dirt particles may appear that must be removed, while cleaning the coyoyo. Sometimes, she finds out the worm inside that did not manage to get out as a butterfly (Fig. 25 shows the inside of a coyoyo with dirt particles and Fig. 26 presents a coyoyo with the bug inside). Anyhow, she tries not to boil coyoyos with the bug inside giving time to the butterflies to fly. Approximately 4 or 5 months from gathering them, after spring and

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Fig. 25 Opening coyoyo. In the inside, some dirt left by the butterfly or bug

Fig. 26 Opening coyoyo with the bug inside

summer goes by, she cooks them. In these seasons, the butterflies manage to fly. After summer passes and having almost all coyoyos empty, she leaves them aside to make the process of obtaining the fiber, spinning, and weaving it. Soft dry buds are kneaded, one by one by hand, more precisely with the thumb, index, and annular fingers. Doña Pabla tries slowly to disassemble coyoyo, and as she goes on, she starts spreading the fiber and leaving aside the impurities or solid particles in the fleece. By removing the fleece, they are undone, and raw silk is obtained and ready for spinning. As previously mentioned, the shade of the fleece varies according to the plant from which it is fed, but also it can be influenced by climatic factors or sun exposure, among others. In Ancasti, the colors are almost always beige and brownish (Figs. 27 and 28 shows the process of cleaning the fleece and Fig. 29 shows the fleece ready for spinning).

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Fig. 27  Cleaning the fleece Fig. 28  Cleaning the fleece

Artisanal Spinning Process When Doña Pabla has the fiber ready, she starts preparing the thread. Doña Pabla is capable of spinning real thick threads by hand, and all the instruments she uses are made of wood and bones by Don Agüerito. The spinning is done with a traditional spindle; the artisans place the fleece as a bracelet on their wrist and start spinning. The thread obtained depends on the craftwork, the experience, and the hands of each craftswoman. At the same time, the tortero being used influences on the width of the thread; for example, the smaller it is, the thinner the thread.

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Fig. 29  The fleece is ready

Fig. 30  Twisting and making the thread

Doña Pabla mentioned that once she could not sleep thinking how she could afford thinner threads, to improve softness and quality of the fiber and final piece. It was then, when she started thinking and concluded that if she replaced her tortero for a smaller one, the thread will become thinner. So, in this part of the process, she gets the littlest tortero and starts to stretch and twist the thread, while she goes twisting the skein and curling the thread. This part of the process is part of her daily routine, anytime she is sitting, she is twisting her tortero and curling coyoyo’s silk (Fig. 30).

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The final thread Doña Pabla uses is composed by two equal strands; so, she always has more than one skein ready to work with. To continue, she gets two similar strands and starts curling them together, with a bigger tortero. She needs to curl both together, twisting them (Fig. 31). Afterward, in an artisanal winder, she tides the finished skein up. Sometimes, Don Agüerito helps her during this process that needs no special skills, but a little of practice (Fig. 32) (see in Fig. 33, the bigger tortero, the winder, and the final skein). Afterward, she takes the skein from the winder (Fig. 34), and with the final skein ready, she washes it by hand, with soap. She uses cold water and a little of shampoo, wash it well to soften and clean the final thread (Fig. 35). Finally, she leaves it hanging from a tree, to get dry (Figs. 36 and 37). It is important, to cover it from sunlight. After that, the thread is ready to start the creative process of weaving (Figs. 38 and 39).

Fig. 31  Twisting the final thread

Coyoyo Silk: A Potential Sustainable Luxury Fiber Fig. 32  Don Agüerito tiding up the skein

Fig. 33  Tortero, winder, and final skein

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Fig. 34  Taking the skein from the winder

Fig. 35  Washing the skein

Weaving Process The weaving process is the most artistic one; it is freestyle in comparison with the spinning process. It is the moment when, craftswomen play, and continuously discover new techniques. The best-known pieces are scarves or belts, made in creole loom. There are also some pieces made in macramé – elaborately patterned lacelike webbing made of hand-knotted cord – by artisans. It is important to highlight the precision and devotion of these artisans and remark that both during spinning and weaving processes, the personal trace of each craftswoman can be observed. Each final piece and creation is unique.

Coyoyo Silk: A Potential Sustainable Luxury Fiber Fig. 36  Drying the final thread

Fig. 37  Drying the final thread

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78 Fig. 38  Tiding the thread

Fig. 39  Final thread

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Fig. 40  The loom

For example, Fig. 40 shows Doña Pabla’s loom. At the moment this picture was taken she was working with wool, so the authors could not see coyoyo silk in the loom. However, she expressed that the process of weaving is really demanding for her, at her age. She remembered her self-weaving all day and she wants to transmit her passion to women in her neighborhood. As mentioned above, this is hard because they see the whole process very difficult and prefer other materials or quitting artisanal craftsmanship and countryside. The process of macramé is about cutting several equal-length threads (or not it depends on the piece they are about to create), and with one chord they set transversal the other ones, and start knotting one with another. For example, you can get two, three, four, or as many as you want and make a knot, and repeat. After making a line, you go back with the first knot and continue this process. There are different types of knots that give you different finished products. Doña Pabla presents this technique in a little piece (Figs. 41 and 42). Usually, she makes the piece on the loom, and to tide up the sides she uses macramé. When she has a final piece ready she irons it, combs it, and leaves it hanging until the next interested client gets there (Figs. 43, 44, 45, and 46). In Doña Pabla presents the whole process and the different stages of this wonderful technique and material (see Figs. 47 and 48).

80 Fig. 41 Macramé

Fig. 42 Macramé

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Coyoyo Silk: A Potential Sustainable Luxury Fiber Fig. 43  Final piece

Fig. 44  Final piece

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82 Fig. 45  Combing and Finishing the piece

Fig. 46  Final piece

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Fig. 47  Doña Pabla presents the materials and the process

An Undiscovered Luxury at Risk After analyzing coyoyo silk through the light of sustainable luxury, it may be concluded that Ancasti Catamarca and Doña Pabla have a hidden treasure. It might be considered that it is missing the sustainable management vision which could empower artisans and enlighten this talent, bringing hope to local communities and production of a region that is being actually forgotten. Latin American countries like Peru have strong devotion for communities, artisans, and sustainability. They have a country benchmark to promote local artisanal goods globally. Peruvian crafts, Peruvian food, and Peruvian therapies are globally recognized and positioned in luxury sector. Argentina has the opportunity to show a traditional ancestral technique, but instead, it is being lost. And it will disappear if there is no support from cultural policies, nongovernmental organizations, and the commitment of individuals with devotion to promote cultural heritage. Luxury as a territory seems unlimited. This is why luxury has obligations, to contribute to the sustainable development of the planet. Luxury brands should develop and train and retrain artisans of underdeveloped countries in Africa, Asia, and elsewhere, where so many talents have not emerged. [16, p. 417]

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Fig. 48  Materials and process

In the first place, luxury implies excellence and high quality, and Doña Pabla and coyoyo silk ensure these attributes. The oldest, and most recognized, woman, at least known is in Ancasti, Catamarca, Argentina. At the same time, this is the only place where coyoyo silk is obtained and processed. Second, if we focus on ancestral culture, and the knowledge that transcends and passes through generations, coyoyo silk implies a wonderful technique and ancestral wealth. It already has the potential story that luxury must communicate and preserve. Moreover, craftsmanship and the natural landscape are evident in this product. Scarcity, iniquity, and exclusivity are ensured by this process and material. The beauty and aesthetics of the artisanal craftsman are unique. The handmade object is marked by its solid oneness in the world, and is a sign of consumer distinction in a globalized marketplace increasingly marked by a lack of product differentiation: the handmade appeals to people in search of the unique. [12, p. 69]

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5  Conclusions Sustainable luxury is about products that “offer a connection to the maker through the skill and learning apparent in their construction and they demonstrate time spent in a way in which other objects cannot” [18, p. 80]. In Ancastí, Doña Pabla and coyoyo silk taught us about time, honesty, and simple life. She opened up her heart and made us witnesses of coyoyo silk and the ancestral knowledge behind. As the research exposes, there are difficulties that set coyoyo silk at risk. The process is very different from the one of mulberry silk, and in order to maintain this virgin and noble material, the process should be as pure and original as it is p­ resented in this chapter. However, feasibility of coyoyo silk depends on the vision, particularly the business and social vision - of an individual, a group of individuals, or even government decision to invest in this area and discover this fiber - that could transform this unique technique in a source of work, access, and social integration. Revaluing this fiber, and teaching Doña Pablas technique to other neighboors, organizing for example a cooperative, might be part of the solution to local poverty, lack of resources, loss of cultures and diversity. The artisanal work is hard and communities try to work easy fibers such as wool, so, people need to see the potential of continuing with this cultural heritage. It is a wild process which does not require a great inversion on technology, but it requires people wanting to learn and produce, and investors who believe and support projects of this nature. The outcome of a social enterprise on coyoyo silk could be really significative and transformative. At the same time, the possibility to afford an ecological study of the bug and the variety of plants that they eat today in order to recreate a positive environment for this silk should be considered. As it should be maintained as natural as possible, time is obviously basic for processing this fiber and make it incomparable with mulberry silk. Through a sustainable vision, coyoyo silk could become a sustainable luxury benchmark of the country. Somehow, innovation and the art of telling stories are missing. Doña Pabla and artisans in Ancastí have the story to tell but lack the way and means to communicate it. At the same time, innovation and design could be applied in the final product, bringing new possibilities and expanding artisan’s knowhow. The suggested process of adaptation of the product should be very respectful, trying to meet the balance between ancestral craftsmanship and global luxury market. “When innovation is focused on the human capital of the company, each individual is placed at the center of every decision, due to his relevance in terms of knowledge, experiences and skills useful for innovation strategy” [8, p. 63]. Introducing product innovation and a value proposition strategy of sustainable branding and communication, coyoyo silk has the potential to become a strong sustainable luxury fiber. Sustainable vision is needed to preserve this ancestral knowledge in order to revalue cultural traditions, empower communities, and enrich the sustainable luxury textile fibers. Coyoyo silk could be considered as a sustainable luxury fiber from Catamarca, empowering people, enlightening their culture, preserving and promoting traditions, and enriching cultural heritage.

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Bibliography 1. Corcuera R (2000) Ponchos de América. De los Andes a las pampas. Fundación CEPPA Ediciones, Buenos Aires 2. Corcuera (2006) Mujeres de seda y tierra. Editorial Argentina, Buenos Aires 3. Erhenfeld JR (2013) Flourishing, a frank conversation about sustainability. Standford University Press, Stanford 4. Fletcher K (2008) Sustainable fashion and textiles, design journeys. Eathscan, London/New York 5. Gardetti MA (2011) Sustainable luxury in Latin America. In: Conference delivered at the seminar sustainable luxury & design within the framework of IE, Instituto de la Empresa, Business School MBA, Madrid, Spain 6. Gardetti MA, Rahman S (2016) Sustainable luxury fashion: a vehicle for salvaging and revaluing indigenous culture. In: Gardetti MA, Muthu SS (eds) Ethnic fashion. Springer, Hong Kong 7. Gardetti MA, Torres AL (2015) Introduction. In: Sustainable luxury, managing social and environmental performance in iconic brands. Greenleaf Publishing Ltd, Sheffield 8. Giacosa E (2014) Innovation in luxury fashion family business, processes and products innovation as a means of growth. Palgrave Pivot, New York 9. Kapferer JN, Bastein V (2009) The luxury strategy: break the rules of marketing to build luxury brands. Kogan Page, London 10. Littrell MA, Dickson MA (1999) Social responsibility in the global market, fair trade of cultural products. SAGE Publication Inc, Thousand Oaks 11. Littrell MA, Dickson MA (2010) Artisans and fair trade, crafting development. Kumarian Press, Sterling 12. Luckman S (2015) Craft and the creative economy. Palgrave Macmillan, Melbourne 13. Meléndez M (2005) Visualizing difference: the rhetoric of clothing in colonial Spanish America. In: The Latin American fashion reader. Berg, New York 14. Muratovski G (2015) Sustainable consumption, luxury branding as a catalyst for social change. In: Gardetti MA, Torres AL (eds) Sustainable luxury, managing social and environmental performance in iconic brands. Greenleaf Publishing Ltd, Sheffield 15. Root RA (2005) The Latin American fashion reader. Berg, New York 16. Som A, Blanckaert C (2015) The road to luxury, the evolution, markets, and strategies of luxury brand management. Wiley, Singapore 17. Thomas D (2008) Deluxe, how luxury lost its luster? Penguin, London 18. Turney J (2009) The culture of knitting. Berg, Oxford/New York 19. Turunen LLM (2018) Interpretations of luxury exploring the consumer perspective. Palgrave Macmillan, London

Hemp Fiber as a Sustainable Raw Material Source for Textile Industry: Can We Use Its Potential for More Eco-Friendly Production? Görkem Gedik and Ozan Avinc

Abstract  Sustainable production defines an environmental friendly production that we produce without changing the balance of the nature. Processes and the utilized materials should be renewable, and our whole production should be harmless so that nature can recover itself in an indigenous way. All natural fibers are biodegradable and sustainable, and consequently, they are commonly called as biofibers. Providing a sustainable production chain for textile processes requires individual attention for each input in the first place. One of the most important parts of these inputs is raw material selection and therefore fiber supply. Right at this point, hemp fiber step forwards and shines out with its huge sustainable production potential for textile industry. In this chapter, sustainable and biodegradable hemp fiber, which is an alternative to cotton and petroleum-based synthetic fibers, for textile raw material sourcing is reviewed in detail. The parameters that make this fiber sustainable are also investigated. Present common and special uses and possible future innovative alternatives of hemp fibers for technical textiles production are also stated. Mainly, composite material production with this sustainable fiber is reviewed for a replacement of nonsustainable synthetic competitors. When sustainable composite materials are produced not only ecofriendly textile production is carried out but also other materials can be produced with an ecofriendly path leading to more sustainable world. Keywords  Hemp · Hemp fiber · Sustainable · Sustainability · Hemp composites · Hemp textiles

G. Gedik · O. Avinc (*) Textile Engineering Department, Pamukkale University, Denizli, Turkey e-mail: [email protected] © Springer Nature Switzerland AG 2020 S. S. Muthu, M. A. Gardetti (eds.), Sustainability in the Textile and Apparel Industries, Sustainable Textiles: Production, Processing, Manufacturing & Chemistry, https://doi.org/10.1007/978-3-030-38541-5_4

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1  Introduction Besides the recent technological developments and the blessings of the modern world, we are the same human beings like our ancestors who lived 10,000 years ago. However, there is a small difference between us and them: they (our ancestors) fought against the nature to survive, but now we are fighting to save the nature so our planet can survive future generations. Unfortunately, we are consuming our limited sources irresponsibly especially in the last century. We built our modern world on nonsustainable petrol industries, and consequently, we pollute air, water, and soil. World population rises at an incredible velocity, and feeding and clothing of every individual with conventional production methods are not sufficient. Synthetic fiber research accelerated during the mid-1900s, accompanied by the petroleum-depended textile industry. On the other hand, researches focused on improving agricultural yield including cotton plant. Pesticide, herbicide, and man-­ made fertilizer usage becomes unfortunately our reliable guns to shot the nature. We forgot that we had been a part of the nature which we tried to restrain. Now, sustainable production in every branch of industry might be a solution for a better tomorrow. Sustainable production defines an environmental friendly production that we produce without changing the balance of the nature. Renewable energy sources are used, and overloading of the nature’s production capacity is unacceptable. Processes and the utilized materials should be renewable, and our whole production should be harmless so that nature can recover itself in an indigenous way. On the other hand, we should supply the demanded products on time with desired quality respecting the nature. One of the most criticized industries is textile industry, due to the toxic chemical usage, high water consumption, and nonsustainable raw material consumption. The most consumed natural fiber in the world is cotton, and one-third of the agricultural chemicals used is consumed for cotton plant cultivation. Petroleum is mostly involved in polyester production, which is world’s most produced and consumed fiber. Though the current circumstances for textile industry are pessimistic, the situation can be eluded with sustainable fiber alternative search approach. Biodegradation is the decomposition of a material due to the biological activity of microorganisms such as bacteria, fungi, and other biological agents. Biodegradable fibers could be broken down by microorganisms. All natural fibers are biodegradable and sustainable, and hence, they are commonly called as biofibers. However, natural fiber manufacturing is not enough to meet the biodegradable and sustainable fiber supplies of the textile sector. Therefore, enhancing the diversity of biodegradable synthetic fibers manufactured from renewable sources has become one of the primary goals of researchers to meet this demand. The following issues interrupt a sustainable production chain for textile industry: inappropriate and excessive use of water; inattentive use of pesticides, herbicides, and other agricultural chemicals; toxic chemical load during processes; consuming nonrenewable sources; wrong waste management; and incorrect transportation ­policies [1].

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Textile industry is an interpenetrating network of various industry branches such as chemistry, agriculture, mechanics, and so on. Only if all these processes work in harmony in terms of sustainability, we would obtain a sustainable production. From this perspective, providing a sustainable production chain for textile processes requires individual attention for each input in the first place. The most important inputs are raw material selection and, therefore, fiber supply. Some of the natural fibers, regenerated fibers, and man-made fibers have unique characteristics and they have potential for sustainable production. About one-fourth of the total insecticide and one-tenth of the total pesticide production of the world are consumed for cotton cultivation. Irrigation is an additional ecological problem since 7000–29,000 liters of water is consumed to obtain 1 kg of cotton fiber [1, 2]. These parameters make cotton fiber the leader of the agrochemical and water consumption when compared with other plants cultivated in the world [3]. The toxicity of a pesticide is its capacity to result in injury or illness. Pesticides may exhibit toxic effects by absorption through ingestion and inhalation and through the skin. Pesticide exposure is possible at various stages of production including manufacture, packaging and distribution, use, storage, and disposal [4]. Especially, pesticides that are used for cotton cultivation around the world such as parathion, cypermethrin, methyl-o-dematon, methamidophos, monocrothophos, thiofanex, and triazophos are listed in extremely hazardous class by World Health Organization(WHO) [5]. Other additional sustainability problems related to conventional cotton production are the following: land degradation due to salination and erosion relevant to irrigation, excessive use and eutrophication of surface water, degradation of natural habitat, contamination of wildlife (fish, mammals, birds, and so on) with pesticides, and negative effects to human health by direct or indirect pathways related to agrochemicals [4, 6]. Polyester is the most consumed synthetic fiber in the world, and the main problem with synthetic fibers is their nonsustainable nature. Oil consumption dependent on the  synthetic fiber production has significantly raised.  Their discovery results in the translocation of carbon from ground to air leading to an increase on the emissions of other hazardous materials such as sulfur, nitrogen oxides, or hydrocarbons. Fossil fuels also have the major guilt of greenhouse gases emissions which causes the global warming. In addition to sustainability issues, synthetic fibers can cause serious disposal problems [7]. The study of Li et al. revealed that the biodegradability of polyester fabrics was very bad that tested polyester fabric had been intact after biodegradability test under laboratory conditions and the compost environment [8]. On the other hand, right at this point, hemp fiber step forwards and shines out with its huge sustainable production potential for textile industry. In this chapter, sustainable and biodegradable hemp fiber, which is an alternative to cotton and petroleum-based synthetic fibers, for textile raw material sourcing is reviewed in detail. The sustainability issues of hemp plant cultivation are discussed. The effects of irrigation, pesticide, and fertilizer usage to the environment are mentioned. Retting processes are compared for eco-friendly production. New efforts on retting processes for higher quality fiber production and sustainable processing are intro-

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duced. The parameters that make this fiber sustainable are investigated. The present common and special uses and possible future innovative alternatives of hemp fibers for technical textile production are stated. Conventional textile applications and composite and construction material production with this sustainable fiber is reviewed for a replacement of nonsustainable natural and synthetic competitors.

2  General Properties of Hemp Plant and Hemp Fiber Hemp belongs to Cannabaceae family and is an annual herbaceous plant which is diploid and dioecious (male and female plants) [9, 10]. Among divergent species of hemp plant, Cannabis sativa is the one which is used for industrial applications, including fiber production. On the other hand, Cannabis indica cultivation is banned all over the world due to the distinct antidrug laws since Cannabis indica is utilized for marijuana production [11, 12]. The first signs of hemp agriculture and its use have been traced to 8500 years ago. Hemp spread all over the world from its origin Central Asia, thanks to its adaptability to various climate conditions and soil structure. Hemp cultivation commenced in Europe around the 1500s and then hemp was migrated to New World by the colonists. Back then, hemp was a crucial industrial plant as a fiber source. Maritime countries used hemp fiber for canvas and cordage production for naval applications. Hemp production decreased in the United States due to new cotton production developments and declined demand of naval industry associated with the replacement of sailing ships with modern ships that were equipped with petrol and steam motors. In 1937, the United States restricted hemp agriculture with Marijuana Tax Act justifying the abuse of hemp as a drug [10]. Tetrahydrocannabinol (THC) is the psychoactive compound present in marijuana. In Europe, hemp cultivars having less than 0.2% THC are legally allowed for cultivation. On the other hand, marijuana varieties may contain 1–20% or higher THC in the dry mass. Many countries fund research dealing with low THC-­ containing hemp varieties along with high fiber yield and quality, high seed quality, and so on [10]. Registered hemp cultivar number rose to 51 (2013) from 12 (1995) in almost 20 years [13]. Though fiber hemp is more robust and marijuana often has a bushy appearance, these strains look identical and may cause confusion; hence, lawmakers have been defending the restriction of hemp cultivation [5]. As a result of the aforementioned breeding studies carried out by various countries, the yield of hemp dramatically increased after 1990. China led the hemp production with over 3000 tones mean between 2000 and 2017 [14, 15]. However, the cultivation area and production amounts still remain in low levels than expected. In most Western countries, the cultivation of hemp was disregarded as a result of competition with other fibers such as cotton and synthetics, high labor costs, and narcotic abuse of cannabis. Even though hemp has a huge potential for sustainable, eco-friendly, and economically feasible production as a multipurpose crop, there are some bottlenecks on cultivation, processing, and marketing that have to be beaten to

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use hemp plant with its full potential. Hemp fiber production consists of different stages, and these stages should be investigated with regard to sustainability and environmental protection.

Fiber Hemp Cultivation Hemp is a multipurpose, low input crop which is cultivated for its fibers, seeds, shieves, and hurds. Hemp needs no care between sowing and harvesting. Herbicide requirement is minimum due to the diligent growth of hemp plant which suppresses the growth of the weeds. Irrigation is rarely needed since the sophisticated root system of the plant allows it to extract water deep in the soil up to 140 cm [16–20]. Harvested and dried hemp stems are seen on Fig. 1. Hemp plant has primary and secondary fibers. Primary fibers are used for textile production. The count of the primary fibers does not change during the growing period of the plant; however, the fiber length increases with the increasing distance between internodes [16]. When the internode growing stops, secondary growing starts and the proportion of the primary fibers decreases. Therefore, the elongation period of the internodes should be well monitored [16]. A single fiber matures from outside to inside developing layers of secondary wall. Mature stem cells have small lumens and thick walls. Maturation of the fibers vary with the harvest time, so harvest time should be chosen according to required fiber quality [16]. If the purpose of the cultivation is fiber production, crops are harvested just after the end of flowering [18].

Fig. 1  Harvested and dried hemp stems from Turkey

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Due to the high interest on hemp plant lately, scientists have focused on the development of new hemp cultivars according to the purpose of the cultivation. Genotype and environment strongly affect the fiber and the seed quality. The longer the vegetative phase the higher the stem yield. Therefore, late flowering cultivars are preferred for fiber production. Also, a cultivar with high bast content is desirable for cellulose rich and low lignified long fibers [13]. The lately interest on hemp fiber has arisen from its superior sustainable production potential. However, hemp is a native plant of Central Asia, and just like every culture plant, hemp may need some extra care such as the fertilization, irrigation, or so on during its cultivation in different places around the world. Even though hemp is able to grow without any human intervention, the quality of the seeds or the fibers might not be of the desired quality. At this point, it is important to ensure an economically feasible but yet sustainable production by keeping the inputs at optimum levels. If the balance is broken, ecofriendly properties of hemp may overturn or low economic value products may be obtained which will serve no objective. Thus, the researchers focus on this issue and try to figure out optimum conditions for hemp production from field to final textile product. Though hemp plant is a very low input crop and is able to grow without irrigation and fertilization, human interference is needed to obtain high-quality fibers. Fertilizers and other input amounts stated in different studies are presented in Table  1. Ten tons of hemp crop in 1 hectare consumes 90  kg nitrogen, 25  kg ­phosphate (P2O5), 90 kg potash (K2O), 60 kg calcium, 10 kg magnesium, and 10 kg sulfur. These nutrients return to soil during retting operations in the field [19] as a pair of the sustainable production. According to the field experiments performed in the Netherlands, Italy, and Poland, 150–210 kg ha−1 N-fertilization resulted in the highest stem yields. On the other hand, the bast fiber content in the stem was reduced with increasing nitrogen due to the self-thinning phenomenon [21]. The average dry biomass yield depending on cultivar and conditions is 6000–11,000 kg.ha−1 with a maximum yield of 13,900 kg ha−1 [19]. Trunen and van der Werf [22] practiced the environmental impacts of hemp and flax yarn production on the field. According to their results, eutrophication (kg PO4-eq), climate change (kg CO2-eq), acidification (kg SO2-eq), and energy use (MJ) values were 3.04, 1350, 7.38, and 25,500, respectively, for conventional water retted hemp. These values were 3.02, 1810, 9.01, and 35,800, in the same order for bio-retted hemp [22]. In order to provide environmentally friendly production of hemp, reduction of eutrophication should be the first priority whereas reduction of climate change, acidification, and energy use in the second order [11]. Table 1  Inputs of some fiber plants [11, 22, 23] Inputs (kg. ha−1) N P K Pesticide Diesel

Hemp (France) [11] 75 38 113 0 65

Hemp (Central Europe) [22] 68 30 114 0 55

Flax [22] 40 30 46 2.6 57

Cotton (Turkey) [23] 218.3 70.7 50.8 2.02 274.7

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Hemp can be adapted to many types of soil unless the pH is under 5. Hemp plant can endure dry conditions thanks to its root system; however, the most convenient relative humidity range for hemp plant is 40–80% [18, 20]. Plant growth is disrupted in wetland and saturated soils. Also, crusting soils may restrain emergence of the sprouts [18, 20]. Cannabis likes short days; it generally blooms in autumn when the photoperiod drops below 12–13  hours/day. Ideal temperature for hemp is 21–27 °C during the day and 13–21 °C during the night [20].

Production of Hemp Fiber As mentioned earlier, hemp is a multipurpose crop and is cultivated for its fibers, seeds, hurds, and shieves for medicinal parts or so on. Of course, in textile industry we focus on the fibers. For fiber purpose, hemp is harvested just after the blooming season, since after this period, the fiber quality decreases [16]. Subsequent to harvesting, fibers should be extracted with proper methods. Unlike unicellular cellulose fiber cotton, hemp fiber is a multicellular, which means a crude hemp fiber consists of multiple cells concreted with each other with noncellulosic substances. The cell count may be reduced during processing or storing [24]. Crude fibers present in the stem are glued together with pectic gum. First, fibers should be separated by the elimination of pectic substances. The layers in the hemp stem are shown in Fig. 2. This process is managed by the

Fig. 2  SEM image of a hemp stem; c cambium, ep epidermis, fb fiber bundle, and p parenchyma [26]

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retting (sometimes termed as degumming) of hemp stems [24]. Pectin hydrolyzing enzymes, pectinases, such as polygalacturonases, pectin esterases, pectin lyasases, and pectate lyasases, involve in the retting step. Retting is a fermentation process which is driven by several microorganisms. These microorganisms are present on the plant or in the soil [25]. Hemp fiber is as an alternative for synthetic fibers; however, hemp fiber is expensive due to the various stages involved in the fiber extraction from hemp stem. The most important and energy intensive step is retting [27]. Retting is one of the most criticized steps of the hemp fiber production, since the retting step involves rotting of the woody parts of the stem by different procedures and effluents of these procedures may include high chemical or biological waste loads. There are several retting methods such as dew retting, cold water retting, warm water retting, chemical retting, steam retting, enzyme retting, bio retting, and mechanical retting. Also, the combination of these retting applications and controlled interventions are possible. Among these techniques, dew retting and water retting are considered as traditional retting methods. Additionally, frost retting applied to standing hemp stems in cold regions might be counted as a third traditional method [28]. For sure, there is no certain retting method to attain optimum results in the matter of time, fiber quality, environmental protection, and low cost [24]. However, advantages and d­ isadvantages of retting systems should be well understood to improve new techniques and achieve optimum results with sustainability and economic feasibility. Retting process has a strong influence on fiber quality. The fiber properties such as color, strength, uniformity, reproducibility, and so on mostly depend on retting operations. The hemp fibers exist in the bast layer of the stem. Epidermis, primary fiber cells (cortex layer), secondary cells, and parenchyma cells form together to constitute the bast layer of the hemp stem. Primary and secondary fiber cells are glued together with a pectin-based matrix called middle lamella. Retting operations target this pectinaceous layer to separate fibers by degrading parenchyma cells between fibers. After retting, fibers are able to be separated by mechanical processes [29]. Water Retting Water retting is an anaerobic process [25] predominantly driven by Clostridia species. Traditionally, hemp sheaves are soaked into tank filled with water and kept for up to 14 days. Naturally occurring organisms loosen the pectic substances in the middle lamellae which results in the separation of the fiber cells. When the optimum degree of retting has been achieved, the partly decomposed straw is ready for scutching step where the fibers are extracted from stem after drying. An hectare of hemp requires 1300–1350 h to grow; therefore, its cultivation should be handled by extended families who are capable to provide labor in harvesting, retting, and scutching in a traditional manner. The operations should be mechanized, and water retting process should be modified in terms of quality and sustainability [30].

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Di Candillo et al. [30] studied the effect of different water retting alternatives and the modification of water retting process. The retting operations were applied in open tank with pond water, covered tank (to raise the temperature) with pond water, open tank with well water and addition of C. felsineum microorganisms, and in open tank with well water without controlled microorganisms. The temperature of the covered tank was 4 °C higher (28 °C) than the uncovered tank. Retting was attained in 4 days in covered tank and in 6 days in uncovered tank. Pond water provided more effective retting than well water. Retting was done in 10 and 12 days in well water filled and bacteria introduced tank and in only well water filled tank, respectively [30]. Covering of the tank had a notable impact on retting time without any further energy consumption which is an important contribution to sustainable production chain. In the practice of Trunen and van der Werf [22, 31], retting pools were filled with the 28  °C mix of thermal water and cold water with a stem:water ratio of 1:14. Retting remained 5 days with 10% dry matter loss. Some parameters of the wetting liquor effluents are as follows: COD: 1827 mg/L, BOD: 932 mg/L, and pH: 7.5 [22, 31]. Utilizing the thermal water for retting operations is a brilliant idea which reduces energy need for heating. Fermentation caused pollution, and high labor costs and drying costs caused this method to be abandoned to dew retting. Dew Retting (Field Retting) In dew retting, hemp stems are laid in the field for a long period of time depending on the harvesting season [33]. Dew retting is an aerobic process, and pectin hydrolyzing enzymes, pectinases such as polygalacturonases, pectin esterases, pectin lyasases, and pectate lyasases involve in the retting step. Retting is a fermentation process which is driven by several microorganisms. These microorganisms are present on the plant or in the soil [25]. Ribeiro et al. detected Escherichia coli, Pantoea agglomerans, Pseudomonas rhizosphaerae, Rhodobacter sp., Pseudomonas fulva, Rhizobium hautlense, and Massilia Timonae bacteria along with Clodosporium and Cryptococcus fungi in the field retting environment of hemp. Same species were observed in various samples with different quantities [25]. Prolongation of the retting duration poses the risk of fiber damage due to the cellulolytic enzymes secreted by the microorganisms in the retting environment [25, 33]. The quality of the hemp fibers increases in the early stage of retting; however, rapid decrease is observed by extending the retting process [33]. Mazian et al. [33] performed a 9 week long retting study in summer season at the beginning of flowering growth and investigated the fiber properties week by week to understand the effect of retting duration on the quality of the hemp fibers. The mechanical properties of the extracted fibers changed as well as other properties such as cellulose content and color. Unretted fibers were green whereas the color of the fibers turned to gray at ninth week. They attained optimum results at fifth week [33]. Likewise, Liu et  al. [34] investigated the effect of field retting duration on early harvested

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(harvested at the beginning of flowering season, on July) and late harvested (after seed maturity, on September) hemp stem samples. They stated that 50 days of retting provided favorable tensile strength elongation and stiffness results compared with 70 days retting, for the early harvested samples. On the other hand, mechanical properties dramatically decreased after 7 days of retting for the late harvested samples. The hot and dry summer season prolonged the retting duration [33]. These results indicate the weather and exogenous factors dependence of the field retting technique. Thus, it is complicated to acquire assumed quality fibers for industrial applications. New controlled methods with specific microorganisms and enzymes should be adapted to retting for high-quality fiber production and reproducibility, thereof [35]. Different Approaches to Hemp Retting As mentioned above, traditional hemp producers prefer either water retting or dew (field) retting due to economic reasons and ease of application. However, field retting induces uncontrolled quality of fibers and water retting is not a very environmental-­friendly method and needs high filtration and labor costs. These circumstances pushed the researchers to modify present methods for better more convenient results. Bleuze et  al. [26] carried out hemp retting under controlled temperature and humidity conditions with simulated rain. They tracked CIELAB color properties and infrared absorbance of the stem surface for 42 days at 15 °C. Moreover, chemical composition and enzymatic activity were monitored. The results of this study were correlated with microorganism colonization, enzymatic activity, and disintegration on the plant tissues [26]. This study was an example for the efforts to monitoring the progression of the retting process for a standardized quality production. In other respects, studies were performed to carry out retting with selected enzymes and microorganisms for controlled retting operations. Di Candilo et al. [30] used Clostridium felsineum bacterial strains for controlled retting of hemp. They stated that the use of certain microorganisms at suitable temperatures would lead to a reduction of time, standardization of the process, and ensured product quality. Liu et al. [29] compared traditional field retting with controlled retting with Phlebia radiata Cel 26 and pure pectinase enzymes. As stated, Phlebia radiata Cel 26 is the most selective in pectin degradation and leads to high fiber strength. This microorganism releases less cellulase enzyme compared to its wild relatives leading to lower damage to the hemp cellulose. The lowest strength among the composites produced from retted hemp fiber samples belonged to the traditional retted samples. Controlled fungi retted sample’s strength was lower than enzymatic retted sample [29]. Enzymes could be expensive and unattainable for an exact time; therefore, controlled microorganism retting could always be considered as an alternative. Another prospect could be the combination of the techniques. Nyker et al. compounded enzyme treatment, dry heat application, and steam explosion with field

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retting and frost retting. The cellulose content rose to 78% with steam explosion application of enzyme treated hemp fibers [28]. Liu et al. [36] applied hydrothermal pretreatment prior to an endo-polygalacturanase and pectin lyase enzyme treatments. As stated, the hydrothermal pretreatment at 100 kPa and 121 °C prior to an enzymatic treatment resulted in highest ultimate tensile strength of 780 MPa, consequently high-quality composites. These studies aimed to overcome the disadvantages of field retting described earlier. However, it is hard to say that these methods including controlled microorganism application, pectinolytic enzyme treatment, controlled environment experiments, and combination of these methods have been widely adopted by the farmers in the commercial manner. Thus, the search for alternative retting process continues. One of the suggested degumming alternatives is cryogenic and mechanical treatment of the hemp fibers. Hemp stems were cooled to –80  °C with a cryogenic ­chamber and then kept at that temperature for 2 hours. In this process, micropores and microcracking appeared. Subsequent to the cryogenic treatment, hemp stems were fed into a decortication system where the woody parts of the stem were cleaned out. In the next step, fibers were mechanically cleaned. As a final step, fibers were steeped in 20 g/L NaOH solution at 50 °C for 1 hour and then rinsed with clean water. As stated, cellulose content increased to about 79% from 66% with lower tensile strength. Besides pectin, hemicellulose and lignin could be removed [37]. Cryogenic degumming has notable advantages since biological processes are eliminated and water consumption lowered. From this perspective, cryogenic application seems to be suitable for a standardized degumming process. However, energy consumption during freezing should be calculated carefully. Besides, the fiber quality must be evaluated intensively and characterization of the obtained fibers should be done before commercial use of this technique. Microwave energy opens an alternative road for degumming of hemp fibers. Water soaked hemp stems are subjected to microwave energy. Water acts as a solvent, and presoaking ensures an even distribution of the water inside the stems. Water aids effective retting by reducing the glass transition temperature of the components such as pectin, lignin, and hemicellulose. Following the microwave treatment, hemp stems were rinsed, dewatered, and dried to 8% moisture content. The optimum results were observed at 24  hours of soaking time, 2  W/g microwave energy, and 20 minutes microwave application [27]. Microwave energy is an effective way of intensive heating in a short period of time. By this way, energy and time could be saved. On the other hand, microwave energy can be applied to a limited size of samples at a time. This situation restricts its applicability in an industrial scale with today’s technology. Perhaps, water retting would be still in use if the pollution and fresh water scarcity problems were eliminated, since high-quality fiber extraction is possible with water retting. To overcome these problems, Zhang et al. [38] suggested seawater retting as an alternative to freshwater retting. Retting process were carried out in fresh seawater at 28 °C for 2 weeks. Seventy-nine percentage of cellulose component was detected for seawater retted hemp. The retting was attained by means of microorganisms (S. malthopilia and O. anthropi) introduced by hemp stem into the seawater.

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Steam explosion could be another alternative retting method. In an example application, Garcia-Jaldon et al. [39] impregnated semiretted and decorticated hemp bundles to 2% NaOH solution for 1 hour at room temperature. After alkali treatment, hemp bundles were steamed at 200 °C with 1.5 MPa pressure. High temperature softened the noncellulosic material and mechanical action of the steam carried out the separation. Electrolytic degumming is another interesting approach to hemp fiber degumming. The process is driven by redox reactions. On an example study, 0.01 and 0.1 M hydrochloric acid and sodium hydroxide were used as electrolytes, respectively. The best results were obtained at 0.1 M NaOH solution with 4.5 V, 48 hours waiting time at 20–25 °C. 8.5–10.3 tex fibers were produced by this method [7]. Even though, not very common for hemp fiber retting, chemical retting is an alternative among bast fiber retting systems such as flax, ramie, or kenaf retting. These methods include sodium hydroxide boiling with sodium sulfite, sodium bisulfite, or EDTA existence, boiling with sodium hydroxide subsequent to a hydrochloric acid treatment, and boiling in oxalic acid [32, 40–44].

Breaking Subsequent to retting process, hemp stalks are transferred to breaking operation. Sheaves are opened and stalks are fed into the vertical positioned breaking rollers. Breaking operation is carried out by the force applied by the smooth and ribbed breaking rollers. Smooth rollers split the stalk longitudinally and ribbed rollers break hurds to smaller pieces. Most of the crushed hurds are separated from the fiber before next application. The wastes of this process, hurds, are not thrown away, they are collected for further applications. Unretted hemp stalk can be treated in this step; the fiber yield is around 60%. In this case, the fibers obtained from unretted stalks are suitable for paper industry. Also, green stalks are processible, and fiber content is around 50–55% in green stalks. Fibers produced from green stalks are suitable for spinning. Anyway, the best results are obtained with previously retted stalks [45].

Scutching All hurds that remain from breaking step of the hemp fiber is removed by scutching process. Another contribution of scutching is opening and softening the fibers. In scutching, broken fibers are passed through a pair of bladed turbines which rotate in opposing directions, by a vertical belt. The turbines are operated in two pairs, whereby after passing the first pair of turbine blades, the fibers are reversed to pass through the second pair facing in the opposite direction. The main product of scutching is long

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hemp fiber (line fibers). As a by-product, short hemp fibers (tow fibers) are produced. These are lower quality fibers and utilized for coarse yarns or ropes [46].

Hackling Fibers have to be cut to a certain length (usually 60–70 cm) before hackling. Cutting is done in cutting machines by hand. Bad tips of the scutched fiber are also removed during cutting. Cutting machine actually tears the fibers instead of cutting. Subsequent to cutting, hemp fibers are processable in hackling frames. Hackling is the hemp processing analogue of combing process applied to cotton or wool fibers. Hemp fibers are held and drawn by pins on wooden plates. Hemp fibers leave hackling in the form of sliver [45].

Uses of Hemp Fiber for Textile Purposes Hemp fabric is too coarse in its traditional untreated form for apparel production. However, thanks to the improved techniques, lighter and softer hemp fabric production is possible today. Hemp fabric is very suitable for furnishing, upholstery, and draperies. Hemp fiber is also utilized for casual wear such as jeans and sportswear. Hemp fiber could be used in its 100% form in textile products or also could be blended with other fibers such as cotton, wool, or synthetics [47]. Hemp fabric is seen on Fig. 3. Fig. 3  100% hemp fabric

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3  Composite Applications of Hemp Fiber Composite material is a multiphase material which has at least two components bound together. Final properties of the composite material are divergent from its original components [48]. Textile composites are reinforced textile materials bonded with a matrix. The matrix component could be polymer, metal, or ceramic. Polymer matrix composites are more common since the fabrication temperature is low and production cost is low. Polymer matrix keeps reinforcing material or materials together and steady. Degradative properties are mostly determined by polymer matrix. Polymer types could be basically sort out as thermoset polymers and thermoplastic polymers. Thermoset polymers, which have dimensional and thermal stability, solvent-resistant, well-fatigue strength properties, constitute a highly stable cross-linked structure after curing. Polyesters, vinyl esters, epoxies, phenolics, and polyamides could be given as examples to thermoset polymers applied in composite production. On the other hand, thermoplastic polymers are able to be molded, melted, and remolded without losing their properties. Polyesters, polyamide-imide, polyetherimide, polyphenylene sulfide, and liquid crystal polymers are examples of this class. Thermoplastic composites are less brittle than thermosets and have high impact and damage resistance [48]. Matrix selection for natural fiber reinforced composites is restricted by the temperature. High temperatures above 200 °C may cause the degradation of natural fibers such as hemp; however, in some cases, it is possible to work short times at high temperatures with natural fibers [49]. The textile material here could be in fibers, yarns, filaments, or fabric forms. Growing interest on the textile reinforced composites is due to the cost-performance ratio of these materials, since the textile materials are produced in modern facilities at low costs in short periods. Therefore, textile-based composite materials provide low manufacture cost with easy applications [50, 51]. Fiber reinforced composites are preferred due to high strength, high aspect ratio (length to diameter), and high flexibility [51]. Hemp fiber products from fiber to composite are seen on Fig. 4. Extrusion, injection molding, structural foam molding, rotational molding, thermoforming, compression molding, open mold processing, and some other tech-

Fig. 4  Hemp fiber from stem to composite (From left to right: Hemp fibers on stem, hemp fiber, hemp yarn, hemp woven fabric and hemp fiber reinforced epoxy composite)

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niques can be used for composite manufacturing. These techniques also branch to various application methods in themselves [52]. Parameters like the technique of composite material construction, the polymer matrix chosen, the density of textile material, and the form of the textile material directly affect the final product specifications. It is hard to build a distinct correlation between production parameters and the end use of produced composite material. The composite material should be carefully engineered for industry needs including sustainability and environmentally friendly production, considering these parameters. Only if your raw material is sustainable, you can go on a sustainable production. As a sustainable and high strength fiber, hemp is a salient alternative for composite reinforcements. Composite industry opened a wide window upon us in the new century. We started to produce the lighter, cheaper, and even stronger substitutes of traditional materials such as solid metals or wooden objects. It would be a waste to use sustainable fiber sources such as hemp only in textile sector. By adapting sustainable fibers to composite reinforcement, we are able to produce various sustainable materials that we use in our daily life. Besides ordinary objects, high-tech applications such as in aerospace industry, automotive industry, naval industry, defense applications, sports tools, and so on are possible with hemp fiber composites. Natural fibers are unquestionably eco-friendlier than glass or carbon fiber composites. In brief, natural fiber composites are superior to glass fiber composites due to the following reasons: natural fibers have lower environmental impact; natural fiber composites contain more fiber for equivalent mechanic properties with those made of glass fibers that results in lower polymer consumption for matrix material; and natural fiber composites are lighter which reduces fuel consumption. Moreover, at the end of service life of a natural fiber composite, there are several recycling alternatives. If the matrix consists of a thermoplastic polymer, composite material can be grounded and reused in injection molding. As another alternative, natural fiber composites can be composted considering the components of the composite material. When no recycling options are available, burning of a composite for heat energy is final alternative. Burning a glass fiber causes artificial problems, the residue of burnt glass fiber requires additional treatments. On the other hand, natural fibers as well as polymer matrix are burnt without any residues but ashes [53]. The comparison of glass fiber and flax fiber are shown in Fig. 5. Biocomposite term expresses wide range of composite materials which are partly or completely constituted from low environmental resources: polymeric matrix, reinforcement textile material, or both could be derived from sustainable sources. Biocomposites have gained great interest due to important advantages compared to traditional composites such as, low environmental impact, cheapness, reduced machinery expenses, and low density. Consequently, composites with excellent weight-specific stiffness and strength are able to be produced. Green composites are a specific area of biocomposites. Matrix polymer is fully biodegradable in these materials. Although biodegradable polymers generally cost higher than others, cheap natural fiber reinforcement balances the total cost [54].

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Terrestrial ecotoxicity

Land use

Abiotic depletion 100.0 80.0 60.0 40.0 20.0 0.0 –20.0 –40.0 –60.0

Acidification

Eutrophication

Photochemical oxidation

Global warming (GWP100)

Ozone layer depletion (ODP)

Fresh water aquatic ecotox. Human toxicity Hackled flax fibres

Glass fibres

Fig. 5  Environmental impacts of glass fiber and flax fiber [53]

Hemp fibers cost 40% lower than glass fibers and also have good mechanical stress, high tenacity properties, and low elongation at break. Moreover, it was reported that hemp fibers exhibit high vibration damping capacity which makes them useful alternatives for production of sports objects and musical instruments [53, 56]. Cumulated energy demand of hemp fibers is 10% of those glass fibers [55]. With regard to sustainable biocomposites or green composites production, hemp fibers possess a significant potential. It is not surprising to see the intensive ­acceleration of hemp fiber reinforced composites studies not only for its eco-friendly properties but also for its aforementioned superior mechanical behaviors. Eco-friendly precedence of hemp fibers glitter, especially for composite applications, compared with glass fibers. For 1  kg hemp fiber mat, the environmental impacts are 0.0006  kg PO4 eq eutrophication potential, 0.531  kg CO2 eq global warming potential, 0.136 kg 1.4 DB eq human toxicity potential, 0.0571 kg 1.4 DB freshwater aquatic ecotoxicity potential, 6.88E-8 kg CFC11 eq ozone layer depletion potential, and 8.89 MJ eq cumulative energy demand. These values are quite higher for glass fiber than hemp fiber mat. The environmental impacts of 1 kg glass fiber are 0.04 kg PO4 eq eutrophication potential, 2.95 kg CO2 eq global warming potential, 9.52 kg 1.4 DB eq human toxicity potential, 0.684 kg 1.4 DB freshwater aquatic ecotoxicity potential, 2.49 E-7 kg CFC11 eq ozone layer depletion potential, and 51.3 MJ eq cumulative energy demand [57]. Selection of proper hemp fiber and suitable chemical or mechanical preparation of the selected fibers to composite production is an important step to attain high-­quality hemp fiber reinforced composite production. Musio et al. [58] investigated the effect of the selection of the fiber type to the hemp/epoxy composite properties. They stated that strength at breaking point of hemp/epoxy composites is strongly affected by the harvest time which determines fiber maturity. Also, long hemp fiber bundles exhibiting similar

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properties to flax fibers are suitable for high performance composite applications. In this case, yellow hemp varieties that have high decortication yield step forward for composite applications [58]. Pretreatment of hemp fibers is another significant factor that affects the composite quality. Alkalization is mostly applied chemical pretreatment for preparing the hemp fibers for composite production. Noncellulosic impurities such as lignin, hemicellulose, and waxes in hemp fibers are removed with alkali treatment. Surface roughness increases and covered hydroxyl groups emerge. As a result, higher interfacial adhesion with coupling agents occurs leading to  the improvement of mechanical properties [54, 59]. Various approaches are available in the literature on the pretreatment of natural fibers for composite applications [60–63]. Hybrid composite applications are another solution when the mechanical properties of hemp reinforced composites are not adequate. Natural fiber composites could be modified for technical applications such as for automotive parts through hybridization with small amounts of synthetic fibers. Panthapulakkal and Sain [64] produced 40% fiber (hemp and glass fiber) reinforced PP composites. Fifteen percent glass fiber reinforcement provided 101 MPa flexural strength to hemp/glass fiber composites. Besides, impact strength of hybrid composites exhibited notable improvement by 34%.

Green Composites from Hemp Fibers As mentioned, eco-friendly green composites consist of sustainable matrix and sustainable reinforcement material. We started to see biocomposites especially in automotive applications due to the lightweight material application need [65]. Mohanty et al. [65] fabricated 30% hemp fiber reinforced composite material that has cellulose acetate matrix. They used powder impregnation and extrusion followed by injection molding methods. Hemp fiber reinforced cellulose acetate composite exhibited 78.3  MPa flexural strength and 5.6  GPa modulus of elasticity, and its polypropylene counterpart with the same hemp fiber ratio exhibited 55.3 MPa and 3.7 GPa flexural strength and modulus of elasticity, respectively. In the study of Sawpan et  al. [66] short and long hemp fiber reinforced PLA composites were produced. Young’s modulus and impact strength of short fiber reinforced composites enhanced with increased fiber content up to 30%. They also stated that alkali and silane treatments modified tensile and impact properties by virtue of increased adhesion and matrix crystallinity. Thirty percent alkali treated fiber reinforcement gave the best results with 75.5 MPa tensile strength. Thirty-five percent long alkali treated hemp fiber reinforced PLA composite exhibited 85.4 MPa tensile strength and 7.4 j/m2 impact strength. Hu and Lim [67] also investigated the effect of volume fractions and the alkali treatment of the hemp fibers on the properties of green hemp fiber/PLA composites. In parallel with the findings of Sawpan et al. [66], best results were attained by 40% alkali treated fiber reinforcement. That specimen exhibited 54.6  MPa tensile strength, 8.5  GPa elastic modulus, and 112.7 GPa impact strength. The composite material had low density (up to 1.25 g/

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cm3) [67]. Another work on environmentally friendly composites was performed by Islam et al. [68] who investigated short and long hemp fiber reinforced PLA composites produced by injection molding. They stated that the best results have been attained with 30% fiber reinforcement. Also, alkali treatment improved interfacial bonding between fiber and polymer matrix leading to improved mechanical properties. The best results were attained with 30% long fiber reinforcement by film stacking technique (tensile strength of 82.9 MPa). Mazzanti et al. investigated the effect of hemp fiber morphology on the composite structure. They introduced alkali treated and untreated short hemp fibers to PLA polymer matrix and figured out that fiber quality significantly affects the composite mechanism; alkali treated fiber filled composites had higher tensile values [54]. Despite the fact that PLA predominates hemp reinforced green composite studies, other green polymers also applied hemp composites as well. Sarasini et al. [69] utilized hemp and sisal fibers for poly(ɛ-caprolactone) (PCL) composites for orthotic purposes. They carried out injection molding with the addition of 10–30% fiber. They attained 29.5 MPa tensile strength with 30% hemp fiber reinforcement. Thermoplastic starch (TPS) is another alternative to synthetic and biopolymers. TPS is generally used for goods that do not require long-term use and do not expose high mechanical loads. Girones et al. [70] observed for TPS/hemp composites that homogeneity and distribution of the fibers in the matrix have more significant influence than intrinsic mechanical characteristic of hemp fiber. Li et al. [71] observed 1500% increase on tensile strength of the 25% hemp fiber reinforced organoclay filled poly(butylene succinate) PBS compared with neat PBS. They applied pultrusion process for composite production.

4  Utilization of Hemp in Construction Materials Fighting against climate change is not only the concern of textile engineering but also the first priority of several United Nation organizations. Sustainability and energy consumption of built environment issues were debated intensely in UN Habitat III Conference in 2016. It is expected that, the urge for green buildings will increase markedly. The definition of a green building is “a building that, in its design, construction or operation, reduces or eliminates negative impacts, and can create positive impacts, on our climate and natural environment.” This definition comprises both energy saving architecture and ecofriendly construction materials. Therefore, the increased search of scientists for biomass-based production for construction materials continues [72]. Generally, hemp shivs/hurds which are the waste of hemp fiber extraction are utilized for hemp concrete production. Hemp concretes (hempcrete) have different characteristics from conventional building materials such as bricks and cement blocks. The porous structure of hemp shivs brings in several advantages. Besides its ecological benefits, hemp concrete offers good thermal and acoustic insulation, lightweight, low density, and good moisture buffer capacity [72–74]. Hemp con-

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crete is both environmentally and technically efficient. It stores CO2 which has been captured by the plant biomass and utilizes it to a construction material [75]. Hempcrete is generally produced by the mixing lime and hemp shivs in proper ratios. The main disadvantage of the hempcrete is its poor mechanical properties. Thus, new studies focus on the improvement of mechanical behaviors of hempcrete to overcome this problem [76]. In load bearing, hemp concrete materials’ more aggregate or binder addition aids to increase mechanical strength [77]. Baduge et al. investigated the performance of alkali activated cenosphere binder addition to carbon-­negative nonload bearing hempcrete applications. They stated that cenosphere binder added sample exhibited similar compressive strength result with those of cement or lime binder. Authors stated that, alkali activated cenosphere binder could be a sustainable alternative to conventional binders [78]. Another alternative for hemp concrete binders were presented by Sinka et al. They applied magnesium binders alternatively to conventional lime-based binders. Concrete samples with magnesium binders were two times stronger with similar density and thermal properties. Magnesium phosphate cement resulted in worse environmental impact among other samples; however, magnesium oxychloride cement exhibited negative carbon dioxide with –37 kg CO2/m3 [79]. Grubesa et al. investigated the fire resistance of hemp concrete. Hemp fibers were partly disintegrated when heated which provides reduced crack propagation at elevated temperatures and results in fire resistance [80].

5  Conclusion We consume world’s sources in a rapid way. Global problems such as environmental pollution and climate change have knocked our door in the twenty-first century. One of the solutions is sustainable production. In textile industry, not only profit should be expected but also sustainable production must be the top priority. A sustainable production starts with sustainable raw material, and hemp fiber stands out and shines out with its huge sustainable production potential for textile industry. The word “potential” should be underlined with thick lines in here. Like every culture plant, cannabis do also need human intervention for an economically feasible production. The important point here, with regard to sustainable production, is the size of this intervention. Fertilizer and irrigation amounts and pesticide or herbicide requirements should be carefully selected so that sustainable production chain should not be damaged. One of the most criticized processes of bast fiber production is retting. The effluents of retting, especially water retting effluents, are heavy in biological waste. More ecological ways have to be chosen for sustainable production. Studies on hemp retting processes continue. We are able to produce the lighter, cheaper, and even stronger substitutes of traditional materials such as solid metals or wooden objects thanks to the development of composite technology. By adapting sustainable fibers to composite reinforcement, we are able to produce various sustainable materials that we use in our daily life. Besides the ordinary objects, the

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creation of high-tech applications such as in aerospace industry, automotive industry, naval industry, defense applications, sports tools, and so on is now possible with the utilization of hemp fiber composites. Especially, combining hemp with biodegradable polymers resulted in completely biodegradable green composite production leading to sustainable future.

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Sustainable Antifungal and Antibacterial Textiles Using Natural Resources Fatma Filiz Yıldırım, Ozan Avinc, Arzu Yavas, and Gökcin Sevgisunar

Abstract  The structure and use of textile products can provide necessary conditions for microorganism, which can easily live in many environments leading to proliferation. Bacteria and fungi are the most important microorganisms for textile industry. Body temperature is an important factor for the growth of fungi and bacteria in the body, but also the amount of sweat released from the sweat glands and the chemical content of the sweat are also important factors. These media conditions pave the way for easier growth of bacteria, especially in cellulose-based textile materials. While fungus causes staining and biodegradation on the textile material, bacteria also can result in undesirable bad odors. These organisms can cause color change, bad odors, and staining as well as lower the strength of textile products. In order to prevent these negative effects, antimicrobial property can be imparted to textile products through different methods. Although antimicrobial chemicals can provide protection benefits to textiles, chemical usage during textile production can cause potential problems to environment. Therefore, various sustainable alternatives to chemical usage were investigated to obtain antimicrobial effects on textiles. Prevention of microbial attack on textile material has become increasingly important for both consumers and textile manufacturers as well as for the textile material itself. By giving antimicrobial properties to textile products, negative effects caused by microorganisms can be prevented or eliminated. Antimicrobial agents prevent the development of fungi and/or bacteria. The majority of antimicrobial agents exhibit potent activity against both bacteria and fungi, but the number of substances that equally affect all microorganisms is quite small. Antimicrobial agents are used to eliminate or inhibit microorganisms by destroying the cell wall, inhibiting cell wall synthesis, inhibiting enzyme activity, or inhibiting protein and nucleic acid synthesis. It is more common that antimicrobial effect is achieved through antimicrobial finishing. Many chemical antimicrobial agents such as commercial triclosan, silver, polyhexamethylene biguanide-PHMB, F. F. Yıldırım Research and Development Centre, Ozanteks Textile Company, Denizli, Turkey O. Avinc · A. Yavas (*) · G. Sevgisunar Textile Engineering Department, Engineering Faculty, Pamukkale University, Denizli, Turkey e-mail: [email protected] © Springer Nature Switzerland AG 2020 S. S. Muthu, M. A. Gardetti (eds.), Sustainability in the Textile and Apparel Industries, Sustainable Textiles: Production, Processing, Manufacturing & Chemistry, https://doi.org/10.1007/978-3-030-38541-5_5

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and quaternary ammonium compounds are generally used in finishing processes. Besides, chitosan, N-halamine, and peroxyacid can also be used as noncommercial antimicrobial agents. However, antimicrobial agents, to be used in textile products, should not threaten human health. Moreover, obtained antimicrobial effects should be stable to repeated washing cycles and ironing conditions. These antimicrobial agents should be resistant to caring conditions and do not directly or indirectly create toxic effects on the environment and consumers. For these reasons, to provide antimicrobial effect to textile surfaces, several natural alternatives are investigated as an alternative for chemicals. For this reason, biological active components of plants have been utilized for imparting antimicrobial activity to textile materials. Several studies show the obtained antimicrobial effects on textile products that were imparted by ecologic, antiallergic, harmless to human and environment, sustainable, renewable, and biodegradable substances such as natural dyes and other natural substances. It is important to point out that the usage of sustainable natural resources in textile processing will add immensely to the efforts for protecting our planet for future generations. This chapter provides information in detail about antimicrobial activity (antifungal and antibacterial activities) on textile products imparted by natural dyes and natural resources and their application methods to textile materials. First, several plant extracts such as acacia, pomegranate, gallnut, neem tree, aloe vera, turmeric, walnut, barberry, basil, rhubarb, ratanjoti, gromwell, peony, Arnebia nobilis, ashoka, and Madhuca indica that impart antimicrobiality to textile fabrics and their application types to textile materials are discussed, and then animal extracts such as chitosan that provide antimicrobial effects to textile materials and their related applications are reviewed. Keywords  Antifungal textiles · Antibacterial textiles · Sustainable · Renewable · Biodegradable · Turmeric · Sourcing

1  Introduction Microorganisms can be found on surfaces such as body, air, and soil [1, 2]. Textile products have suitable temperature, humidity, and nutrients for microorganisms to live and grow. This may cause the textile product to damage itself and may harm the consumer [1–3]. Bacteria and fungi are the most important microorganisms which may be related to the textile industry [1]. If simple conditions such as moisture, oxygen, food, and temperature are present, bacteria and fungi that grow and multiply in natural fibers can produce an unpleasant odor, skin infection, product degradation, staining, allergic reactions, and other related ailments [2, 4–15]. Preventing microbial attacks on textile material is becoming increasingly important for not only the textile material but also both consumers and textile manufacturers [16, 17]. By providing antimicrobial properties to textile products, it is possible to reduce or eliminate the negative effects caused by these microorganisms (Fig. 1) [2–15]. The majority of antimicrobial agents have strong activity against both bacteria and fungi,

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Fig. 1 Antimicrobial fabrics [30–33]

but the number of antimicrobial agents acting uniformly on all microorganisms is quite low [18]. Antimicrobials based on their antimicrobial activity are classified into two types: the first (controlled release mechanism) consists of molecules that are released slowly through the fiber or from the reserve on the surface of the fabric, and the second consists of molecules that chemically bind to the fiber surface. The second type of antimicrobials can only control microbes on the surface of the fabric and do not affect the surrounding microbes. The adequacy of antimicrobial finishing processes can range from inhibiting cell production, blocking enzymes, interacting with the cell membrane to destroy the cell wall, and internally poisoning the cell [19]. Antimicrobial substances used in textile products should not threaten human health and directly cause toxic effects on consumers and environmental damage. Besides these requirements, textile products should be durable to washing and ironing [1]. For these reasons, several natural alternatives are explored to impart antimicrobial properties to textile surfaces instead of chemicals; recently, biologically active components of plants have also been utilized for antimicrobial activity on textile products [20]. In fact, the use of antibacterial agents on fabrics dates back to ancient times. For example, fabrics, formerly known as Pomcha, dyed with turmeric were presented as scarves or veils to young mothers who had just given birth in Rajasthan. Turmeric is believed to impart antiseptic properties to fabrics, and so the newborn child and his mother were wrapped with these fabrics to protect them from infections [21]. Antimicrobial properties can be imparted to the fabrics with the help of natural dyes (Fig. 1). Novel methods such as plasma application, enzymatic treatment, cationization, microcapsulation, and crosslinking can be used to impart antimicrobial properties besides ordinary traditional methods (natural staining, etc.) [5, 22–24]. When the antimicrobial properties of natural dyes are examined, the most common components that provide antimicrobiality are phenolics and polyphenols (simple phenols, phenolic acids, quinones, flavonoids, tannins, and coumarins), terpenoids, oils, alkaloids (e.g., berberine), leptins, carotenes, and polypeptides [4, 5, 9, 10, 14,

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25–29]. Flavonoids can perform a variety of functions including antioxidant, antiallergenic, antioxidant, and antimicrobiality. Phenolic extracts were found to be effective against both gram-negative and gram-positive bacteria. Phenolic compounds exhibit antibacterial functions by mechanisms such as destabilization of cytoplasmic membrane, inhibition of extracellular microbial enzymes, and inhibition of microbial metabolism. The presence of quinone in plants also provides antimicrobial protection. These compounds have high reactivity, are easily subject to oxidation and reduction reactions, and exhibit color changing capability. They act as antimicrobial substance by inactivating proteins and by targeting cell membrane polypeptides and membrane-binding enzymes [26]. Chitosan, as an effective nontoxic biopolymer, can be used for an antimicrobial finishing process and sometimes its usage may lead to increase on the dye uptake on fabrics [19, 28, 29, 34–36, 48]. Chitosan has free amine (–NH2) groups that provide active sites for several chemical reactions [29]. The application of chitosan to woolen fabrics increases the dye uptake of woolen fabrics and the antimicrobial properties of the dyes are significantly improved [19, 36, 48]. Chitosan amino groups clash with bacterial metabolism by aggregating on the cell surface and binding to DNA to inhibit mRNA synthesis. In fact, the causes of the antimicrobial character of chitosan are controversial and there are two hypotheses. In the first hypothesis, the polycationic chitosan consumes the electronegative charges on cell surfaces and the cell permeability is altered, hence this interaction leads to the leakage of intracellular electrolytes and pertinacious constituents [29, 35, 45, 49]. In the second hypothesis, chitosan enters fungal cells and then essential nutrients are adsorbed, followed by hampering or slowing down of mRNA and protein synthesis [45, 49]. The antimicrobial activity of chitosan is influenced by factors such as chitosan type, degree of deacetylation, molecular weight, and other physicochemical properties. At the same time, the antimicrobial activity of chitosan is sensitive to pH (providing higher efficacy at low pHs) [29, 35]. In addition, the chain length of chitosan is important for factors such as species of microorganisms tested, temperature, concentration, environmental conditions, substrate and/or nutrient composition, cations, and polyanions [35]. For instance, tannin is the chief constituent of the pigment extracts from pomegranate peel and walnut shell, and it was reported that tannins could result in antibacterial effects. The astringent characteristic of tannin might induce complexation with enzymes or substrates. In other words, many microbial enzymes are inhibited when mixed with tannins [55]. Therefore, pomegranate (Punica granatum) (derived from ellagic acid and tannin) and other known natural dyes have also been reported to have a strong antimicrobial effect due to large amount of tannin presence [2, 9, 14, 26, 50–57, 86]. Vegetable (plant) dyes containing naphthoquinones (naphtoquinones) such as lawsone in henna tree, juglon in walnut, and lapachol in beef tongue display antibacterial and antifungal properties [2, 9, 14, 44, 52, 55, 58–71]. Red sandalwood oil has been found to prevent the harmful effects of chemicals in mice warts. This plant oil has shown to inhibit the development of skin cancer in mice besides its antiviral properties [4, 22]. Scientific research has shown that aloe vera leaves contain 75 nutrients and 200 active ingredients, as well as 20 minerals, 12

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vitamins, and 18 amino acids [28, 29]. High antibacterial activity of aloe vera gel may be due to the presence of amino groups.These amino groups in the weak acidic environment are converted to positive amino group ions which will interact with the negatively charged protoplasm of the microorganism, thereby breaking the cell wall. As a result, the microorganism is destroyed [72]. The dyed fabric with berberine also exhibits effective antimicrobial activity. The mechanism of berberine is the structure of positively charged quaternary ammonium salts in berberine molecules destroys the negatively charged cell membrane of the bacterium by disrupting the charge balance of the cell membrane [7, 73–75]. Other detrimental effects of quaternary ammonium compounds on microbes are denaturation of proteins and disruption of cell structure. During the inactivation of bacterial cells, quaternary ammonium groups remain intact and maintain their antimicrobial properties as long as they are bound to the constituent textile material [74]. Although the mechanism of antibacterial activity of turmeric (the active ingredient of curcumin, Fig. 2) is not deciphered, it is stated that monitored antimicrobial activity may be due to the presence of methoxyl and hydroxyl groups [76, 77]. Many researchers have indicated that chiconine, alkanine, and their derivatives impart an inactive property against both gram-positive and gram-negative bacteria. This is because chiconine has a naphthoquinone structure that promotes the mammalian topoisomerase II-mediated DNA cleavage in  vitro. Thus, naphthoquinone exhibits cytotoxic and antimicrobial activity by altering the DNA conformation of microbes. However, metabolic inactivation and permeability in the cell are different between the ornatic naphthoquinone components. Therefore, the chiconin family containing deoxycyconin does not have the ability to penetrate gram-negative cells due to the outer membrane (membrane) of liposaccharide and protein which the gram-positive cell wall does not possess [6]. Antimicrobial plants, briefly counted, some acacia species (Acacia catechu, Acacia nilotica, and Acacia auriculiformis) [2, 9, 59, 79, 80], mallo tree (Mallotus philippinenis) [2], Rheum emodi L. [81], Tamarindus indica L. [82], amla (Emblica officinalis G.) [61], oak slate (Quercus infectoria) [2, 9, 27, 50, 59, 83–85], myrobalan (karahalile, Terminalia chebula) [2, 53, 60, 86], pseudo rosary tree or neem tree (Azadirachta indica) [46, 49, 51, 86–90], Achyranthes aspera L. [86, 91], some aloe species (Aloe arborescens, Aloe barbadensis) [47, 48, 60, 72, 92, 93, 95, 96],

Fig. 2  The chemical structure of curcumin [78]

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Mexican chamomile (Tridax procumbens L.) [87, 97], peony, clove (Eugenia caryophyllata) [14, 50], the female saline (Rhizoma coptidis is the established root stem of Coptis chinensis Franch) [50, 73], Berberis vulgaris [74, 98–100], turmeric (Curcuma longa L.) [5, 6, 8, 14, 17, 47, 48, 51, 58, 61, 69, 71, 77, 82–102], Ocimum sanctum [43, 57, 102], onion (Allium cepa L.) [52, 58, 103], teak tree (Tectona grandis L.) [20, 80], ratanjoti or barbados nuts (Jatropa curcus) [80, 105], tobacco (Nicotiana tabacum L.) [106, 107], eucalyptus (Eucalyptus odorata Behr and Eucalyptus cinerea F. Muell. ex Benth) [108], mint [52], annatto (Bixa orellana) [109], Euphorbia humifusa [110], rosemary (Rosemarinus officinalis), rose (Rosa damascena), and thyme (Thymus vulgaris) [14] have also been reported by researchers to exhibit antimicrobial properties [11, 12, 25, 28, 111–113]. Research has generally shown that treated fabrics exhibit more antimicrobial activity to gram-­positive bacteria than gram-negative bacteria [5, 51]. This is due to the fact that the cell membranes of gram-positive bacteria are single-layered, and that the cell-­membranes of gram-negative bacteria are surrounded by multiple layers of the outer cell membrane [5]. However, some scientists have stated that this effect can vary in both types of bacteria depending on the plant content [51]. Antimicrobial fabrics can also be produced with natural dyes, but these fabrics possess problems regarding the strength of the antimicrobial properties [5]. Moreover, the antimicrobiality of the fabrics is generally reduced due to multiple washes or light exposure of the fabrics [5].

2  N  atural Resources That Impart Antimicrobiality to Textile Fabrics and Their Applications Natural resources based on plant and animal extracts that impart antimicrobiality to textile fabrics and their applications are explained in following sections.

 lant Extracts That Impart Antimicrobiality to Textile Fabrics P and Their Applications Antimicrobial textile fabrics with the treatment of plant extracts and the applications of these extracts are reviewed in this section. Acacia The extract obtained from pseudoacacia (Acacia catechu) (Fig.  3) was used for natural dyeing of textile, and the antibacterial effects of dyed fabric against Klebsiella pneumoniae, Escherichia coli, and Proteus vulgaris gram-negative

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Fig. 3  Acacia catechu [114]

b­ acteria were investigated [2, 115]. The plant extract exhibited antibacterial activity against Klebsiella pneumoniae and Proteus vulgaris bacteria [2]. The antibacterial activities of wool fabrics dyed with extracts obtained from false acacia (Acacia catechu L., Willd., Oliv.) (2005) against B. subtilis, E. coli, K. pneumoniae, P. vulgaris, and Pseudomonas aeruginosa were examined. False acacia extract is reported to exhibit antibacterial effect against all tested bacteria, except P. aeruginosa. After applying the extract to wool fibers, it was observed that between 10% and 15% bacterial growth reduction was achieved. The dye concentration of 9.2% used for fabrics did not provide sufficient effect [9]. In another study (2005), extracts of ten plant species (Acacia catechu, Acacia nilotica, Punica granatum, Quercus infectori, Terminalia chebula, Kerria lacca, Mallotus phil ippinensis, Rheum emodi, Rubia cordifolia, and Rumex maritimus) were obtained, and their UV transmittance and antibacteriality (Pseudomonas aeruginosa, Bacillus subtilis, Klebsiella pneumoniae, and Proteus vulgaris according to AATCC 147 method) were examined. The results of the study showed that A. catechu was effective against all microorganisms except Pseudomonas aeruginosa. In addition, fiber treated with A. catechu provided activity against microorganisms in range 0.6–1.6  mm (inhibition zone) [59]. Antimicrobial activity (using disc diffusion method) against Escherichia coli, Streptecocus aureus pathogenic bacteria, and Candida albicans and Candida tropicalis pathogens of wool yarns treated with false acacia plant with mordant and without mordant presence (iron sulfate and tin chloride mordant with premordanting method) was investigated (2011). This natural dyestuff exhibited significant antimicrobial properties compared to standard antifungal and antibacterial drugs. The yarns dyed at 20% dye concentration exhibited antimicrobial activity in range 85–90% for bacteria and 93–95% for fungi [79]. In another study, the antibacterial activities (against S. aureus, Shigella flexneri, Bacillus subtilis, and E. coli) of cotton fabrics (mordanted with copper sulfate and iron sulfate using premordanting and postmordanting methods) dyed with the extract of Acacia auriculiformis were explored in 2011. Results showed that fibers dyed with the extract provided an

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i­ nhibition zone of 18 mm against S. aureus, 21 mm against Shigella flexneri, 18 mm against Bacillus subtilis, and 20 mm against E. coli [80]. On the other hand, cotton fibers were dyed using the extract obtained from another acacia species (Acacia nilotica), and the antibacterial activity of the extract and treated fibers against Klebsiella pneumoniae, Escherichia coli, and Proteus vulgaris gram-negative bacteria was investigated. Results showed that the extract did not provide antibacterial activity against any studied bacterial species [2]. Indigo The possible antimicrobial property of indigo which is extracted from indigo plant was also discovered by various researchers and scientists (Fig. 4). In a study in 2004, cotton fibers were dyed using indigo (Indigofera tinctoria) extract and antibacterial activity of the fibers against gram-negative bacteria was examined. Results showed that the extract did not provide antibacterial activity against any bacterial species studied [2]. On the other hand, in another study, bleached cotton and cotton/modal blended knitted/woven fabrics were dyed with

Fig. 4  Indigofera tinctoria [116]

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natural extracts obtained from kum kum, indigo, and bar berry;moreover, hot and cold dyeing reactive dyes and sulfur dyes and their antibacterial activities were examined (according to the AATCC 147 test method). Results displayed that all tested samples provided a higher inhibition zone against S. aureus bacteria than E. coli. Modal fibers provided higher inhibition zone than cotton and cotton/modal blend. Synthetic dyes provided higher antibacterial effect than natural dyes. It was concluded that, amongst natural dyes, indigo dye (between 29 and 35 mm) exhibited higher antibacteriality than that of kum (in range 25–33 mm) [117]. In a study conducted in 2008, cotton fabrics were treated with Terminalia chebula extract and Pterocarpus santalinus Linn. f. (Rath handun) extracts. Results showed that fabrics treated with the combination of Pterocarpus santalinus displayed bacterial reduction values ranging from 59% to 68% against gram-negative bacteria and from 59% to 63% against gram-positive bacteria [60]. Pomegranate Pomegranate (Punica granatum) is another plant whose antimicrobiality has been studied (Fig.  5). Pomegranate (Punica granatum) extract was applied to cotton fibers. Extract and dyed fibers exhibited antibacterial activity against 3  gram-­ negative bacteria: Klebsiella pneumoniae, Escherichia coli, and Proteus vulgaris [2]. Extracts obtained from pomegranate (Punica granatum L.) were applied to cotton fabrics as functional finishing process, and antibacteriality of the treated fibers was examined according to AATCC 147-1988 method, agar diffusion, Hohenstein test method, and burying method. Treated fabrics also displayed antibacterial activity with 90% bacterial reduction and 2.9 mm inhibition zone, and the antibacterial activity of the samples is reduced by half after the sixth wash [86]. In another study, cotton, wool, and silk fibers were dyed with the pomegranate extract for 60 minutes at 80 °C, and their antibacterial activity of the fibers against Staphylococcus aureus and Klebsilla pneumoniae bacteria were examined. Pomegranate extract has an efficacy of 99.9–96.8% against Staphylococcus aureus and 95.7–99.9% against Klebsilla pneumoniae. Cotton fibers dyed with pomegranate displayed 99.9% bacteriostatic reduction rates against Staphylococcus aureus and 95.8% against Klebsilla pneumonia. In the case of silk fibers, bacteriostatic reduction rates were 99.8% against Staphylococcus aureus and 99.5% against Klebsilla pneumoniae. Moreover in the case of wool fibers, bacteriostatic reduction rates were 99.9% against Staphylococcus aureus and 99.8% against Klebsilla pneumoniae [50]. It has been reported that this measured antibacterial activity of pomegranate extract may be due to ellagic acid and tannin presence [50, 51]. Antibacterial activity of wool fabrics dyed with natural dye obtained from pomegranate was investigated according to disc diffusion method (NCCLS-1997) against S. aureus, Shigella sonnei, E. coli, Bacillus megaterium, B. subtilis, Bacillus cereus, Streptococcus epidermidis, Salmonella 21.3, and P. aeruginosa [52]. Results show that the inhibition zone of the natural dye obtained from pomegranate against all bacterial species varied between 10.5 and 17.9  mm and also provided a 4–80%

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Fig. 5  Pomegranate [118]

bacteriostatic rate decrease in the case of wool fibers. Results exhibited that natural dye obtained from pomegranate led to significant antibacterial activity against gram-positive bacteria and provided less inhibitory effect against gram-negative bacteria. This is because the cell wall structure of gram-negative bacteria is essentially constructed with LPS, which prevents the accumulation of antibacterial agents in the cell membrane [52]. Scientists have studied not only the natural dyeing with pomegranate (Punica granatum L.) extract but also nature-friendly and natural antibacterial finishing processes using pomegranate (Punica granatum L.) extracts [57]. For instance, plant extracts obtained from the peel of pomegranate were applied to cotton fabrics with direct application (pad-dry-cure impregnation-drying-thermophysics), microcapsulated dyestuffs, resin cross-linking, and their combinations (microencapsulated dye-­ resin cross-linking). Also their antibacterial activities against gram-positive and gram-negative bacteria (according to AATCC-100 and AATCC 147 test methods) were evaluated. Antibacterial test results showed that antibacterial activities of the treated fabrics are in good level: 99.9% against Staphylococcus aureus and 90.8% against Klebsilla pneumoniae as a result of its  direct application, 99.8% against Staphylococcus aureus and 85.2% against Klebsilla pneumoniae as a result of

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microencapsulation, 98.2% against Klebsilla pneumonia as a result of cross-linking, finally bacterial reduction by 89.2% against Staphylococcus aureus, and 87.1% against Klebsilla pneumoniae as a result of cross-linking and microencapsulation combination [57]. It is noted that there is no significant change in the combined (microencapsulated dye-resin cross-linking) processes, although there are some reduction in the tensile strength of the resin-treated fabrics and the creaseability of the microencapsulated dyes treated fabrics. While fabrics can exhibit washing resistance to 15 washing cycles and above, fabrics treated with the direct application method do not exhibit washing resistance, and therefore it is indicated that this method would be more suitable for disposable fabric production (such as surgical clothes, gauze, and sanitary napkins) that do not need to be washed. One of the other techniques (microencapsulated paint, resin application, or both) was more appropriate for the production of fabrics requiring repeated washing cycles (e.g., hospital bed sheets, pillowcases, and socks) [57]. In another study using impregnation-drying-thermophysis method, extracts of pomegranate (P. granatum) leaves and shells via water and methanol were obtained and applied to cotton fabrics. Antibacterial activity of treated fabrics against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Proteus vulgaris, and Salmonella typhi bacteria [according to AATCC 100-2004-SN 195920 agar diffusion test and Hohenstein Modified Challenge test (JIS L 1902)] resistance was investigated [53]. Agar test results showed that the fabrics treated with extracts obtained with both water and methanol provided an inhibition zone of 27–32 mm in diameter against all bacterial species. Pomegranate has been shown to reduce the bacterial activity with 99.9% against Staphylococcus aureus. Extracts obtained with methanol provided higher antibacterial activity than extracts obtained with water. Results showed that the durability of the process applied to fibers after washing was reduced. It has been reported that this method can be quite effective and inexpensive if the treated fibers are commercialized for use in various forms such as disposable bandages and surgical masks [53]. Aqueous extracts of pomegranate (P. granatum) peel, rich in tannins, were applied with exhaust dyeing technique to cotton fabrics. Potassium bichromate, copper (2) sulfate, iron (2) sulfate, iron (3) sulfate, tin (2) chloride, aluminum sulfate, and tannic acid mordants (premordanting) were used as a mordant material. Antibacterial properties of the fibers (according to the AATCC 100-1993 method) have been investigated against S. aureus gram-positive and E. coli and Pseudomonas aeruginosa gram-negative bacteria [55]. The major component of pomegranate is tannin, and structural activity studies showed that tannins can provide antibacterial effect. The inhibitory property of the grain which gives an antibacterial effect promotes its formation with enzymes and substrates. Many microbial enzymes in crude culture or purified forms can be inhibited when combined with tannins. Results showed that 20% pomegranate extract provided significant antibacterial activity (74.80% against S. aureus, 83% against E. coli, and 99.40% reduction against Pseudomonas aeruginosa). However, the antibacterial activity of the process decreases with washing and light exposure. These results indicated that pomegranate peel extracts can be used in hospital textiles as

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a­ ntibacterial agents instead of artificial alternatives, and in sports and home textiles as effective antiodor agents [55]. Dyes extracted from Punica granatum (pomegranate) plants were applied to cotton and synthetic fabrics with various mordants (iron sulfate, copper sulfate, and lemon mordants: premordanting, simultaneous mordanting, and postmordanting) [56]. Clitoria ternatea and Targetes erecta Linn (marigold) were also applied on fabrics. The washing, rubbing, and light fastness and antibacteriality of the fabrics according to disc diffusion method against E. coli and Klebsiella sp. (gram-­negative) and S. aureus and Bacillus sp. (gram-positive) bacteria were investigated. The study results showed that pomegranate natural dye displayed antibacterial activity in solution and fabric (8 mm against E. coli, 8 mm against Klebsiella sp., 10 mm against S. aureus, and 12 mm against Bacillus sp. zone). In addition, it has been reported that fibers dyed with Clitoria ternatea displayed 37–50% and 7–57% bacteriostatic reduction against E. coli bacteria and S. aureus, respectively. In the case of fibers dyed with Targetes erecta Linn (marigold), bacteriostatic reduction rates were 25–44% and 22–50% against E. coli and S. aureus, respectively [56]. Gallnut Oak pasture (Quercus infectoria) (Fig. 6) was used to impart antibacterial properties to cotton fibers. Results showed that the extract was effective against all studied bacterial species [2]. Gallnut extract was applied to the fabrics containing copper and iron sulfate mordants. Results showed that the antibacterial activity of cotton fibers dyed with this extract increases with increasing dye concentration [2]. It was stated that the bacteriostatic reduction activity against E. coli bacteria was 97.4% and against P. vulgaris was 99.5%. These results were higher than the commercial antibacterial agent used in their study. However, a strong reduction in bacterial activity occurred with the use of mordant. It is thought that this may be due to the Fig. 6  Gallnut [119]

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coupling of the dyestuff and the metal salt. The only functional groups present in these dyestuffs are hydroxyl groups, and as is well known, ortho hydroxyl groups become the regulator of bond formation for the chromophore, for example, as chromium purple dyes. Therefore, the formation of these coordinated bonds may block the groupings necessary for antibacterial activity [2]. Wool fabrics were dyed with oak slate (Q. infectoria Olivier) extract in order to examine the antibacteriality [9]. The treated wool fabrics resulted in 15–25% reduction in bacterial growth. The oak slate, which exhibits bactericidal activity in the form of extract, can only inhibit the growth of bacteria on the fabric. This is due to the fact that the concentration of 5.3% on the fabric is not sufficient for bactericidal activity. In this study, pseudoacacia extract was used in addition to oak slate, and although both dyes were tannin based, their antibacterial activities showed significant differences. This is an interesting finding and requires further investigation into the effect of the dyestuff structure on the antibacterial property. Antibacterial activity appears to be closely related to the dye structure and particularly to the presence of functional groups in the dye structure [9]. Quercus infectori extract provided efficacy against all studied microorganism species [59]. On the fiber, Quercus infectori extract treated fibers displayed efficient bacteriostatic effect against all microorganism species in range 1.2–2.9 mm [59]. Woven cotton fabric was treated with extracts obtained from tannin-rich oak (Q. infectoria Olivier) (with a concentration of 12%) in company with alum, copper, and iron sulfate mordants and their antibacterial activities against E. coli and B. subtilis bacteria were explored [83]. In the qualitative method (test method AATCC 147), the greater the inhibition zone, the higher the antibacterial activity. Dyed fibers in the presence of iron and copper sulfate mordants exhibited microbial growth. Samples in which gallnut was used alone at a concentration of 12% showed the highest inhibition region. The effects of treatment with gallnut were not resistant to washing. Only in the case of gallnut presence, it infiltrates onto treated cotton fabrics to give a zone (inhibition zone). When mordant is used, the dyestuff forms complex through coordinated bonds with the mordant and thus becomes insoluble [83]. In another study, examining the antibacteriality of oak slate, cotton, wool, and silk fibers was dyed with the extract obtained from oak slate, and the activity of the fibers against Staphylococcus aureus and Klebsilla pneumoniae bacteria was examined. It has been observed that the extract provides 99.9% activity against all studied bacterial species [50]. In another study examining the antimicrobiality of oak slate (Quercus infectoria Olivier), the extract was applied to wool yarns [85]. Gallnut consists of a mixture of gallotanin, gallic acid, ellagic acid, starch, and glucose, and is generally used in tanning, mordanting, dyeing, and ink making. Tannins in the gallnut have been found to have antimicrobial activity. Washing resistance of treated fabrics and their antimicrobial activity (with minimum inhibitor concentration and disc diffusion analysis) against the Escherichia coli, Staphylococcus aureus, and Candida albicans, a common fungus, were investigated. In addition, two tin chloride (SnCl2.2H2O) and screed (K2Al2 (SO4)4.24H2O) mordants were also used in this study [85]. Antimicrobiality provided by gallnut to wool fibers is given in Table 1.

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Table 1  Antimicrobial activity provided by gallnut to wool fibers [85] Sample Control sample Treated fibers with 6% gallnut extract +1% SnCl2 +10% alum Treated fibers with 12% gallnut extract +1% SnCl2 +10% alum

E. coli 0.7 78.6 72.4 69.1 87.2 83.6 82.4

S. aureus 3.8 76.6 69.4 60.7 94.8 91.3 93.2

C. albicans 6.8 84.3 77.4 74.6 96.2 90.2 87.8

Results show that gallnut exhibits antimicrobial activity against all microorganisms studied. The antimicrobiality of the fibers was found to be semiresistant to washing. Mordanting negatively affected antimicrobial activity but also improved washing resistance [85]. In another study, the extract was applied on wool and cotton fabrics (pad-dry-­ cure method). In addition, plasma-treatment has been applied to improve the finishing effect of the fabrics [84]. Results showed that the treatment with gallnut extract increases antibacteriality. However, wool fibers treated with gallnut extract showed activity against S. aureus (91.2% bacterial reduction) but relatively more passive to K. pneumoniae (78.6% bacterial reduction). It was also stated that after the plasma treatment, antibacterial activity against K. pneumoniae in wool fibers decreases considerably. This is explained by the fact that plasma treatment increases the hydrophilicity of the wool fiber and therefore more bacteria may be adsorbed onto plasma-treated woolen fabrics during antimicrobial testing. However, this decrease was not observed in the antibacterial activity against S. aureus, even the bacterial reduction of 91.2% increased to 99.9% after plasma treatment. Antibacteriality of plasma treated or untreated cotton fabrics varied between 91.9% and 99.9% for both bacteria [84]. Myrobolan Another plant whose antimicrobiality was examined was myrobalan (myrobalan, black-halile, Terminalia chebula) (Fig. 7). Plant extract was applied to cotton fibers. Antibacterial activity of the extracts and dyed fibers against Klebsiella pneumoniae, Escherichia coli, and Proteus vulgaris bacteria was investigated, and they displayed antibacterial activity against Klebsiella pneumoniae and Proteus vulgaris [2]. Terminalia chebula extract and the  combinations of this extract with other plant extracts were applied to cotton fiber fabrics (by pulping and prescoring, screed mordanting) and the antibacteriality of these cotton fabrics (E. coli as gram-negative and S. aureus as  gram-positive bacteria) was investigated  according to AATCC 100-1999 method. According to the study results, combinations of T. chebula extract and other extracts showed bacterial reduction values ranging from 56.8% to 68% [60].

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Fig. 7  Myrobolan [120]

In another study, extracts in water and methanol were obtained from Terminalia chebula, and these extracts were applied to cotton fabrics using pad-dry-cure. Antibacterial activity of treated fabrics against Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Proteus vulgaris, and Salmonella typhi [according to AATCC 100-2004  - SN 195920 agar diffusion test and Hohenstein Modified Challenge test (JIS L 1902)] was investigated [53]. The results of the agar test showed that the ethanol-extracted Terminalia chebula treated fabrics provided an inhibition zone for all microorganism species in range 32–38 mm, and the water-­ extracted Terminalia chebula treated fabrics in range 32–34  mm. According to another method, T. chebula showed a decrease of 99.36% against Staphylococcus aureus and 98.11% against E. coli. According to both methods, the extracts obtained with methanol provided higher antibacterial activity than the extracts obtained with water. Results showed that after washing, the durability and antibacterial efficacy of the treated fibers are reduced [53]. In addition, extracts obtained from karahalile (Terminalia chebula Retz.) fruits in water and methanol were applied to cotton fabrics by using citric acid as crosslinker [121]. Antibacterial components in the extract were analyzed and antibacterial activity of treated fabrics against S. aureus (gram-positive), E. coli, Klebsiella pneumoniae, P. vulgaris, and Salmonella typhi (gram-negative) bacterial species using agar diffusion (SN195920) and quantitative analysis (by AATCC-100) [121]. Analysis of the study confirmed the presence of saponin, ascorbic acid (vitamin C), and gallic acid. Agar diffusion test results showed that the treated cotton fabrics provided inhibition zone in range 27–32  mm against all species, and displayed 99.36% bacterial reduction effect against S. aureus, and between 86% and 98.11% against E. coli. Fibers treated with Terminalia chebula exhibited both bactericidal (bactericidal) and bacteriostatic (inhibiting bacterial growth) properties. Results

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also showed that treated fabrics have poor washing resistance [121]. The combination of Terminalia chebula extract and Vitex negundo L. extract was also applied to cotton fabrics to impart antibacteriality. According to the study results, fabrics treated with combinations of plants showed bacterial reduction values ranging from 61% to 69% against gram-negative bacteria and from 57% to 64% against gram-­ positive bacteria [60]. Madder Madder dyeing (Fig. 8), which has several species, is another plant species whose antimicrobiality has been studied [123]. The main chemical component of the root dye is quinones [65]. Indian madder (Rubia cordifolia), a type of root dye, is one of the plants whose antibacteriality has been studied. In one study, the extract of the plant was applied to cotton fibers. Results showed that the extract did not provide antibacterial activity against any bacterial species [2]. In another study, woolen fabrics were dyed with extracts from Indian madder (Rubia cordifolia), and the extracts and treated fabrics were isolated from common pathogens such as B. subtilis, E. coli, K. pneumoniae, P. vulgaris, and Pseudomonas aeruginosa. The study results showed that R. cordifolia extract provided only minimal activity against K. pneumoniae [9]. According to the results of another study conducted in 2005, R. cordoflia provided almost no effect on fiber [59]. In another study (2008), the combination of Terminalia chebula extract and Rubia cordifolia extract were applied to cotton fabrics and their antibacteriality was investigated. According to the study results, fabrics treated with the combination of R. cordifolia showed bacterial reduction values between 57% and 64% against gram-negative bacteria and between 59% and 68% against gram-positive bacteria [60]. Grain obtained from dried fruits of Amla (Emblica officinalis G.) was used as a mordant, and cotton and silk fibers were premordanted  with a combination of tannin and copper sulfate mordant  along with amla, and then the fibers were dyed with root dye (Rubia cordifolia) extract [61]. The results are given in Table 2.

Fig. 8  Madder [122]

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Table 2  Antibacterial activity of un mordanted and mordanted and dyed cotton and silk fibers [61] Samples Unmordanted 15% amla mordanted 15% amla mordanted +0.5% Cu 15% amla mordanted +1% Cu

S. aureus Cotton 37.5 87.50 98.33 100

Silk 41.26 94.57 100 100

E. coli Cotton 30.55 84.02 97.91 100

Silk 39.45 92.01 100 100

Table 2 shows antibacterial activity increased with the presence of copper. Copper displayed effective antibacterial, antiseptic, and bactericidal properties. The antibacterial activity of the fibers decreased after 20 washes [61]. Antibacterial activity of wool fabrics dyed with natural dyestuff obtained from Rubia tinctorum L. was examined against S. aureus, Shigella sonnei, E. coli, Bacillus megaterium, B. subtilis, Bacillus cereus, Streptococcus epidermidis, Salmonella 21.3, and P. aeruginosa. Root dye extract showed activity against B. megaterium, S. aureus, and B. subtilis. It was reported that the effect of reducing bacterial growth on fiber in range 32–52% is observed [52]. In another study (2010), using the impregnation method, root dye (Rubia tinctorum L.) was applied to premordanted cotton knitted fabrics with various mordants (iron sulfate, copper chloride, zirconium oxide chloride, aluminum chloride, and screed), and the antibacterial antibacterial efficacy of the fibers was analyzed according to AATCC 100-1999 test method [58]. In this study, the order of sensitivities of tested microbes that died by contacting the surface of the dyed sample was given as gram-positives (S. aureus) (bacterial growth reduction 96.9%) and gram-negatives (E. coli) (bacterial growth reduction 95.2%). This is probably due to the fact that the gram-positive bacterial cell wall consists of a single layer. The gram-negative cell wall is delimited by the outer cell membrane to a plurality of layers, so higher concentrations of dyeing may be required to kill such bacteria. In addition, antibacterial activity decreased after washing [58, 62]. In order to see the effect of plasma treatment, wool fibers were treated with R. tinctorium and budding flower extracts with copper sulfate (CuSO4) mordant, and antibacteriality of fibers (against S. aureus and E. coli) was measured. The study results showed that plasma treatment improves the dyeing properties of wool fiber and increases the antibacterial activity of the fiber. Bacterial reduction values of both untreated and plasma treated fibers with natural dyes against both bacteria species were found to be over 99% and the inhibition zone above 4  mm. Bacterial reduction values and inhibition zone values of the dyed fibers were measured above 99% and 3  mm, respectively. The structure of the dyestuff is responsible for the antimicrobial activity [63]. To provide UV protection and antibacterial antibacterial properties, screed, zinc-sulfate, and tannic acid mordants and premordanted polyamide 6 fabric were dyed by root dyeing. Results showed that the dyes/mordants exhibited good fastness values and provided good antibacterial activity against S. aureus and E. coli bacteria as well as effective UV protection. Results showed that the highest antibacterial effect was achieved with zinc sulfate mordanted dyed fibers (14 mm for E. coli, 15.1 mm for S. aureus inhibition zone) [64]. Wool fabrics

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were dyed by using dye extract and aluminum sulfate (as mordant), and antibacterial effect of the dyed samples against gram-negative bacteria Pseudomonas aeruginosa, Escherichia coli, and gram-positive bacteria Staphylococcus aureus was studied using AATCC 100-1993 method [65]. The study results showed that the madder dye displayed a very high antibacterial activity against three bacteria (95–99.8% for Pseudomonas aeruginosa, 96.8–99.7% for Escherichia coli, and 95.7–99.5% for Staphylococcus aureus). This activity is associated with the chemical constituents of alizarine (hydroxy anthroquinone) in the root dye. Alizarin in the root dye is in the quinone category, which is known as the antibacterial component. The stability of the dyestuff is increased by mordants used in the study. It was also observed that antibacterial activity increased after mordanting. In addition, increased dye concentration also positively affected antibacterial properties [65]. Many metallic salts inhibited the growth of microorganisms even at very low concentrations. Metals can have toxic effects when they are independent or as metallic compounds. It was claimed that the effect of metals may be through binding to proteins or through groups having reactive oxygen common properties. In the first mechanism, metal ions covalently bind to SH groups of cellular enzymes and eliminate their activity and alter bacterial metabolism, which ultimately leads to cell death. The second effect is based on the pro-oxidant accelerator effect of aluminum. Aluminum-induced mitochondrial dysfunction changes the common properties of reactive oxygen. The high active oxygen radicals produced as a result of this reaction attack and destroy the chemical structure of the bacteria [65]. Some researchers have claimed that antibacterial properties are reduced after mordanting, and this is due to the formation of complexes between the active functional groups of the metal salt mordants and the dyestuffs. In this study, it has been suggested that the metal ions have great antibacterial properties and that the aforementioned mordants decrease the antibacteriality may have resulted from the test method applied. After dyeing, the fibers were subjected to washing resistance test and light fastness test. It has been observed that the antibacterial activities of the processes performed with natural dyes are not resistant to washing and exposure to light. However, there is not much reduction in the antibacteriality of mordant fibers [65]. Neem Tree False rosary tree or neem tree (Azadirachta indica A. Juss.) (Fig. 9) is one of the plants whose antimicrobiality has been studied [86]. Extracts obtained from pseudo rosary tree (or neem tree, Azadirachta indica A. Juss.) were applied to cotton fabrics as functional finishing (by dipping), and the antibacterialities of the fibers were examined according to AATCC 147-1988, Agar diffusion, Hohenstein test method, and soil by the embedding method [86]. Results showed that fabrics treated with neem tree extract exhibited good antibacterial activity according to the agar test method with inhibition zone 5.8 mm against S. aureus and 3.3 mm against E. coli. According to the other test method, the neem extract showed a 100% reduction, and

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Fig. 9  Neem tree [193]

the fibers treated with the neem extract showed resistance to microbial attack, and the antibacterial activity of the samples decreased after washing [86]. Extracts obtained from pseudo rosary tree (Azadirachta indica A.  Juss.) were applied as microencapsulated dyestuffs on cotton fabrics using pad-dry-cure impregnation-drying-thermofix method [87]. The antibacterialities of the fibers were analyzed using the AATCC 100 agar diffusion method (against S. auereus and E. coli). Results showed that neem extract produced 100% bacterial reduction against S. auereus and 78.44% against E. coli. Microencapsulated neem extract displayed a bacterial reduction of 93.45% against S. auereus and 55.21% against E. coli. Extracts applied directly to the fibers did not show antibacterial activity after 10 washes. This is because extracts only cover the surface without any bonding and washed away. Fibers using citric acid in direct application showed little efficacy after ten washes. Microcapsulated fibers exhibited antibacterial activity in range 59–78% after 15 washes [87]. Again, the extract obtained from the seeds of the false rosary tree (Azadirachta indica A. Juss.) was used to improve the biofunctionality of the polyester/cotton blend fabrics [88]. Glyoxal/glycol was used as a cross-­ linking agent in this study. Bacillus subtilis gram-positive and Proteus vulgaris gram-negative bacteria were used to test antibacterial activity according to AATCC 147-1997. The main components of the neem tree, azadirachtin, salanin, and meliantriol are antifeedants for insects. Results showed that all unwashed blend fabrics exhibited 95% antibacterial activity against Bacillus subtilis and about 80% against Proteus vulgaris. After one wash, the efficiency of all fabrics decreased. However, only the wetted fabrics with no cross-linker exhibited no antibacterial activity after a wash. In the Buddha neem extract, the active compounds (necessary for bacteriostatic or bactericidal) did not have affinity to the fabric, so the mixture cannot bind to textile structures in the absence of crosslinkers [88]. In another study, the combinations of Terminalia chebula and Azadirachta indica extracts were

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applied to cotton fabrics. Results of the study showed that fabrics treated with the combination of Azadirachta indica showed bacterial reduction values ranging from 57% to 64% against gram-negative bacteria and from 60% to 68% against gram-­ positive bacteria [60]. In another study (2010), natural antibacterial finishing procedures using false rosary tree (Azadirachta indica A.  Juss.) extracts were applied [102]. In this study, microcapsules encapsulated with extracts of plants were applied to silk and cotton fabrics by pad-dry-cure impregnation-drying-thermophysis method [microcapsules were fixed to fabrics with binder (UF Silpure FBR-S PA) at 120  °C] and antibacterial activities of the fabrics against S. aureus, E. coli, and Pseudomonas was examined using disc diffusion and parallel steak methods (AATCC 143-1993). Results showed that neem-treated fabrics exhibited antibacterial against all bacterial species [102]. In another study (2010), to prevent the possible damages caused by fungus (Aspergillus sp., Fusarium sp., and Trichoderma sp.) and bacteria (Pseudomonas sp.), neem tree extract and some chemicals (cadmium chloride, zinc sulfate, boric acid, and urea formaldehyde) were applied to cotton fibers [89]. Results showed that plant extracts exhibited potential antimicrobial activity but provided low efficacy, while chemicals already have effective antimicrobial activity. It was reported that the strength of the fabrics treated with neem extract increased by 10–12% [89]. The extract of neem leaves was applied to premordanted cotton fabrics in order to produce medical textiles by selecting the appropriate mordants using the extraction method [51]. Plant extracts such as pomegranate and turmeric were also used in this study, and results showed that fabrics treated with neem extract exhibited less antibacterial activity than pomegranate-­ treated fabrics, and this may be due to the binding properties of the extract [51]. In another study, chitosan nanocomposites were produced with extracts obtained from pseudo rosary tree (Azadirachta indica A. Juss.), and these nanocomposites were applied to 100% cotton fabric by pad-dry-cure method [46]. Antibacterial AATCC 100 and 147 methods were used for antibacterial activity. Results showed that fabrics treated with neem and chitosan nanocomposites exhibited more antibacterial activity (93% reduction against E. coli and 100% bacterial reduction against S. aureus) than other studied fabrics. After 30 washes, fabrics treated with neem-­ chitosan nanocomposite yielded 86% bacterial reduction against E. coli and 97% against S. aureus [46]. Antibacterial finishing was applied to cotton fabric with nanoparticles obtained from pseudo rosary tree (Azadirachta indica A.  Juss.) extracts and antibacterial efficacy of the treated fabrics (with AATCC 100 and 147 against E. coli and S. aureus) and their washing resistance were evaluated [90]. Results showed that fabrics treated with false rosary tree nanoparticles provided maximum antibacterial activity against bacteria (87.4% against E. coli and 100% against S. aureus). In addition, fabrics treated with pseudo rosary tree nanoparticles have been reported to retain their antibacterial activity up to 25 washes [90].

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Aloe Vera Another plant investigated is aloe vera (Aloe barbadensis Mill.) (Fig. 10). Terminalia chebula extract was applied to the cotton fabrics and the antibacteriality of these fabrics was examined. According to the study results, fabrics treated with the combinations of plants showed bacterial reduction values ranging from 59% to 69% against gram-negative bacteria and from 58% to 64% against gram-positive bacteria [60]. In another study, in addition to natural dyes, substances such as aloe vera (L.) Burm. f., chitosan, and turmeric (Curcuma longa L. active ingredient in turmeric) were applied alone or in various combinations to cotton, wool, and angora fibers. In this study, the method defined by Quinn was used as the antibacterial test. Aloe vera treated fabrics provided good antibacterial activity. Components such as acemannan, anthraquinone, and salicylic acid in the aloe vera help promote antimicrobial activity, and the presence of amino acids, zinc, and saponin content led to increase on antimicrobial activity [47]. In another study, aloe vera (Aloe barbadensis Mill.) extract, which was prepared by using methanol solvent, was applied to bleached 100% cotton fabric (with pad-dry-cure for 30 minutes at 60 °C) [72]. The agar diffusion and quantitative analysis methods were used as antibacterial test for S. aureus. The 5% concentration of the treated fabrics provided excellent antibacterial activity (exhibited bacterial reduction values ranging from 97% to 99.1% for various concentrations), and their washing resistance was good (98% bacterial reduction after Fig. 10  Aloe vera [124]

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50 washes). In this study, it was stated that bacterial inhibition might be due to the slow release of active substances on the surface. It is thought that the high antibacterial activity of aloe vera gel might be due to amino groups. In a weak acidic environment, the amino groups are converted to positive amino group ions which will interact with the negatively charged protoplasm of the microorganism, thereby breaking the cell wall and thus destroying the microorganism [72]. Aloe vera gel combined with citric acid can be used to produce environmentally friendly, natural antimicrobial finish on cotton fabric [93]. Results obtained with the application of this method showed that antibacterial results provided 89% efficacy against gram-­ negative organisms, 20% against gram-positive organisms, and 82% against fungal pathogens. Aloe vera (L.) Burm. f. gel may be an alternative to synthetic antimicrobial agents. Bioactive fabrics produced by this method can be used in hospitals, sportswear, household jugs, carpets, nonwoven surfaces, etc. [93]. In the studies related to the application of natural products to cotton fabrics as finishing process, Aloe vera (L.) Burm. f. gel (two separate gels, commercial and foliar, 75% gel, 100% gel and leaf extract) were applied to the cotton fabric by pad-dry-cure method (with citric acid). The antimicrobiality of the fibers was analyzed by AATCC 100, 147, and 30. The study results indicated that fabrics treated with 100% gel extract exhibited the highest antimicrobiality [94]. In another study, 100% cotton fabrics were treated with extracts from the leaves of Aloe vera (L.) Burm. f at different concentrations (2%, 4%, and 6%). Antibacteriality against S. aureus and K. pneumonia bacteria was measured using AATCC 100-parallel steak method. The treated fabrics exhibited bacterial reduction of 50% (at 2% concentration), 78% (at 2% concentration), and 90% (at 2% concentration). Fibers showed 58.5%, 39%, and 0% antibacterial reduction after washing [95]. Aloe vera (L.) Burm. f extract was applied solely as well as with the combination of turmeric and chitosan on cotton, wool, and angora fibers (2012). The study results showed that aloe vera, which was applied to the fibers alone, had better antimicrobial efficacy than the others. It was also observed that antimicrobial activity increased with the addition of aloe vera extract and turmeric and chitosan. Antimicrobials based on the method of attacking microbes were divided into two types. The first type (controlled release mechanism) is slowly released through the fiber or from the reserve on the surface of the fabric. This type of storage of antimicrobial can be highly effective against microbes on the fiber surface or the environment. The second type consists of molecules that chemically bind to the fiber surface. These products can only control microbes on the surface of the fabric, but do not affect the surrounding microbes. The adequacy of antimicrobial finishing processes can range from inhibiting cell production, blocking enzymes, interacting with the cell membrane to destroying the cell wall, and internally poisoning the cell [48]. In another study, cotton and organic cotton fabrics were coated with a mixture of Aloe vera (L.) Burm. f gel and Terminalia chebula powder (dip-dry method) [96]. In this study, antibacteriality of fibers was examined by AATCC 147 method (against E. coli and S. aureus). The results of the study showed that antibacterial activity (bacteriostatic region) is 18 mm in cotton against

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S. aureus, 29 mm in organic cotton, 20 mm in cotton against E. coli, and 27 mm in organic cotton. This shows that organic cotton provided excellent and good bacterial protection when compared to normal cotton [96]. Substances such as Aloe vera (L.) Burm. f., chitosan, and turmeric (Curcuma longa L.) were applied alone or in various combinations to cotton, wool, and rabbit hair fibers. Turmeric has only phenolic groups capable of forming hydrogen bonds with amino/hydroxyl groups in protein polymers and hydroxyl groups in cellulose polymer. In addition, since the molecular weight of turmeric is smaller than chitosan, its extraction to all fibers is greater than that of chitosan, which makes its antibacterial activity slightly higher than chitosan [47]. Aloe arborescens Aloe arborescens (Fig. 11) is another plant whose antimicrobiality has been studied. Various fabrics (cotton, nylon, acetate, wool, rayon, acrylic, silk, and polyester polyester) were treated with the extract obtained from the dry leaves of Aloe arborescens Mill. Antibacterial activity of fibers against K. pneumoniae and S. aureus was investigated. Results showed that among the treated fabrics, silk, wool, and rayon fabrics exhibited darker shades when compared to other fabrics. In addition, dyed silk and rayon fabrics exhibited strong antibacterial activity [92]. Soybean fabrics were premordanted with iron turkey (Tamarindus indica L.) seeds, Emblica officinalis Gaertn., and tannin mordants obtained from Myrobalan fruits plants and dyed with marigold extract. The antibacteriality of the fibers was evaluated according to the AATCC 100 method. Results showed that amla extract yielded 60–88.65% bacterial reduction against S. aureus and 60.10–86.25% bacterial reduction against E. coli. Antibacterial activity decreased after washing [8]. Fig. 11  Aloe arborescens [125]

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Turmeric Turmeric, which is another plant (Fig. 12), is one of the plants whose antibacteriality has been studied. Indian saffron (curcumin) in turmeric (Curcuma longa L.) was applied to woolen fabrics with the help of dyeing and functional finishing process [77]. The antibacterial activity of treated fabrics against E. coli and S. aureus microorganisms, commonly known as pathogens, was investigated using the AATCC 100-1999 method. The washing resistance of the acquired antibacterial activity was also explored. Although the mechanism of antibacterial activity of turmeric is not fully understood, it was stated that the antimicrobial activity might be due to the presence of methoxyl and hydroxyl groups. The study results showed that wool fabrics treated with castor saffron provided antimicrobial activity against S. aureus (85% against bacteria) and E. coli (90% against bacteria) and subspecies of these bacteria. Furthermore, it was observed that antibacterial activity increases with increasing dye concentration. However, after 30 washes, antibacteriality decreased (in range 30–45%) [77]. In another study in 2009, woolen fabrics were dyed using turmeric (Curcuma longa L.), and antibacterial properties of extracts and treated fibers against Staphylococcus aureus, Shigella sonnei, Escherichia coli, Bacillus

Fig. 12  Turmeric [126]

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megaterium, Bacillus subtilis, Bacillus cereus, and S. epidermella were tested using diffusion method. Results showed that the extract produced from turmeric had an antibacterial effect against all bacterial species studied except Bacillus cereus [71]. In another study, cotton-knitted fabrics were dyed with turmeric (Curcuma tinctoria Guibourt) extract with various mordants using impregnation method. The study results showed that fibers provided a reduction in range 96.6–99.0% against bacteria [58]. In another study (2010), microcapsules encapsulated with the extract of turmeric (Curcuma longa) plants were applied to silk and cotton fabrics by pad-dry-­ cure method (UF silpure FBR-5 was used as binder), and antibacteriality of treated fibers was examined. Results showed that fabrics treated with turmeric extract exhibited antibacteriality against all studied bacterial species [102]. Cotton and silk fibers were dyed with turmeric extract in another study [59]. This study reported that the bacterial reduction in mordanted and unmordanted cotton and silk fibers varies between 89.58% and 100% against Staphylococcus aureus and 87.50–100% against Escherichia coli [61]. In another study (2011), where turmeric extract was applied to cotton fabrics by exhaustion method, the extract-treated fabrics provided antibacterial efficacy [51]. In another study, polyamide (nylon 6.6) fabrics were dyed with different Curcuma longa rhizome (turmeric) extract concentrations with the presence of different mordants. The study results showed that turmeric and polyamide fabric exhibited excellent antibacterial activity (against S. aureus and E. coli) and good fastness properties in the presence of iron sulfate, copper sulfate, and potassium aluminum sulfate mordants. In addition, turmeric was found to affect RNA and DNA of microorganisms [101]. In another study realized in 2013, curcumin (turmeric, castor saffron), which is both dyestuff and antimicrobial agent, was applied to cotton as antibacterial agent and antibacterial activities of the treated fibers were examined. Results showed that curcumin-treated cotton fabric provided antibacterial activity against S. aureus and E. coli bacteria, but after the fifth wash, antibacterial activity decreased to 40% against S. aureus and 50% against E. coli. In addition, curcumin dyed fabrics displayed low light fastness values [17]. In another study (2013), viscose fabrics were dyed with turmeric under different conditions and some of these fabrics were treated with silver nanoparticles, and then the antibacterial activities of these treated fabrics were examined. Results showed that wallnut-dyed fibers resulted in 81.89% bacterial reduction [69]. In another study realized in 2014, wool fibers were dyed using turmeric extract in the dyeing process where aluminum sulfate was used as mordant and antibacterial activities of the treated fibers were examined. The study results showed that the treated fibers exhibited bacterial reduction in range 90–99.5% against P. aeruginosa, 93–99.8% against S. aureus, and 90–99.6% against E. coli [65]. Unlike the above studies, this study examined the antimicrobiality of the pigment produced from a microorganism, not a plant (2009). Sclerotinia sp. cotton fabrics were dyed with the pigment obtained from microorganism (fungus). The antimicrobial activity of the treated fabrics against different pathogens (Bacillus cereus, Bacillus circulans, Bacillus megaterium, Escherichia coli, Staphylococcus aureus, Pseudomonas fluorescens, and Alkaligenes sp.) was examined. As a result of dyeing with p­ igments,

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fabrics displayed antimicrobial activity against E. coli bacteria [127]. In another study (2011), Streptomyces virginiae bacterium was used in the dyeing process (in order to form brown pigment dye). Results showed that dyed and printed fabrics exhibited good fastness values under optimum conditions. In addition, treated fabrics exhibited antimicrobial activity against Aspergillus niger [128]. In another study, extracts obtained from tannin-coated iron turkey (Tamarindus indica L.) seeds were applied to cotton, wool, and silk fibers with various mordant combinations, and the fibers were dyed with turmeric and pomegranate natural dyes. Results showed that turmeric-treated fabrics exhibited resistance to bacterial attack (Table 3) [82]. Table 3 shows the antibacterial activity of treated fibers was good. Fabrics treated with copper sulfate mordant could exhibit good antibacterial activity up to 20 or more washings when dyed with natural dyes. However, it is right to point out that antibacterial resistance of the treated fabrics after washing can reduce [82]. Wallnut Another plant investigated for textile antibacteriality is Juglans regia L. (Fig. 13). Woolen fabrics were dyed using the extracts from Juglans regia L., Urtica dioica, and Matricaria chamomilla. Antibacteriality of treated fibers and extracts was investigated. Results showed that extracts did not exhibit antibacterial effect [71]. In another study, wool fibers were treated with the aqueous extracts obtained from walnut shell in the presence of potassium bichromate, copper (2) sulfate, iron (2) sulfate, iron (3) sulfate, tin (2) chloride, aluminum sulfate, and tannic acid mordants. The antibacteriality of treated fibers against S. aureus, E. coli, and Pseudomonas aeruginosa bacteria was examined. Results showed that unmordanted fibers exhibited a bacterial reduction in range 50–76.50% against all studied bacteria. In addition, potassium bichromate treated and dyed fibers displayed 70% reduction against S. aureus alone; copper (2) sulfate treated and dyed fibers led to 99% reduction against all studied bacterial species. Iron (2) sulfate treated and dyed Table 3  Antibacterial properties of turmeric-treated fabrics [82] Reduction (%) Cotton Natural colorants Mordants S. aureus E. coli Curcumin Unmordanted 89.58 87.50 Tannin 94.44 93.75 Tannin +0.5% Cu 99.30 100 Tannin +1% Cu 100 100 Pomegranate Unmordanted 90.27 88.88 Tannin 93.75 91.66 Tannin +0.5% Cu 100 100 Tannin +1% Cu 100 100

Wool S. aureus 90.90 96.36 100 100 93.22 96.72 100 100

E. coli 88.36 95.45 100 100 92.72 96.36 100 100

Silk S. aureus 92.46 96.23 100 100 91.52 95.78 100 100

E. coli 88.19 95.78 100 100 90.96 95.48 100 100

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Fig. 13  Wallnut [129]

fibers exhibited 71.50% reduction against S. aureus, 94% reduction against E. coli, and 100% reduction against P. aeruginosa.Also, iron (3) sulfate and tin (2) chloride treated and dyed fibers displayed over 98% reduction against all studied bacterial species. Moreover, aluminum sulfate treated and dyed fibers resulted in over 97% reduction against all studied bacterial species. And finally, tannic acid treated fibers displayed 48% reduction against S. aureus, 94% reduction against E. coli, and 99% reduction against P. aeruginosa [55]. Wallnut shells were used for cotton natural dyeing with the presence of chitosan [44]. Results showed that the treated fibers exhibited antibacterial properties [44]. In another study in 2013, viscose fabrics were dyed with wallnut under different conditions and some of the fabrics were treated with silver nanoparticles. Moreover, the antibacterial activities of these fabrics were examined according to AATCC 100 test. Results showed that wallnut-­ dyed fibers displayed 81.73% bacterial reduction [69]. Henna Antibacteriality of henna has been investigated and proven in earlier studies (Fig. 14). For instance, wool fabrics were first coated with chitosan and then dyed with henna at a liquor ratio of 1:50 at 60°C for 90 minutes. Results showed that the treated fabrics are antimicrobial [66]. In another study, cotton-knitted fabrics were dyed with henna (Lawsonia inermis) with various mordant existence using the impregnation method. The study results showed that the treated fibers reduced the bacterial growth against S. aureus by 96.6% and against E. coli by 96.4% [58]. In another study on henna, tannin obtained from the dried fruits of amla (Emblica officinalis G.) was applied to cotton and silk fibers with the combination of tannin and copper sulfate mordant and then dyed with henna extract [61]. An increase in the antibacteriality of the fibers was observed with the application of mordants. Bacterial reduction on fibers treated with henna extract alone was in range 30.55–42.77%,

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Fig. 14  Henna [130]

while bacterial reduction on dyed fibers accompanied by amla mordant and 1% copper sulfate mordant was observed to be 100% [61]. In other study, henna extract was applied to wool yarns with the involvement of iron sulfate and alum mordants, and the antibacterial activity of treated fibers against Staphylococcus aureus, Escherichia coli, and Candida albicans was examined. In addition, commercial antibacterial agents (ampicillin and fluconazole) were also applied to wool yarns for comparison. The study results showed that henna-dyed fibers at 20% concentration yielded bacterial reduction in 91–93% range (this amount was in range 94–98% for commercial products). Henna exhibited antibacterial activity in solution, and this activity persists when applied to wool yarns [67]. In another study, the dyeing behavior of gamma irradiated bleached and mercerized cotton woven fabrics utilizing Lawson dye extracted from henna leaves was explored [68]. Cotton fabric and dye powder obtained from henna leaves were irradiated to different absorbed doses of 2, 4, 6, 8, and 10 kGy using Cs-137 gamma irradiator [68]. In order to improve the color fastness and colorimetric values of the dyed fabrics, various mordants (iron, copper) were included, and the antibacterial activity of irradiated and nonirradiated dyed samples was examined against S. aureus, Bacillus subtilis, E. coli, and Pasteurella multrocida. It was stated that cotton fabrics dyed with henna extract provided antibacterial activity. In addition, an increasing trend was observed in the antibacteriality of irradiated samples relative to the antibacteriality of nonirradiated samples [68]. Moreover, it was reported that gamma ray process of cotton dyed with extracts of henna leaves has considerably improved the color yield as well as enhanced the rating of fastness levels [68]. Viscose fabrics were also dyed with henna under different conditions in another study. Here, some of the fabrics were treated with silver nanoparticles, and then the antibacterial activities of these treated fabrics were examined. Results showed that before and after washing, fabrics dyed only with these natural dyes and then treated with silver nanoparticles exhibited excellent antibacterial activity. In the case of bacterial concentration reduction, it was stated that fabrics dyed with turmeric under alkaline

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conditions displayed higher effect than fabrics dyed with turmeric under acidic conditions; on the other hand, fabrics dyed with turmeric under neutral conditions did not exhibit good antibacterial activity [69]. In another study realized in 2014, aluminum sulfate (as mordant) was applied via premordanting method and premordanted wool fabrics were dyed with henna extract [65]. Antibacterial effect of dyed samples on gram-negative bacteria Pseudomonas aeruginosa, Escherichia coli and gram-positive bacteria Staphylococcus aureus was tested (using AATCC 100-1993 method). The study results showed that henna resulted in 80–99.8% bacterial reduction for Pseudomonas aeruginosa, 90–99.4% bacterial reduction for Escherichia coli, and 99–100% bacterial reduction for Staphylococcus aureus. It was reported that this antibacterial activity was associated with the chemical component of Lawsone (2-hydroxy-­1,4naptokinone) in henna [65]. Citrus grandis L. is another plant examined except henna. In the study realized in 2010, Citrus grandis L., which is used to improve the skin health of people, was applied to textile material (cotton-knitted fabric) at different temperatures, time, pH values, and concentrations (100%, 300%, 600%, and 800%  kwf). Antibacterial effect of the treated fibers was investigated against S. aureus and K. pneumaniae. The study results showed that the treated fabrics at concentrations of 600% and 800% provided bacterial reduction. It was stated that the dyed fabrics with a concentration of 800% resulted in a bacterial reduction of 98.3% against S. aureus. This indicates that these dyed fibers can be considered sufficient for hygienic uses. However, it is important to state that bacterial reduction values decreased after washing [70]. Barberry (Berberis vulgaris) Berberis vulgaris (Fig. 15) is another plant whose antibacteriality has been studied. Berberine natural dyes extracted from Berberis vulgaris L. with the involvement of Hymenosepalus torrey biomordant were applied to wool fabrics; and color yields, color fastness, and antibacterial properties of dyed wool fabrics were examined [74]. Results showed that darker colors can be obtained by increasing dyeing time, temperature, and pH, and also fastness values can be increased by the use of mordants. In addition, treated fabrics exhibited high antibacterial activity against all studied bacterial species [74]. Berberine dyestuff is a quaternary ammonium component and contains a positive charge at the N atom. This charge destroys the negatively charged cell membrane of the bacteria by disrupting the charge balance in the cell membrane. Other harmful effects of the quaternary ammonium component on microbes are degradation of proteins and cell structure breakdown [7, 74, 75]. Bleached cotton and cotton/modal blended knitted/woven fabrics were dyed with the natural extracts obtained from Berberis vulgaris, hot and cold dyeing reactive dyes, and sulfur dyes, and the antibacteriality of the dyed fibers was explored according to the AATCC 147 test method [132]. Fabrics dyed with Berberis vulgaris extract provided higher antibacteriality against S. aureus (with 28–35  mm inhibition zone) than E. coli (with 26–32 mm inhibition zone) [132].

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Fig. 15  Bar berry [131]

In another study realized in 2013, berberine, which is a natural cationic dye with excellent antibacterial activity, was obtained from the roots of Berberis vulgaris and cotton fibers were treated with this extract [75]. It is known that cationic dyes are normally not suitable for cotton dyeing. Plasma treatment and acrylic acid grafting, utilizing plasma technique for pretreatment, were performed in order to enhance the dye ability of cotton fiber. The influence of pretreatments on the dye ability of cotton fabric was investigated. The antibacterial efficiency of the dyed cotton fabrics was monitored using AATCC test method 100-2004. The samples dyed after acrylic acid grafting displayed the highest antibacterial activity with 99.2% bacterial reduction against S. aureus and 99.1% bacterial reduction against K. pneumoniae [75]. In other study, dyes obtained from Berberis vulgaris L. root extract was applied to wool fibers with the involvement of alum, copper sulfate, and potassium bichromate mordants, and the antibacteriality of the treated fibers was tested against K. pneumoniae and S. aureus with the utilization of AATCC 100-2004. The study results showed that treated and mordanted fibers exhibited excellent levels of antibacterial properties (bacterial reduction in range 99.4–99.6% against both bacterial species) [7].

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Basil (Ocimum sanctum L.) Another plant species tested for textile antibacteriality is Ocimum sanctum L. (Fig.  16). Extracts obtained from Ocimum sanctum L. were applied to cotton fabrics with direct application (pad-dry-cure: impregnation drying-thermophysics), microcapsulated dyestuffs, resin cross-linking, and their combinations (microencapsulated dye-resin cross-linking). Results obtained from all treated fabrics showed that the fibers have a bacterial reduction of 99.2–99.9% against S. aureus and 92.6–95.3% against K. pneumoniae [57]. In another study (2010), microcapsules encapsulated with Ocimum sanctum L. extract were applied to silk and cotton fabrics by pad-dry-cure (impregnation-drying-thermophysis method), and antibacterial activities of treated fabrics were examined. Results showed that Ocimum sanctum L.-treated fabrics exhibited antibacterial properties against all studied bacterial species [102]. In another study, alginate-chitosan nanoparticles with Ocimum sanctum L. extract obtained by using various extraction methods were applied to cotton fabrics (pad-dry-cure method). It was stated that 98–100% bacterial reduction were achieved as a result of the application of nanoparticles and Ocimum sanctum extract together, and 72–98% bacterial reduction was achieved only in fabrics treated with Ocimum sanctum [43]. Two other plants (Acorus calamus L. and Trigonella sp.) Fig. 16  Basil [133]

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were also examined for their antimicrobial activity against fungi (Aspergillus sp., Fusarium sp., Trichoderma sp.) and bacteria (Pseudomonas sp.) on cotton fibers. Results showed that plant extracts exhibited potential antimicrobial activity but provided low efficacy [89]. Onion Onion (Alium cepa L.) (Fig. 17) is another plant whose antibacteriality has been investigated. In a study realized in 2007, cotton fabrics were pretreated with low-­ temperature microwave plasma and then dyed using extracts obtained from onions with the graft method, and their antibacteriality (using the JIS L1902-1998 method) was examined against S. aureus. The highest inhibition zones against tested bacteria were 0.8–1.1 cm inhibition zone, which was obtained on the 10 minutes grafted cotton fabric sample with onion peel extract, and 0.5–0.8 cm inhibition zone, which was obtained on the 30 minutes grafted cotton fabric sample with onion waste peel extract [103]. Antibacterial activity of wool fabrics dyed with natural dyestuff obtained from onion was also investigated. S. aureus, Shigella sonnei, E. coli, Bacillus megaterium, B. subtilis, Bacillus cereus, Streptococcus epidermidis, Salmonella 21.3, and P. aeruginosa microorganisms were used in the examination of antimicrobials. Results showed that onion extract provided a reduction in range 32–52% against tested bacteria [52]. Cotton-knitted fabrics were dyed with onion (Alium cepa L.) with the involvement of various mordants (such as iron sulfate, copper chloride, zirconium oxy chloride, aluminum chloride, and alum) using the impregnation method. The antibacterial activity of the treated fibers was analyzed by the AATCC 100-1999 test method. Bacterial growth reduction on the treated fibers was 96.6% against S. aureus and 94.7% against E. coli. In addition, the fibers showed good antibacterial properties after 20 washes [58]. In another study in 2013, wool and cotton fabrics treated with chitosan (low, medium, and high molecular weights and different concentrations) were dyed with onion extract. It was reported that the growth of pathogens was reduced on pretreated and dyed cotton fabrics Fig. 17  Onion [134]

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(88–100% for all pathogens) and woolen fabrics (60–75% for all pathogens) with the application of high molecular weight chitosan at the highest concentration [45]. Rhubarb Another plant examined for antimicrobiality is Rheum emodi (Fig.  18). Iskin (Rheum emodi) extract was applied to cotton fibers. The extract of Rheum emodi displayed very little antibacterial activity. For instance, although Rheum emodi extract displayed antibacterial activity against Klebsiella pneumoniae, this extract exhibited no antibacterial activity against gram-negative bacteria Escherichia coli and Proteus vulgaris [2]. Wool yarns were dyed with extracts obtained from Rheum emodi L. using alum, copper chloride, and iron sulfate mordants. The antimicrobial activities (according to disc diffusion analysis) of treated fabrics and yarns against S. aureus and E. coli bacteria and C. albicans and Camdida tropicalis fungi were examined. The study results showed that R. emodi extract and treated wool yarns had efficacy against all microorganisms after the application (24.8–82.3% reduction against E. coli, 44.2–90.1% reduction against S. aureus, 26.8–93.4% reduction

Fig. 18  Rhubarb [135]

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against C. albicans, and 48.4–95.3% reduction against C. tropicalis). Compared with bacteria, the extract of this plant was relatively more effective against fungi. The mordants used also had a positive effect on color yield and color fastness properties and caused some decrease in antimicrobiality [81]. Golden Dock (Rumex maritimus L.) Rumex maritimus L. (Fig.  19) is one of the plants whose antimicrobiality has been studied. The extract of the Rumex maritimus L. was applied to cotton fibers. The study results showed that the extract did not provide antibacterial activity against any studied bacterial species [2]. In another study, wool fabrics were treated with extracts from Rumex maritimus L. The antibacterial activity (using agar diffusion test) of the extracts and treated fabrics against B. subtilis, E. coli, K. pneumoniae, P. vulgaris, and Pseudomonas aeruginosa was investigated. The study results showed that the extract only provided efficacy against K. pneumoniae [9]. The study results showed that R. maritimus had almost no antibacterial effect on the fiber [59]. Prickly Chaff-Flower, Apamarga (Achyranthes aspera L.) There are also studies investigating the antimicrobial activity of Achyranthes aspera L. (Fig. 20). Extracts obtained from Achyranthes aspera L. plant were applied to cotton fabrics as functional finishing process (dipping-by dipping), and the antibacteriality of the fibers was examined utilizing AATCC 147-1988, Agar diffusion and Hohenstein test method, and burying method. Fabrics treated with Achyranthes aspera extract displayed a 3 mm inhibition zone according to AATCC 147. In addition, results showed that the fabrics were resistant to microbial attacks [86]. It is Fig. 19   Golden dock [190]

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Fig. 20  Prickly chaff-flower [191]

stated that natural antimicrobial substances display not only ecological but also renewable properties. The extract from the leaves of Achyranthes aspera L. was applied with citric acid as a cross-linker to cotton fabrics as an antibacterial finishing process [91]. The antibacterial properties of the treated fabrics were tested using gram-positive S. aureus and gram-negative E. coli according to AATCC 100, AATCC 147, and agar diffusion (SN 195 920) tests. The study results of the study showed that finished cotton fabrics exhibited a 92% bacterial reduction against S. aureus and a 50% bacterial reduction against E. coli. It was also found that the plant extract exhibited antibacterial character due to the presence of a chemical substance called betaine [91]. Daisy Mexican chamomile (Tridax procumbens L.) (Fig. 21) is another plant studied for possible antibacterial effect. Mexican chamomile (Tridax procumbens L.) extracts were applied as microencapsulated dyestuffs to cotton fabrics as antibacterial finishing process using pad-dry-cure method (2007) [51]. The antibacterialities of the treated fibers were analyzed using the AATCC 100 agar diffusion method (against S. auereus and E. coli bacteria). Results showed that Mexican chamomile extract produced 98.75% bacterial reduction against S. auereus and 69.25% bacterial reduction against E. coli. Microencapsulated Mexican chamomile extract provided 92.15% bacterial reduction against S. auereus and 53.85% bacterial reduction against E. coli [87].

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Fig. 21  Daisy [136]

Chineese Goldthread (Coptis chinensis) Coptis chinensis (Fig. 22) is another plant whose antibacteriality has been studied. In a study in 2006, wool fabrics were dyed with extract of lady saline (Rhizoma coptidis: established root stem of Coptis chinensis Franch) with the involvement of iron (Fe+2) mordant, and the antimicrobiality of the treated fibers (using modified Quinn’s method) was examined. The results of the lady-dyed wool fabrics showed good antimicrobial activity against the E. coli (gram-negative bacteria) and C. albicans (fungus). This indicates that lady-saline can be used as a natural dye for medical applications. In fact, berberine-dyed fibers showed a higher antimicrobial activity and inhibition rate to E. coli than C. albicans. This outcome could be expressed as follows: the structure of quaternary ammonium salts in berberine molecules destroys the negatively charged cell membrane of the bacterium by disrupting the charge setting of the cell membrane [73]. In another study in 2009, cotton, wool, and silk fibers were dyed with the extract obtained from Coptis chinensis and the antibacterial activity of the dyed fibers against Staphylococcus aureus and Klebsilla pneumoniae was examined. It was stated that the antibacterial activity of Coptis chinensis may be because of berberine presence, which is known to display good antibacterial activity. The study results indicated that Coptis chinensis provided antibacterial reductions in range 95.7–99.9% against all studied bacteria [124]. Teakwood (Tectona grandis L.) Silk yarns were premordanted with copper sulfate, alum, tin chloride, and iron sulfate mordants and dyed with Tectona grandis L. (teak) (Fig. 23) extract. The antibacterial properties of dyed silk yarns were explored against K. pneumoniae, E. coli,

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Fig. 22 Chineese goldthread [137]

Fig. 23    Teakwood [192]

C. albicans, and A. niger according to the method AATCC 30 and 100 [104]. The treated yarns resulted in 1.5–1.8 mm inhibition zone for all microorganism species [104]. In a study (2011), cotton fabrics (mordanted with copper sulfate and iron sulfate according to premordanting and postmordanting methods) were dyed with the extract of green leaves of Teak (Tectona grandis L.) and their antibacteriality was examined. Results showed that the fibers dyed with the extract provided 17 mm inhibition zone against S. aureus, 18 mm against Shigella flexneri, 16 mm against Bacillus subtilis, and 18 mm against E. coli. In the same study, chawalkodi, orange narcissus (Calendula officinalis), and banana (Musa acuminate, Musa balbisiana) were also used. The study results showed that chawalkodi provided bacterial resistance to all studied bacterial species and banana displayed bacterial resistance against only S. flexneri, B. subtilis, and E. coli [80].

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Ratanjoti (Jatropa curcus) Ratanjoti or barbados hazelnut (Jatropa curcus) is another plant species studied for its possible antibacteriality property (Fig. 24). Cotton fabrics were dyed with the extract of Ratanjoti (Jatropa curcus), and their antibacteriality was examined. Results showed that the fibers dyed with the extract showed no inhibition against S. aureus and Shigella flexneri, and displayed 15  mm inhibition zone against Bacillus subtilis and 14 mm inhibition zone against E. coli [80]. In another study in 2013, Barbados hazelnut (Jatropha curcas L.) leaf extract was applied to cotton fabrics as a finishing process and its antibacteriality was examined. The study results showed that this extract contains components such as phenolic, terpenoids, flavonoids, alkaloids, glycosides, steroids, and tannins, and these contents exhibit antibacterial property. Some of these components function as bactericides (bacteriocytes) and some of them function as bacteriostatic. The study showed that treated fibers provided a considerable inhibition zone [105]. Green Tea The antibacteriality of the cotton fibers treated with green tea [Camellia sinensis (L.) Kuntze] (Fig. 25) extracts using pad-dry-cure method, and citric acid as a crosslinker was examined. The study results showed that the treated fibers exhibited antibacterial properties [141]. In another study, wool fabrics were dyed with green tea extract by applying aluminum sulfate. The fibers were then tested against gram-­ negative bacteria Pseudomonas aeruginosa, Escherichia coli, and gram-positive bacteria Staphylococcus aureus using the AATCC 100-1993 method. The study results showed that green tea led to 80–99.3% bacterial reduction for Pseudomonas aeruginosa, 85–99.3% bacterial reduction for Escherichia coli, and 90–100% bacterial reduction for Staphylococcus aureus [65]. Apart from green tea extract, the extracts of Ricinus communis L., Senna auriculata (L.) Roxb., and Euphorbia hirta L. plants were prepared with methanol solvent. These extracts were applied to four Fig. 24  Ratanjoti [139]

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Fig. 25  Green tea [140]

different (68% cotton + 32% polyester, 68% cotton + 32% polilycra, 68% cotton + 32% lycra, and 100% cotton) denim fabrics, and the antibacterial activity of treated fibers against S. aureus and E. coli bacteria was examined according to AATCC 147 method. According to the results of the studies, the majority of the treated fabrics exhibited antibacterial activity [142]. Gromwell (Lithospermum erythrorhizon) Silk fibers were dyed with shikonin (provides red ink) obtained from pearl (Lithospermum erythrorhizon Siebold. & Zucc.) (Fig. 26), and antibacteriality and UV protection properties of the treated fibers were examined. The fabrics were postmordanted, and the antibacterial activity of silk fabrics against S. aureus and E. coli bacteria was investigated. The percentage of E. coli reduction on dyed silk fabric was found to be 91–95.9%, and the percentage of S. aureus decrease was 86.7–92.2% [144]. In another study, cotton fabrics were dyed with extract obtained from the roots of pearl grass (Lithospermum erythrorhizon Siebold. & Zucc.). The results showed that pearl, which provides a dark purple color, provided good antibacterial properties. The fibers showed a bacterial reduction of 99.8–99.9% against S. aureus and 29.2–98.9% against K. pneumoniae. In addition, these properties can be improved by using gallnut mordant [6]. Spurge (Euphorbia humifusa) Euphorbia humifusa (Fig. 27) is another plant whose antibacterial activity has been examined. An investigation was performed on the bacterial suppressor concentration of the natural antibacterial components extracted from Euphorbia humifusa Willd. According to the results of the experiments, silk fabric exhibited good ­antibacterial activity when treated for 60 minutes at pH 4 with 90% extract concen-

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Fig. 26  Gromwell [143]

Fig. 27  Spurge [145]

tration at 90 °C. However, in the case of silk fabrics after 30 washes, the rate of suppression of growth of S. aureus bacteria decreases from 100% to 61.8%, and the rate of suppression of growth of E. coli reduced from 89.31% to 67.86% [110]. Red Kamala/Kum Kum Tree (Mallotus philippinenis) Cotton fibers were dyed with mallo tree (Mallotus philippinenis) (Fig. 28) extract. The antibacterial activity of the extract and the fabrics treated with this extract tested against Klebsiella pneumoniae, Escherichia coli, and Proteus vulgaris using ATCC

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Fig. 28  Red kamala/kum kum tree [146]

6538: SN 195 920 (agar diffusion test). The results showed that mallo tree extract was effective against all studied bacterial species. Cotton fiber dyed with this extract showed an effective biocide effect [2]. Tamarind (Tamarindus indica) Extracts were obtained from the tannin coated seeds of Tamarind (Tamarindus indica L.) (Fig. 29). And tannin extract of Tamarind (Tamarindus indica L.) seeds, tannin mordant, and their combinations with copper sulfate were used as mordant materials for dyeing cotton, wool, and silk fibers using turmeric and pomegranate rind. In addition, the antibacterial activity of dyed fibers against Staphylococcus aureus and Escherichia coli bacteria (using the AATCC 100-2004 test method) and their washing resistance were investigated [82]. The premordanted fabrics resulted in higher color yield, wash, and light fastness than unmordanted fibers. It was reported that the minimum inhibition concentration was 1% against both Staphylococcus aureus and Escherichia coli bacteria. The mordanted (with 0.5% and 1% copper sulfate mordant) and dyed fabrics led to nice antibacterial activity up to 20 washings [82]. Noni Fruit (Morinda citrifolia) Silk yarns were dyed with Morinda citrifolia (Fig. 30) using various mordants and antimicrobial properties of the dyed yarns against K. pneumoniae, E. coli, C. albicans, and A. niger were examined. Silk fibers (at 10% concentration) displayed 1.43–2 mm inhibition zone for all studied microorganism species. In the same study, Terminalia catappa and Artocarpus heterophyllus were also used. The fibers treated with these extracts provided 1.7–2.26  mm inhibition zone against studied four microorganisms. In addition, extracts were also used together in this study and the combinations also provided antimicrobial activity [104].

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Fig. 29  Tamarind [147]

Fig. 30  Noni fruit [148]

Peony Peony (Fig. 31) is another plant species whose antimicrobiality has been studied. Cotton, wool, and silk fibers were dyed at a 1:100 liquor ratio and 80 °C for 60 minutes with the extract of peony, and the antibacterial efficacy of dyed fibers against Staphylococcus aureus and Klebsilla pneumoniae bacteria was examined [50]. Peony-treated cotton fabrics displayed 98.8% and 0% bacterial reduction against

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Fig. 31  Poeny [149]

Staphylococcus aureus and Klebsilla pneumoniae, respectively. Similarly, peony-­ treated silk fabrics exhibited 99.7% and 0% bacterial reduction against Staphylococcus aureus and Klebsilla pneumoniae, respectively. In line with the results of dyed cotton and silk fabrics, peony-treated wool fabrics showed 99.4% and 0% bacterial reduction against Staphylococcus aureus and Klebsilla pneumoniae, respectively. Although there is no known specific component that provides the antibacterial activity of peony extract, this activity might be due to the unknown minor components such as tannin and steroid [50]. Knotweed (Polygonum cuspidatum) Resveratrol (RES), known to exhibit antibacterial, antifungal, and anti-­inflammatory properties and obtained from Polygonum cuspidatum (Fallopia japonica Houtt. (Ronse Decr.)) (Fig. 32) extract, was also applied to textile materials. Extracts were applied to the cotton, bamboo, and silk knitted fabrics by exhaustion method. Results showed that silk and cotton fabrics can be functionalized with resveratrol [151]. Amla Cotton and silk fibers were premordanted with tannins obtained from the dried fruits of amla (Emblica officinalis G.) (Fig. 33), tannin, copper sulfate, and their combinations and then dyed with pomegranate extract [61]. Antibacterial properties of these dyed fibers against Staphylococcus aureus and Escherichia coli were also investigated utilizing AATCC 100-2004. Bacterial reduction against Staphylococcus aureus and Escherichia coli in the case of mordanted and unmordanted cotton fibers were 90.27–100% and 88.88–100%, respectively. On the other hand, in the case of

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Fig. 32  Knotweed [150]

Fig. 33  Amla [152]

mordanted and unmordanted silk fibers, bacterial decrease against Staphylococcus aureus and Escherichia coli were 91.52–100% and 90.96–100%, respectively. It was reported that the antibacterial activity observed in the fibers continues, albeit with a reduction of up to 20 washes [61].

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Tobacco Various extracts were obtained from tobacco (Nicotiana tabacum L.) (Fig.  34) leaves using solvents such as water, acetone, DMF (N,N-dimethylformamide), and ethanol, and cotton fabrics were treated with these extracts. Treated fabrics displayed antibacterial activity against gram-positive (S. aureus) and gram-negative (E. coli) bacteria by providing a zone of inhibition of 21.33–23.46  mm and 18.50–19.67 mm, respectively [106]. Capsaicin Capsaicin (Fig. 35), a natural antibacterial substance, was coated on the surfaces of wool and cotton fabrics using sol–gel technique, and the antibacterial properties of these fabrics against E. coli bacteria were evaluated. Results showed that capsaicin-­ coated fabrics exhibited more significant antibacterial activity than the fabrics coated with the sol–gel (silica sol–gel) method without the use of capsaicin. In addi-

Fig. 34  Tobacco [153]

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Fig. 35  Capsaicin [154]

tion, although some reductions in antibacterial effect occurred after washing, capsaicin remained in the fibers after washing [155]. Cloves Clove (Fig. 36) is another plant whose antimicrobiality has been studied. Cotton, wool, and silk fibers were dyed with the extract obtained from carnation, and the activity of the treated fibers against Staphylococcus aureus and Klebsilla pneumoniae was examined. It was stated that the measured antibacterial activity with the presence of clove involvement might be due to phenol component in eugenol. In addition, the study results of the study indicated that carafil provided 99.9% antibacterial reduction against all studied bacteria [50]. Mango Cotton fabrics were dyed with extract of Mango (Mangifera indica) (Fig. 37), and the antibacteriality of the treated fibers was examined. Results showed that the treated fibers displayed 19–24 mm inhibition zone against four bacterial species [80]. Due to environmental factors (such as environmental pollution), the potential of using plant residues as a natural dye in textile dyeing has increased the interest in natural products in the recent years. In another study (2013), the effects of natural dyes obtained from Mangifera indica, Glochidion lanceolarium, and Litsea sebifera plant species on dyeing of silk and cotton yarns by using cationic and anionic surfactants were

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Fig. 36  Cloves [156]

Fig. 37  Mango [157]

studied, and antibacterial properties of dyed fabrics were examined using AATCC 100 method. Dyed yarns were reported to exhibit good bacterial regression. Alum (K2SO4Al2 (SO4) 3.24H2O), copper sulfate (CuSO4.5H2O), tin chloride (SnCl2.2H2O), and iron sulfate (FeSO4.7H2O) were used as mordant substances. Results showed that the interaction of natural dyes with cetyltrimethylammonium bromide cationic surfactant (surfactant) and sodium dodecyl benzene sulfonate anionic surfactant was remarkable. The color yields of the yarns dyed using cationic surfactant were higher than those dyed using anionic surfactant. Results showed that cotton yarns dyed with natural dye from leaves of G. lanceolarium plant using cationic surfactant provided good inhibitory effect against all studied bacteria (K. pneumoniae, S. pyogenes, and S. aureus) except E. coli. It was found that the cotton yarns dyed with these extracts adversely affected S. aureus growth (inhibition: 61–86.7%). M. indica provided the highest blocking effect [158].

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Mimosa It is known that microbes can adhere to textile materials with the sweat coming out of the human body and this may lead to fiber breakdown. Phyllanthus urinaria L. extracts have a positive inhibitory effect on the growth of S. aureus, Typhoid bacillus, P. aeruginosa, etc. Cotton fabrics were dyed with P. urinaria plant (Fig.  38) extract, and treated fabrics were found to have significant antibacterial activity [160]. Atractylodes lancea Atractylodes lancea Thunb. (Fig. 39) extract was obtained using water, methanol, acetone, and hexane, and antibacterial activities of these extracts were examined. Furthermore, these extracts were also applied to cotton fabrics. Results showed that the extract obtained using acetone provided significant antibacterial activity against all studied bacterial species [against E. coli (20.23 mm), for B. subtilis (15.42 mm), and for S. aureus (13.06 mm)]. These extracts were then applied to cotton fabrics, and the antibacterial properties of the fibers were also examined. Results showed that the antibacterial activity of the fabrics treated with copper sulfate provided a zone of inhibition zone of 7.22–9.16  mm. Copper sulfate-treated fibers provided inhibition zones of 8.49–15.42 mm [162]. Arnebia nobilis The dyes extracted from Arnebia nobilis Rech f. (Fig. 40), which were used as natural red dye source, were applied to cotton fabrics as antibacterial finishing process [107]. In this study, the major components of the extract (alkanin β and β-dimethylacrylate) and the extract were applied as an antibacterial finishing process Fig. 38  Mimosa [159]

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Fig. 39  Atractylodes lancea [161]

Fig. 40  Arnebia nobilis [163]

to nylon, polyester, silk, wool, cotton, and acrylic fabrics. Fibers treated with extracted dyestuff and components from Arnebia nobilis Rech f. exhibited antibacterial activity against S. aureus and E. coli. Treated polyester, wool, silk, and acrylic fibers exhibited a bacterial reduction of 99.9–100% against S. aureus, but treated nylon and cotton fabrics showed no bacterial reduction. Treated wool, silk, and acrylic fabrics showed a 99.9–100% bacterial reduction against E. coli, and treated polyester fibers displayed a 75% bacterial decrease; on the other hand, treated nylon and cotton fibers showed no bacterial reduction. Washings were applied to the treated fibers, and the antibacterial activity was not diminished after the applied washings. However, antibacterial activity was considerably reduced when fibers were exposed to light [107].

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Mandarin Hundred percent silk fabrics were dyed with the extracts from the immature fruit of Satsuma mandarin [Citrus unshiu (Swingle) Marcow] (Fig. 41) via both premordanting and postmordanting methods at 200%, 300%, 400%, 500%, and 600% concentrations. Aluminum sulfate, copper sulfate, and iron sulfate were used as mordant materials. All fabrics dyed with 300% dye concentration and more displayed over 99% antibacterial activity against K. Pneumoniae and S. aureus [165]. Eucalyptus Eucalyptus odorata Behr and Eucalyptus cinerea F. Muell (Fig. 42), which contain enriched tannin and flavanoid extracts, are two different species of the eucalyptus plant. Ex Benth.’s extracts obtained from the leaves were applied to cotton and wool fiber fabrics, and their antibacterial activities were investigated. Results showed that only wool fibers treated with Eucalyptus odorata Behr extract exhibited antibacterial properties [108]. European Spruce (Picea abies) Gentamicin sulfate and self-forming essential oil of European spruce (Picea abies (L.) H. Karst.; the natural antimicrobial agent) (Fig. 43) was applied to knitted fabrics (Polyamide 6.6/elastane (80%/20%) as printing material and the antimicrobial properties of the treated fibers against Staphylococcus aureus, Escherichia coli, Klabsiella, and Candida albicans) were examined. Polyamide 6.6/elastane knitted fabrics coated with gentamicin sulfate and essential oil of European spruce was reported to exhibit a broad range of bactericidal, bacteriostatic, and antifungal activity [168]. Fig. 41  Mandarin [164]

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Fig. 42  Eucalyptus [166]

Fig. 43  European spruce [167]

Leadwort Different concentrations of extracts obtained from Plumbago europaea L. (Fig. 44) plant were applied to 100% cotton fabric using pad-batch method. Results showed that the fabrics exhibited antibacterial activity against Helicobacter pylori, E. coli,

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Fig. 44  Leadworth [169]

and S. aureus. P. zeylanica L., the major components of Plumbago europaea, can exhibit antibacterial activity [170]. Anatto Silk fabrics were dyed using annatto (Bixa orellana) seed (Fig. 45) extract. Color fastness levels and antibacterial activities of the fabrics (using AATCC 100 method) were investigated. Dyed fabrics were reported to exhibit antibacterial activity [109]. Champaka Functional finishing processes [as a conventional method with triclosan and as a more sustainable process type utilizing Michelia×alba (DC.) Figlar (Fig. 46) extract] was applied to cotton/organic cotton blend yarn dyed with reactive dyes by using pad-dry-cure method. The antibacterial properties of the treated fibers were investigated according to the AATCC 147 method. Conventionally applied fibers provided an inhibition zone of 25 mm against S. aureus and 20 mm against E. coli. Fibers treated with plant extracts provided an inhibition zone of 23 mm against S. aureus and 25 mm against E. coli [173]. Papaver rhoaes Different combinations of cationization, mordanting, and dyeing processes were applied to cotton fabrics dyed with Papaver rhoaes (Fig. 47) extract, and antibacterial properties of dyed fabrics were examined. Results showed that the poppy plant extract did not exhibit a significant inhibition inhibitory effect, but the inhibitory

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Fig. 45  Anatto [171]

Fig. 46  Champaka [172]

effect increases with mordanting. The highest antibacterial activity was reported to be achieved by cationization followed by mordanting with copper (II) sulfate mordant and subsequent dyeing [175]. Mentha sp. Mint (Fig.  48) has also been studied for textile antimicrobiality obtainment. For instance, antibacterial activities (using disc diffusion method (NCCLS-1997) of the wool dyed with natural dyestuff obtained from mint (Mentha sp.) was tested against S. aureus, Shigella sonnei, E. coli, Bacillus megaterium, B. subtilis, Bacillus cereus, Streptococcus epidermidis, Salmonella 21.3, and P. aeruginosa microorganisms.

164 Fig. 47  Papaver rhoaes [174]

Fig. 48  Mentha sp. [176]

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Results showed that mint displayed a bacterial reduction of 75% against B. cereus, 88% against B. subtilis, 91% against P. aeruginosa, and 28% against S. epidermis [52]. Mahonia The antifungal activity of extracts from the leaves of Mahonia napaulensis D.C. (Fig.  49) against four pathogenic fungal species (Colletotrichum capsici, L. trifoli, Alternariabrassicicola, and Helminthosporium solani) was investigated. This research was carried out using Mahonia sp. plant extract as a natural, environmental friendly antifungal finishing process in order to improve the application of textiles. Results indicated that antifungal efficacy was achieved with Mahonia extract (83.33%) [178]. Boneset Tencel and tencel-viscose fabrics were dyed with natural dye of influenza grass (Eupatorium sp.) (Fig. 50) with different types of mordants, and their antibacteriality against K. pneumoniae and S. aureus according to the AATCC 100 2004 method was investigated. It was stated that microorganisms can be controlled in tencel and tencel-viscose fabrics dyed with Eupatorium sp. Furthermore, it was reported that such effective processes can prolong the service life of the textile material [180]. Ashoka Extracts of Saraca osaca (Fig.  51) and Albizia lebbeck plant species from their leaves and tree barks were used for dyeing silk yarns, and their antimicrobiality against K. pneumoniae, E. coli, C. albicans, and A. niger was tested using AATCC Fig. 49  Mahonia [177]

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Fig. 50  Boneset [179]

Fig. 51  Ashoka [181]

30, AATCC 100, and potato dextrose agar plate. As a result of this study, it was determined that both solution and dyed material had antimicrobial activity. Dyed silk yarns exhibited antimicrobial activity (approximately 38–55% reduction in fungal growth) against Aspergillus niger, a fungal strain [182]. Madhuca indica Silk fabrics were dyed with extract from the bark of Madhuca indica (Fig. 52) plant in the presence of mordants with different concentrations. Madhuca bark was not effective on E. coli, Streptococcus sp., and Salmonella growth, while same substance displayed antibacterial activity against S. leuteus. In addition, Aspergillus nigricans and Candida albicans are dye-resistant microorganisms [184].

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Fig. 52  Madhuca indica [183]

Fig. 53  Legume forages [185]

Legume forages Wool fibers were treated with enzymes (protease) and mordants in the presence of various natural dyes (Grevillea robusta A. Cunn.exR.Br., Spathodea campanulata P. Beauv., Senna auriculata (L.) Roxb. (Fig. 53), and Acacia decurrens (Wendl) .f.) Willd. Mimosa L.), and the antibacteriality of the treated fibers against S. aureus and E. coli was examined. The study results showed that antibacteriality of wool fibers increased significantly after enzyme and mordanting process. The control fabric (dyed only with natural dyes) showed activity only against S. aureus, while enzyme-treated fabrics showed activity against both bacteria [186]. Another study pretreated with citric acid under oxidizing conditions and dyed with the same plants (Grevillea robusta A. Cunn.exR.Br., Spathodea campanulata P. Beauv., and Senna auriculata (L.) Roxb. times via direct method and their antibacteriality of treated fibers against S. aureus and E. coli were also investigated. Results showed that only dyed fibers showed activity only against S. aureus, whereas fibers pretreated with citric acid showed activity against both bacterial species [187].

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 nimal Extracts That Impart Antimicrobiality to Textile Fabrics A and Their Applications Antimicrobial textile fabrics with the treatment of animal extracts and the applications of these extracts are reviewed in this section. Chitosan Chitosan is another natural product that has been investigated for antimicrobiality, and in this review chapter, only studies with natural dyes have been mentioned (Fig. 54). In one study, before and after oxidation of the fabrics, chitosan as biopolymer and citric acid as a cross-linking agent were subjected with pad-dry-cure technique. Results showed that wool fabrics treated with citric acid and chitosan prior to oxidation did not exhibit antibacterial or antiseptic properties. However, it was shown that fabrics oxidized and subsequently treated with citric acid and chitosan exhibited antibacterial or antiseptic properties. In addition, the acquired antibacterial activity decreased after washing [36]. Bleached 100% cotton fabrics using chitosan and chitosan/polyethylene glycol (PEG) is applied as antibacterial finishing. AATCC 100 test was used in this study. The study results showed that chitosan and chitosan/PEG treated fabrics exhibited small bacterial resistance against S. aureus. It was stated that this finishing process could not be used in clothing [37]. In addition to natural dyes, substances such as Aloe vera (L.) Burm. f., chitosan, and turmeric (active ingredient in Curcuma longa L.) were also applied to cotton, wool, and rabbit hair fibers alone or in various combinations. Antibacterial activity of chitosan varied according to fiber structure. The sorption to the cellulosic/protein fiber structures of chitosan occurs with negative charges (–O– hydroxyl anions in the cellulosic polymer and –COO– with carboxylate anions in the protein polymer), and protonated amino groups (NH3 +) of the chitosan, hydrogen bonds, and van der Waals forces. However, the affinity of chitosan is generally considered to be poor, Fig. 54  Chitosan [188]

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and in this case, when administered on its own, it weakens antibacterial activity [47]. Henna, which has proven antibacterial (bactericidal) properties, was applied together with chitosan to impart antibacterial properties to wool fabrics. In this study, wool fabrics were first coated with chitosan (pad-dry-cure) and then dyed with henna. ASTM E 2149-01 method (against S. aureus and E. coli) was used as antibacterial test in this study. Results showed that treated fabrics were antibacterial [66]. In another application of chitosan, chitosan and tannic acid were applied to cotton fabric alone or in combinations. Results showed that tannic acid had higher antibacterial activity than chitosan when applied alone. The highest antibacterial efficacy (for 24.2  mm  S. aureus and 21.1  mm E. coli) was achieved by co-­ administration of chitosan and tannic acid to peroxide treated fabrics [38]. In another study, cotton fabrics were treated with sulfamidine/chitosan (pad-dry-cure impregnation-­drying-thermophysis), and the antibacterial antibacterial activities (AATCC 100) of treated fabrics against S. aureus and E. coli were evaluated. Treated fabrics were found to exhibit more efficacy to S. aureus (bacterial reduction in range 80–98.2%) than E. coli (bacterial reduction in range 70.5–94.3%) [39]. In another study, wool fabrics were treated with chitosan using ultrasonic methods. The paper disk diffusion method was used as an antibacterial test [40]. By using ultrasonic equipment, it was aimed to reduce energy and material consumption and create less damage to the fibers. Results showed that this method reduced the processing time. Compared with other methods, it was noted that the treated fabrics can be dyed better and exhibited better dimensional stability (less shrinkage on woolen fabrics), and also showed that treated woolen fabrics exhibited antibacterial properties against S. aureus and P. aeruginosa. The study results showed that woolen fabrics provided antibacterial efficacy after the application of 15 g/L concentrates against gram-negative P. aeruginosa and provided efficacy after 10 g/L concentration against gram-positive S. aureus [40]. Hundred percent cotton, viscose, and polyester fabrics were treated with nanochitosan pieces as an antimicrobial finishing process (via exhaust method), which is harmless to the environment. AATCC 100-2004 and AATCC 124-2009 standards were used as antibacterial test. The study results showed that the finished fabrics showed significant antibacterial activity against S. aureus. With this finishing process, it was observed that nanochitosan coated antibacterial fabric could be produced. It was stated that the applied process was environmental and resulted in low cost [41]. In another study, nanochitosan pretreatment (by pad dry-cure method) was applied to cotton fabrics followed by direct dyestuffs and nanosilver colloid was applied to the fabrics. The study results showed that dye uptake and washing fastness of nanochitosan treated fabrics improved. Increased antibacterial properties was observed by reducing nanochitosan particles or by combining nanosilver colloids with nanochitosan [42]. Furthermore, Ocimum sanctum L. extract obtained by using various extraction methods was subjected to cotton fabric as functional finishing process with alginate-­ chitosan nanoparticles addition. In this study, AATCC 100 agar diffusion test against B. subtilis, S. aureus, E. coli, P. aeruginosa, A. niger, and Penicillium sp. microorganisms was investigated. The study results revealed that plant-encapsulated nanoparticles acted as biocontrol agents against bacteria in fabrics. It was observed

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that the combination of nanoparticles and Ocimum sanctum extract resulted in a bacterial reduction of 98–100%. It was reported that only nanoparticle-treated fabrics provided bacterial reduction in range 20–24% [43]. In another study in 2013, chitosan was applied to cotton fabric in order to impart antibacterial properties against gram-negative bacteria E. coli. In this study, the effect of chitosan and mordanting on the dyeing properties of cotton fabrics dyed with natural dyes such as wallnut shell and safflower was investigated. Although dyeing of chitosan treated fabrics reduced their antibacterial activity, results showed that chitosan-treated cotton fabrics exhibited antibacterial properties against E. coli [44]. In another study, antimicrobial activity of wool and cotton fabrics treated with chitosan (low, medium, and high molecular weights and different concentrations) were tested against Aspergillus flavus, Aspergillus niger, Penicullium spp fungi, E. coli, and P. aeruginosa bacteria. Color yields, color fastness values, and antimicrobial efficiencies of cotton and wool fabrics treated with chitosan, dyed, and undyed fabrics with onion extracts were examined. It was noted that the growth of pathogens was reduced in high molecular weight and 2% concentration of chitosan pretreated cotton fabrics (88–100% for all pathogens) and woolen fabrics (60–75% for all pathogens). Bacterial reduction increases with increasing molecular weight and concentration of chitosan. In addition, dye adsorption on fabrics increases and fastness values are improved with this process. Antimicrobial activity, expressed as a decrease in the growth of bacteria, can be expressed as follows: the amino groups in the chitosan accumulate on the cell surface and bind to DNA to inhibit mRNA synthesis, which interferes with bacterial metabolism. High molecular chitosan is more prone to settle on the fabric surface, and as a result, bacterial amino groups are more accessible. The causes of the antimicrobial character of chitosan are controversial, and there are two hypotheses. In the first hypothesis, polycationic chitosan depletes the electronegative charges on the cell surface and the cell permeability changes, thereby causing leakage of intracellular electrolytes and stable components. In the second hypothesis, chitosan enters the fungal cells and then adsorbs the necessary nutrients, thereby slowing or inhibiting the synthesis of proteins and mRNA [45]. In another study where Aloe vera (L.) Burm. f extract was applied on its own as well as with turmeric and chitosan combinations (2012), it was reported that aloe vera extract provided higher antimicrobial activity as a result of addition of turmeric and chitosan [48]. Lac (Kerria lacca) The antibacterial activity of the extract obtained from lac (Kerria lacca) (Fig. 55) insect was examined, and cotton fibers were dyed with this extract. Antibacterial activity of dyed samples against Klebsiella pneumoniae, Escherichia coli, and Proteus vulgaris against gram-negative bacteria was investigated. The extract showed a very low activity against Klebsiella pneumoniae alone [2]. In another study (2005), wool extracts were treated with the extracts obtained from lac insect (Kerria lacca Kerr, 1782). The lacquer insect has been shown to exhibit no

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Fig. 55  Lac [189]

antibacterial activity against any selected test bacteria [9]. The results of another study conducted in 2005 showed that K. lacca showed no activity against any tested bacteria [59].

3  Conclusions Bacteria and fungi are the most important microorganisms for textile industry. Body temperature is an important factor for the growth of fungi and bacteria in the body, but also the amount of sweat released from the sweat glands and the chemical content of the sweat are also important factors. While fungus causes staining and biodegradation on the textile material, bacteria also can result in undesirable bad odors. These organisms can cause color change, bad odors, and staining as well as lower the strength of textile products. Although antimicrobial chemicals can provide protection benefits to textiles, chemical usage during their production can cause potential problems to environment. The majority of antimicrobial agents exhibit potent activity against both bacteria and fungi, but the number of substances that equally affect all microorganisms is quite small. Many chemical antimicrobial agents such as commercial triclosan, silver, polyhexamethylene biguanide-PHMB, and quaternary ammonium compounds are generally used in finishing processes. However, antimicrobial agents, to be used in textile products, should not threaten human health. Moreover, obtained antimicrobial effects should be stable to repeated washing cycles and ironing conditions. For these reasons, to provide antimicrobial effect to textile surfaces, several natural alternatives are investigated as an alternative for chemicals. Biological active components of plants have been utilized for imparting antimicrobial activity to textile materials. Several studies showed the obtained antimicrobial effects on textile products that were imparted by ecologic, antiallergic, harmless to human and environment, sustainable, renewable, and biodegradable substances such as natural dyes and other natural substances. Many different natural resources based on plant and animal extracts that impart antimicrobiality to textile

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fabrics have been investigated. Finally, the use of sustainable natural resources for the production of antimicrobial textiles is expected to increase day by day leading to greener planet.

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Index

A Abaca fibers, 43, 44 Acacia, 116–118 Acetylation process, 7 Agave americana fibers cactus, 8 elongation, 10 spectrophotometer measurement, 9 surface treatment, 9 tensile strength, 9 ultrasonic energy, 10 Agave sisalana, 40 Alkali process, 6 Alkalization, 103 Aloe arborescens, 133 Aloe vera, 131–133 Amla, 153 Ancestral knowledge, 50, 55, 62, 85 Animal extracts chitosan, 168–170 lac, 170 Annatto, 162 Antimicrobial fabrics animal extracts (see Animal extracts) natural dyes, 116 plant extracts (see Plant extracts) Antimicrobials activity, 113 properties, 113 textile products, 113 Arnebia nobilis, 158 Artisanal spinning process, 72, 74 Ashoka, 165 Atractylodes lancea, 158

B Bamboo fibers applications, 35 economic species, 34 properties, 35 species, 34 technical fibers, 34 walls and layers, 34 woody grasses, 33 woody stems, 34 Banana fiber, 44 Basil, 141 Berberine, 115 Berberis vulgaris, 139, 140 Biocomposites, 101 Biodegradation, 88 Biofibers, 88 Boneset, 165 C Cannabis sativa, 90 Capsaicin, 155 Cellulose-based fibers, 4 Cellulose-based natural fibers, 46 Champaka, 162 Chineese goldthread, 146 Chitosan antibacterial activity, 168 antibacterial test standards, 169 antimicrobial character, 170 application, 169 biopolymer and citric acid, 168 cell surface, 170

© Springer Nature Switzerland AG 2020 S. S. Muthu, M. A. Gardetti (eds.), Sustainability in the Textile and Apparel Industries, Sustainable Textiles: Production, Processing, Manufacturing & Chemistry, https://doi.org/10.1007/978-3-030-38541-5

181

Index

182 Chitosan (cont.) cotton fabric, 170 nontoxic biopolymer, 114 PEG, 168 ultrasonic methods, 169 Cloves, 156 Coconut fibers, 45 Composite applications, hemp alkalization, 103 biocomposite, 101 biodegradable polymers, 101 carbon fiber composites, 101 chemical/mechanical preparation, 102 environmental impacts, 102 green composites, 103, 104 materials, 101 polyesters, 100 polymer matrix, 100, 101 techniques, composite manufacturing, 100–101 thermoplastic, 100 Cotton fibers chemical structure, 32 conventional textiles, 33 cost-efficient production, 31 hairs, 32 physical structure, 32, 33 production and consumption values, 32 Coyoyo silk artisanal spinning process, 72, 74 caterpillar, 64, 65 cocoons, 63 collecting and weaving, 63 cruelty-free, 62 Doña Pabla, 56, 62 luxury risk, 83, 84 production, 56 Purucha/Pulucha, 56 risk, 85 social enterprise, 85 sophisticated winding tools, 64 sustainable luxury, 85 thread, 65–67, 70, 71 weaving process, 76, 79 Craftsmanship, 54, 55 Cryogenic degumming, 97 Cultural heritage, 50, 54, 55, 83, 85 D Daisy, 145 Degumming, 94, 97 Dew/field retting, 95, 96

E Electrolytic degumming, 98 Environmental sustainability, 2 Eucalyptus, 160 European spruce, 160 F Fiber composites, 4 Fiber modifications acetic acid treatment, 7 alkali treatment, 6, 7 fiber-reinforced composites, 6 hydrophobic aliphatic and cyclic structures, 6 Flax fibers applications, 36 bast, 35 chemical components, 36 crystalline structure, 35 mechanical/retting process, 36 needle-netted headpiece, 35 properties, 36 Fossil fuels, 89 G Gallnut, 122–124 Glass fibers, 5 Golden dock, 144 Green chemistry, 2 Green composites, 103, 104 Green tea, 148 Gromwell, 149 H Hackling, 99 Hemp fibers agriculture, 90 applications, 38 breaking operation, 98 C. sativa, 37 Cannabaceae family, 90 components, 37 composite applications (see Composite applications, hemp) construction materials, 104, 105 cultivation, 91–93 hackling, 99 multicellular structure, 37 production, 37 (see also Retting)

Index properties, 37 textile purpose, 99 THC, 90 Henna, 137–139 I Indigo, 118, 119 Irrigation, 89 J Jute fibers applications, 42 classification, 41 composition, 41 insulating capacity, 41 natural fiber, 41 properties, 42 K Kenaf fibers, 38, 39 acetic acid application, 15 alkali treatments, 14 conventional processes, 14, 15 Malveceae family, 13 mechanical properties, 17 microwave processes, 14, 15 processes, 13, 14 tensile strength, 14 ultrasonic processes, 14, 15 washing method, 14 Knotweed, 153 L Leadworth, 161 Legume forages, 167 Lignocellulosic fibers bonding characteristics, 3 chemical modification, 7 hydrophilic, 3 surface treatments (see Surface treatments) Lili hand-spinning, 64 Luffa fibers conventional methods, 18 fibrousvascular system, 18 mechanical characteristics, 19 mechanical properties, 19 microwave methods, 18 SEM micrographs, 20 subtropical plant, 17

183 ultrasonic methods, 18 uses, 17 Luxury aims, 52 boundaries, 51 craftsmanship, 52 democratization, 51, 52 desire, 51 durable value, 52 environmental and societal crises, 53 idea, 51 purchase, 52 quality product aspects, 52 M Madder, 126 Madhuca indica, 166 Mahonia, 165 Mandarin, 160 Mango, 156 Mentha sp., 163 Microorganisms, 112 Microwave energy, 8, 97 Microwave energy system, 17 Mimosa, 158 Myrobolan, 124–126 N Natural fibers, 3–5 Neem tree, 128–130 Noni fruit, 151 O Okra fibers, 45 Onion, 142 P Papaver rhoaes, 162 Pcutching process, 98 Peony, 152, 153 Pesticides, 89 Petroleum, 88 Pineapple fibers, 45 Plant-based natural fibers, 2 Abaca fibers, 43, 44 advantages, 28 bamboo fibers, 33–35 banana fibers, 44 chemical composition, 30, 31

Index

184 Plant-based natural fibers (cont.) classification, 29, 30 coconut fibers, 45 cotton fibers, 31–33 flax fibers, 35–37 hemp fibers, 37–38 jute fibers, 41–42 kenaf fibers, 38, 39 lignocellulosic fibers, 28 mechanical properties, 30, 31 Okra fibers, 45 pineapple fibers, 45 production process, 30 ramie fibers, 42, 43 sisal fibers, 40–41 sun hemp fibers, 46 sustainable and biodegradable, 46 Plant extracts A. arborescens, 133 A. lancea, 158 A. nobilis, 158 acacia, 116–118 aloe vera, 131–133 Amla, 153 annatto, 162 Ashoka, 165 B. vulgaris, 139, 140 basil, 141 boneset, 165 capsaicin, 155 champaka, 162 Chineese goldthread, 146 cloves, 156 daisy, 145 eucalyptus, 160 European spruce, 160 gallnut, 122–124 golden dock, 144 green tea, 148 gromwell, 149 henna, 137–139 indigo, 118, 119 knotweed, 153 L. forages, 167 leadworth, 161 M. indica, 166 madder, 126–128 mahonia, 165 mandarin, 160 mango, 156 Mentha sp., 163 mimosa, 158 myrobolan, 124–126 neem tree, 128–130 noni fruit, 151

onion, 142 P. rhoaes, 162 peony, 152 pomegranate, 119–122 prickly chaff-flower, 144 ratanjoti, 148 red kamala/kum kum tree, 150 rhubarb, 143 spurge, 149 tamarind, 151 teakwood, 146, 147 tobacco, 155 turmeric, 134–136 wallnut, 136, 137 Polyester, 89 Polyethylene glycol (PEG), 168 Polymers, 3 Pomegranate, 119 AATCC 147-1988 method, 119 antibacterial finishing processes, 120 antimicrobiality, 119 cotton fabrics, 121 efficacy, 119 enzymes and substrates, 121 impregnation-drying-thermophysis method, 121 mordants, 122 wool fibers, 120 Purucha/Pulucha, 56 R Ramie fibers, 42, 43 Ratanjoti, 148 Red kamala/kum kum tree, 150 Renewable and biodegradable substances, 171 Retting approaches, 96–98 dew/field retting, 95, 96 fiber quality, 94 hydrolyzing enzymes, 94 procedures and effluents, 94 traditional method, 94 water retting, 94, 95 Rhubarb, 143 S Sisal fibers A. sisalana, 11, 40 applications, 40, 41 mechanical properties, 12 natural fibers, 11 processing methods, 40 properties, 40

Index tensile strength, 12 washing method, 11, 12 Spurge, 149 Steam explosion, 98 Sun hemp fibers, 46 Surface treatments A. americana fibers, 8–10 enzymes, 7 Kenaf fibers, 13–15, 17 luffa fibers, 17–20 microwaves energy, 8 sisal fibers, 11, 12 ultrasonic energy, 8 Sustainability, 2 definition, 28 ecological environment, 29 ecology and ecological application, 28 global warming, 29 population, 29 Sustainable attributes, 53 luxury, 53 Sustainable luxury business, 53 craftsmanship, 54, 55 definition, 53, 54 skill sets, 54 Sustainable process, 162 Sustainable production definition, 88 energy consumption, 95 hemp fiber, 92 intervention, 105 retting operations, 92 textile industry, 88, 89 Synthetic fiber research, 88 Synthetic fibers, 4

185 T Tamarind, 151 Tannins, 114 Teakwood, 146, 147 Tetrahydrocannabinol (THC), 90 Textile industry branches, 89 hemp fibers, 93 pessimistic, 88 petroleum-depended, 88 Thermoplastic starch (TPS), 104 Tobacco, 155 Turmeric antibacterial activity, 115, 130 antiseptic properties, 113 C. longa rhizome, 135 chitosan, 131, 132 dyeing process, 135 Indian saffron, 134 microcapsules, 135 phenolic groups, 133 U Ultrasonic energy, 8 V Virtual water, 2 W Wallnut, 136, 137 Water footprint, 2 Water retting, 94, 95 Weaving process, 76, 79