New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in Technology [1 ed.] 9781624172663, 9781624172656

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Copyright © 2013. Nova Science Publishers, Incorporated. All rights reserved. New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in Technology,

Copyright © 2013. Nova Science Publishers, Incorporated. All rights reserved. New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

GEOLOGY AND MINERALOGY RESEARCH DEVELOPMENT

NEW DEVELOPMENTS IN QUARTZ RESEARCH

Copyright © 2013. Nova Science Publishers, Incorporated. All rights reserved.

VARIETIES, CRYSTAL CHEMISTRY AND USES IN TECHNOLOGY

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New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

GEOLOGY AND MINERALOGY RESEARCH DEVELOPMENT

NEW DEVELOPMENTS IN QUARTZ RESEARCH

Copyright © 2013. Nova Science Publishers, Incorporated. All rights reserved.

VARIETIES, CRYSTAL CHEMISTRY AND USES IN TECHNOLOGY

BRUNO NOVAK AND

PAVLA MAREK EDITORS

New York New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

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Published by Nova Science Publishers, Inc. † New York New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

CONTENTS Preface Chapter 1

QCM in the Active Mode: Theory and Experiment F. N. Dultsev 

Chapter 2

Nature of Paramagnetic Defects in -Quartz: Progresses in the First Decade of the 21st Century Rudolf I. Mashkovtsev and Yuanming Pan 

Chapter 3

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vii 

Veined Quartz of the Urals: Structure, Mineralogy, and Technological Properties V. N. Anfilogov, S. K. Kuznetsov, R. S. Nasirov, M. A. Igumentseva, M. V. Shtenberg, P. Argishev and A. Lebedev 

1 

65 

105 

Chapter 4

Densification of Quartz Particle Beds by Tapping J. L. Amorós, G. Mallol, M. J. Orts and J. Boix 

Chapter 5

Rapid Detection for Pollutants and Bacteria Based on Quartz Crystal Microbalance Biosensor Zhixian Gao and Nan Liu 

171 

Novel Quartz Oscillator Measurement for Gas Composition Changes Atsushi Suzuki 

193 

Detection/Adsorption of Chemical and Biological Molecules Based on Quartz Crystal Microbalance (QCM) as Sensor M. A. Shenashen and K. K. Shenashen  

213 

Chapter 6

Chapter 7

Chapter 8

Usefulness of the Quartz Crystal Microbalance Technique to Assess In Situ Detergency Process Efficiency Olivier Favrat, Joseph Gavoille, Lotfi Aleya and Guy Monteil

New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

143 

229 

vi Chapter 9

Chapter 10

Contents Very Recent Development and Significant Step in Ultra-Stable Quartz Oscillators Patrice Salzenstein

241 

Gold Analysis After Nanoparticle Adsorption on Quartz Reflectors and Total Reflection X-Ray Fluorescence (TXRF) Analysis Nikolaos G. Kallithrakas-Kontos and Ioanna-Nikol I. Aretaki 

251 

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Index

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263 

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PREFACE In this book, the authors present new developments in quartz research. Topics discussed in this compilation include the nature of paramagnetic defects in a-Quartz; veined quartz of the Urals; QCM in the active mode; densification of quartz particle beds by tapping; rapid detection for pollutants and bacteria based on quartz crystal microbalance biosensors; novel quartz oscillator measurement for gas composition changes; detection/adsorption of chemical and biological molecules based on quartz crystal microbalance QCM as sensor; usefulness of quartz crystal microbalance techniques to assess in situ detergency process efficiency; ultrastable quartz oscillators; and gold analysis after nanoparticle adsorption on quartz reflectors and total reflection x-ray fluorescence (TXRF) analysis. Chapter 1 - QCM as an active element for sensing applications is a promising achievement allowing us to expect essential advances in the development of chemical and biological sensors. Unlike for the conventional method of QCM operation, in the active mode it plays an active part towards an analyte fixed on its surface. This approach ensured a 3 orders of magnitude higher sensitivity of QCM than that achieved using the conventional method. A mathematical model describing the interactions of a point mass attached to the QCM surface was also developed. With this model, it became possible to optimize not only the measurement circuit but also the geometry of the QCM plate involved in measurements. Further upgrading the procedure the authors proposed to use QCM in the threshold mode. An additional gain in sensitivity (by two orders of magnitude) was thus achieved. This made it possible to use QCM as gas sensor for very low concentrations. The major advantage of the use of QCM in this mode is the possibility to measure not only the concentration of an analyte but also the force of its rupture from the surface. With specific surface modifications, this allows us to identify a wide range of objects. The procedure is applicable either for gas sensing or for studies in biology and medicine. The procedure is suitable for identification of phages (10-20 individuals), viruses (e.g. a single herpes virus can be detected), bacteria etc. This procedure allows measuring bond rupture forces; similar to atomic force microscopy, it does not involve the action of electromagnetic radiation and thus it is non-perturbing and well suitable for biological applications to study weak (hydrogen) bonding. In comparison with AFM, the proposed QCM-based procedure is much simpler and cheaper in its instrumentation, and time-saving, as there is no need to search for an object attached to the surface.

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viii

Bruno Novak and Pavla Marek

Chapter 2 - Impurities and other defects in -quartz not only record genetic information of this common mineral but also exert profound (positive or negative) effects on the technological applications of this important material. Also, fundamental defects in -quartz often serve as the testing cases for understanding analogous defects in other silica-based materials. Following the last comprehensive review by Weil (2000), this contribution summarizes new progresses on the nature of paramagnetic impurities and other defects in quartz, made in the first decade of this century. In particular, new data on impurities stem from not only the development of in situ microbeam techniques for compositional analyses but also the application of state-of-the-art spectroscopic methods [high-frequency electron paramagnetic resonance (EPR), pulsed electron nuclear double resonance (ENDOR) and electron spin echo envelope modulation (ESEEM), and synchrotron X-ray absorption spectroscopy] and first-principles theoretical calculations for structural investigations. Other significant progresses include the discovery and quantitative characterization of a large number of new paramagnetic defects related to vacancies at the oxygen and silicon sites. Chapter 3 - There are three major groups of the Ural quartz deposits: the Circumpolar group, the Middle Ural group and the South Ural one. The Circumpolar group is represented by the typical hydrothermal veined deposits. One of the big Circumpolar quartz deposit is “Jelannoie” one. It is located in the monomineralic quartzy sandstone. The quartz vein may be to 100 meters thick. Rutile, turmaline, zircon and sericite are the major accessory minerals. The chief deleterious constituent in quartz is water, which is located in the gas-liquid inclusions. The effective method for H2O elimination is described. High quality quartz glass may be produced after primary quartz enriching. The Middle Ural is represented by giant quartz body “Mounain Chrustalnaia”. Quartz body has a size 380X140X160 m. The content of quartz is 98.89%. Quartz deposit was formed on the big massive of quartz-diorite and granite contact. The main accessory minerals are microcline, muscovite, kaolin, hydrogoethite and pyrite. Quartz has a giant crystalline structure. There is a specific enriching technology for this quartz deposit. The South Ural group of quartz deposits is represented by a large body quartz vein, disposed in East part of the Ufaleisky gneiss-migmatite complex. The length of quartz vein area is 50 km. There are more than 3000 quartz veins on this area. Granulated quartz is prevalent for this group of deposits. Field spars, micas, rutile, sphene, ilmenite and carbonates are the main accessory minerals. Concentration of impurities in granulated quartz is as the IOTA STD. There is standard technology of quartz enriching for these deposits. Chapter 4 - Quartz of different grain size is used to manufacture composite materials. One of the most popular is “engineered stone”, made of inorganic fillers bound together by a polymer resin, being quartz the major filler. A typical composition of engineered stone is 93% quartz and other fillers by weight and 7% resin. In order to eliminate the air of the mixture and use as much percentage of quartz as possible it is very important a high densification of the mixture of fillers. The purpose of this study is twofold, first to determine how the mean particle size of monomodal quartz particle beds and the bed preparation method affect initial and final bed apparent density and the kinetics of densification by tapping. This work was conducted on eight quartz particle size fractions obtained from a commercial quartz powder by sieving, each having a different mean particle size and a very narrow (monomodal) particle size distribution. Densification experiments were conducted on the beds obtained with each fraction, using an assembly designed for this purpose. A kinetic model representing

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Preface

ix

the densification process of monomodal powder beds by tapping is proposed, in which good relations are obtained between the parameters of the model and the foregoing variables. In a second step to study the influence of the composition and mean component sizes of beds of binary mixtures of monomodal quartz particle fractions on initial and final bed fractional bulk densities and on the kinetics of densification by tapping. An equation is proposed that relates initial and final bed fractional bulk densities to the mixture composition; it was verified that these characteristics can be related using the fractional bulk densities of the starting monomodal particle beds and an empirical efficiency factor. The kinetics of densification by tapping of binary quartz particle beds was studied using a kinetic model developed for monomodal powder beds. The relationships between the parameters of that kinetic model and the characteristics of the mixtures were good and unique for both the monomodal and the bimodal powder beds. Chapter 5 - QCM technique is a powerful tool with advantages of high sensitivity, real time measurement, free-labeling, etc. has been widely used in food safety, environment monitoring and veterinary diagnosis. QCM has been used as an active mode sensor for the direct detection of molecular interactions by oscillating the sensor surface and monitoring the acoustic emission produced by bond rupture. Here, QCM biosensors for the rapid detection for pollutants and bacteria are reviewed. As molecular recognitions are mostly occurring on the surface of the quartz crystal, the sensitive recognition elements such as MIP flim, aptamer coated film, micro/nanomaterials coated on QCM chip and carbon nanotubes coated electrode are narrated. It can detect the trace mass change in the nanogram range onto the electrode surface of quartz crystal in air or liquid. The most popular QCM biosensors such as QCM based on immunological method, QCM based on molecularly imprinted technology DNA QCM biosensor and QCM with dissipation (QCM-D) biosensor are discussed in details. Chapter 6 - This chapter reviews quartz oscillator measurement to measure gas composition changes, including hydrogen sensing, hydrogen concentration measurement, humidity measurement, and partial pressure measurement of air-helium, silane-hydrogen, and nitrogen-hydrogen gas mixtures. This measurement is based on the output from the quartz oscillator circuit depending on pressure, viscosity, and molecular weight of the measured gas. This method can be used to detect the changes in viscosity and molecular weight of the measured gas, and can thereby detect hydrogen leakage into air. The partial pressure of each gas in binary gas mixtures can be determined because the viscosity and molecular weight of the binary gas mixtures depend on the partial pressure ratio of each gas. By measuring using quartz oscillator, viscosity and molecular weight of binary gas mixtures can be obtained, thereby, each partial pressure in binary gas mixtures are also derived from the ratio. The principle of this method, experimental apparatus, and results are summarized. The quartz oscillator measurement on hydrogen showed 0.1% minimum detectable hydrogen concentration, under 1 s response time, and measurable concentration up to 100 vol.%. This rapid response is because this quartz oscillator measurement is a physical measurement, and is therefore essential for other measurements using a quartz oscillator. Relative humidity and helium concentration in air-helium gas mixtures were measured for comparison to hydrogen leakage detection into air, and the results showed that the influence of relative humidity and helium are about 1/50 and 1/4 below 20% helium in air, respectively. Working curves to derive each concentration of silane and hydrogen in silane-hydrogen and nitrogen and hydrogen in nitrogen-hydrogen gas mixtures used for production methods for

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Bruno Novak and Pavla Marek

thin silicon film solar cell materials and nitriding materials were obtained, which can be used to optimize process conditions. Chapter 7 - The piezoelectric QCM is an ultrasensitive weighing device around nanograms, consisting of a thin disk of single crystal quartz, with metal electrodes deposited on each side of the disk. The QCM is a simple, cost effective, high-resolution mass sensing technique, based upon the piezoelectric effect. QCM technique has recognized as a standard tool that able to provide both qualitative and quantitative information about their target materials. The high sensitivity and the real-time monitoring of mass changes on the sensor crystal make QCM a very attractive technique for a large range of applications. QCM immunosensors have the ability to work directly measure antibody–antigen binding at the surface of the transducer as label-free, in the same time its surface can be functionalized with organic and inorganic materials to improve its sensitive and selective efficiency toward several targets especially biomolecules. QCM sensor suggested being successfully for early stage clinical diagnosis. Chapter 8 - This chapter presents an application in situ of the Quartz Crystal Microbalance (QCM): the monitoring of a detergency process. A method is developed to investigate the influence of cleaning parameters on the surface contamination removal. To illustrate this method, this work focuses on the influence of detergent concentration and initial contamination on the necessary time to remove stearic acid (C18H36O2) from a gold-plated quartz crystal surface. The different steps of contamination removal were assessed in real time by monitoring the variations of the quartz resonator frequency. These observations highlight i) an adsorption and absorption of water and detergent on the stearic acid layer and ii) the detachment of the fatty acid layer. For this second point, it had been shown that the time of stearic acid removal is a function of the detergent concentration until a critical value. Below this critical concentration, cleaning time decreases while detergent concentration increases. Above the critical concentration, an asymptotic value is reached and adding detergent has no more effect on the cleaning time. Cleaning duration is also strongly influenced by the initial contamination: increasing sample contamination enhances removal time. However, no clear correlation between the two parameters can be obtained. It seems therefore that, thanks to its ability to determine optimal parameters for each detergent, the QCM technique appears to be of great interest in monitoring and optimising cleaning protocols. Chapter 9 - The recent progress in Quartz thanks to the Doubly rotated quartz resonators with a low amplitude-frequency effect called Low isochronism Defect (LD) cut and most of all the very recent development of a new design for integrating a Stressed compensated (SC) cut in an oscillator with the best stability ever obtained with a quartz oscillator, 2.5x10-14 for the flicker frequency modulation (FFM) floor for a 5 MHz Boitiers à Vieillissement Amélioré (BVA) double oven- controlled oscillator open the door to ultra-high stability oscillators for telecommunications, instrumentation and space applications. In this chapter, the authors propose to describe the main guidelines that led to the first significant development in the last fifteen years in terms of ultra-stable quartz state-of-the-art oscillators. These oscillators are realized in France and Switzerland. It includes the choice of the resonators, the development of adequate electronics and how to mechanically and thermally stabilized such an ultra-stable oscillator.

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Preface

xi

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The authors also present how to characterize the expected performances. Finally the authors say some words about the use of these Quartz oscillators for space, telecommunication and metrology applications and how their signal can be distributed in a laboratory without degradation of their noise. Chapter 10 - Gold is a precious metal with many technological applications. Total Reflection X-Ray Fluorescence (TXRF) is a powerful technique for trace element analysis on flat surfaces; gold is among the most effectively analysed elements from its L X-ray lines. Quartz is the most frequent used sample supporter for achieving the Total Reflection conditions. A new method for the determination of gold trace levels is presented. The method has been based on the reduction of gold ions to colloidal nanoparticle suspension; this suspension was adsorbed on quartz surface and analysed by TXRF. More specifically the reflectors were immersed in water solutions containing low concentration of gold and reducing agents were added. By the end of the colloidal adsorption, the reflectors were removed, cleaned with water, desiccated and analyzed by total reflection X-Ray fluorescence. Among various reducing reagents (that they were tested), ascorbic acid and sodium citrate gave the best results. The effects of immersion time and various experimental parameters were examined. The coexistence of other ions does not interfere in the analysis process and the method can be applied in all types of water (ASTM type I, drinking and seawater). Very good linearity in the 1-500 ng.mL-1 gold concentration range was achieved and the minimum detection limit was estimated in low ppb level.

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Copyright © 2013. Nova Science Publishers, Incorporated. All rights reserved. New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

In: New Developments in Quartz Research Editors: Bruno Novak and Pavla Marek

ISBN: 978-1-62417-265-6 © 2013 Nova Science Publishers, Inc.

Chapter 1

QCM IN THE ACTIVE MODE: THEORY AND EXPERIMENT F. N. Dultsev Institute of Semiconductor Physics, Siberian Branch of the Russian Academy of Sciences, Novosibirsk, Russia

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ABSTRACT QCM as an active element for sensing applications is a promising achievement allowing us to expect essential advances in the development of chemical and biological sensors. Unlike for the conventional method of QCM operation, in the active mode it plays an active part towards an analyte fixed on its surface. This approach ensured a 3 orders of magnitude higher sensitivity of QCM than that achieved using the conventional method. A mathematical model describing the interactions of a point mass attached to the QCM surface was also developed. With this model, it became possible to optimize not only the measurement circuit but also the geometry of the QCM plate involved in measurements. Further upgrading the procedure we proposed to use QCM in the threshold mode. An additional gain in sensitivity (by two orders of magnitude) was thus achieved. This made it possible to use QCM as gas sensor for very low concentrations. The major advantage of the use of QCM in this mode is the possibility to measure not only the concentration of an analyte but also the force of its rupture from the surface. With specific surface modifications, this allows us to identify a wide range of objects. The procedure is applicable either for gas sensing or for studies in biology and medicine. The procedure is suitable for identification of phages (10-20 individuals), viruses (e.g. a single herpes virus can be detected), bacteria etc. This procedure allows measuring bond rupture forces; similar to atomic force microscopy, it does not involve the action of electromagnetic radiation and thus it is non-perturbing and well suitable for biological applications to study weak (hydrogen) bonding. In comparison with AFM, the proposed QCM-based procedure is much simpler and cheaper in its instrumentation, and time-saving, as there is no need to search for an object attached to the surface.

Keywords: Quartz crystal microbalance, QCM; bond rupture force; bacteria; rupture event scanning, REVS; quantitation; screening; diagnostics New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

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F. N. Dultsev

ABBREVIATIONS (GLOBAL) QCM AFM ADC TSR EQCM TMM DSA CVD PBS NHS EDC BSA mAb

quartz crystal microbalance; atomic force microscopy; analog-to-digital converter; Thickness Shear Resonator; electrochemical quartz crystal microbalance; threshold mode method; diffusion spectrometer of aerosols; chemical vapour deposition; phosphate buffered saline; N-hydroxysuccinimide; N-ethyl-N'-(3-diethylaminopropyl) carbodiimide; bovine serum albumin; monoclonal antibody.

1. MEASUREMENT OF BOND RUPTURE FORCE WITH THE HELP OF A QUARTZ CRYSTAL MICROBALANCE

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1.1. Introduction What is a bonding force between two molecules or atoms? The questions of this kind arise during investigation of the structure and properties of molecules. The interaction between atoms or molecules is the key problem when the dynamics of interactions is considered either at the molecular level or in the receptor – agent (adsorbent – adsorbate) systems including biological systems. Traditionally these interactions were considered using the thermodynamic approach. However, bond rupture occurring during these interactions is a dynamic process, so it depends not only on the chemical affinity but also on the rate of change of the force applied to the interacting molecules [1, 2]. Different methods of measuring the binding forces between molecules are developing during the recent decades. Different devices were developed to study the surface interactions, for example, "optical tweezers" [3] and atomic force microscope (AFM). The latter instrument has won the widest application; it allows one to perform measurements during the capture and rupture of a separate particle [4-9]. The processes of the formation and breakage of the bonds holding a particle to a surface have been studied for decades. The direct data on binding force can provide an unambiguous characterization of adsorption on the surface under investigation. The conventional approach involves an action (usually electromagnetic) on the system; the response is detected and deciphered (the pulse-response technique using short light pulses). It is very important to decrease perturbation of the system under investigation but to conserve the information content of its response to the action. Perturbation may be reduced by excluding the electromagnetic action, for example by using mechanical action to break a bond. Such a possibility was implemented in AFM. The first works describing direct measurements of the forces of interaction for the case of hydrogen bonds appeared in 1992 [10].

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QCM in the Active Mode

3

Development of these investigations was described in [11-14]. In those works, the surface with the particles attached to it was studied by means of AFM. Binding forces in the case of specific molecular interactions were measured (10-11 to 10-9 N); corresponding bond energies are within the range 1 to 500 kJ/mol. An intermediate result of the perennial efforts to investigate the possibility to directly measure the force of a single bond holding a particle on the surface was the work described in [14]. The advances were due to the development of nanometer-size manipulating instruments, or cantilevers. They allow mechanical conversion of particle rupture events in chemical or biological processes into detectable signals with high accuracy. Nanometer-size cantilevers are used as sensors based on rupture forces to examine the surface topography [15]. Sample surface is scanned along parallel lines with the help of a sharp-pointed cantilever. The tip is either in permanent contact with the surface or oscillates touching the surface only for a short time. The possibilities of this method broadened when an array of cantilevers with the tips coated with a sensitive layer for molecular recognition was developed. Such an instrument is a sensitive nanomechanical sensor for detecting chemical and biological interactions either in the gas phase or in liquid [16-22]. This device can be used in the gas phase as an artificial nose to detect volatile compounds [23-25], or in liquid for molecular recognition (antibody-antigene interactions) [26-28]. This technique is developing; it is actively used to detect volatiles (in particular HF, organic solvents) with the help of micro-cantilevers operating in the static mode [29-31], as well as with the help of piezo-resistive cantilevers [32-34], in biological studies, for example as a sensor for glucose [35-36]. The theory of molecular adsorption on cantilevers is under development [37, 38]. Cantilever technique allows one to study physical and chemical adsorption, or, for example, to determine changes of enthalpy during phase transitions. The authors of [39] develop the application of this technique to biochemical investigations and to medical diagnostics. The nearest goal is to optimize cantilevers as sensors for nanomechanical detection of separate molecules. The use of this technique is held back by the complicated production and high cost of these high-precision devices, as well as by the short lifetime with the necessity of regeneration. The method proposed by us [40], called REVS (Rupture Event Scanning), is based on QCM and has a simpler hardware implementation but nevertheless it allows one to obtain reliable data on the values of bond rupture forces. Similar to AFM, rupture event scanning does not involve electromagnetic radiation. This method records the excitation of oscillations caused by the rupture of bonds between a particle and a substrate. Unlike for usual methods of QCM applications (for example, as a microbalance or as a resonance sensor in biology), in our method the QCM is used not only as a sensor but it also plays an active part with respect to the particles attached to its surface. The piezoelectric properties of the QCM allow detecting the excitation of substrate oscillations caused by bond rupture. These oscillations are converted into the electric signal. The signal points not only to the presence of an analyte (detected particles) on the surface but also to their amount, as well as to their affinity to the receptor attached to the surface. Scanning process requires minimal sample preparation and can be carried out in different media (in vacuum, in air, in liquid); it takes only a few minutes. The method is applicable to measure bond rupture force because the particles on the surface, bound with the analyte to be detected, form an amplifier scheme. To become a working tool for researchers in the areas of chemistry, biology, or medicine, the method needs a mathematical description of the physics of oscillations in a resonator. At present, no mathematical description of the interaction of a low-mass particle with the QCM

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F. N. Dultsev

surface has been developed yet. In our work we used our own semi-empirical model [49], which will be described below.

1.2. Experimental, Theory, Results

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In order to pass to the quantitative measurements of bonding force, at first we are to consider some theoretical aspects concerning the rupture of a particle from the surface. Amplitude of QCM oscillations, A, is set by equation A = (QP/(23f3M))1/2. This equation is based on energy balance assuming the 100 % efficiency of the conversion of electric energy to mechanical one. Here Q is the quality factor, P is the electric power accepted by QCM, f is the resonance frequency of the quartz crystal, M is the effective mass of the quartz plate of the resonator (taking into account the fact that the amplitude in the centre of the resonator is higher than that at its edges). An empirical equation giving the similar result was reported by Borovsky in [41]: А = 1.4 x Q x Ud, where Ud is the amplitude of voltage supplied to the QCM. We determined in our experiments in the air that Q is 5000 – 15 000 at 6 V, depending on the resonator used, and on the load. Accepting Q to be equal to 10 000, we obtain the amplitude of oscillations in the centre of the resonator to be equal to 150 nm (for the excitation voltage equal to 6 V). The order of magnitude of the obtained value corresponds to the results of more complicated calculations described in [42-44], where the displacement value of 132 nm was obtained for the QCM with the resonance frequency of 5 MHz and the Q-factor equal to 100 000 in the absence of load, at the voltage of 1 V.

Figure 1. Geometry of particle rupture from the surface. A. Particle with mass М and radius R, attached at the pivot point, and the arising inertia force F, as well as the tangential acceleration аts causing acceleration ас in the particle centre. B. Case of a single bond, here а is the radius of the sphere, h is the distance between the sphere and the surface, L is bond length, Т is the bond stretch force, N is the force directed along the perpendicular, F is external force,  is rotational moment. Figure B was taken from [38].

New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

QCM in the Active Mode

5

Calculation of inertia forces: Assuming the sphere to rotate or turn around a fixed point (Figure 1-A), we may write the equation for the moment of inertia of the sphere around the centre (axis) as J S =  r 2 dm = 2ρ r 4

R

2 s



 r 2 dr =

2 M s R s2 5

(1)

Here r is the integral radius, RS is the radius of the sphere, МS is its mass,  is the density of the sphere. Acceleration ас in the centre of the sphere is determined as ас = Ft / MS

(2)

where Ft is the total applied force. The angular acceleration s of the sphere is εs =

5a Ft RS Ft RS = = C 2 2R S JS M S RS2 3

(3)

therefore, acceleration аs of the surface of the sphere with respect to acceleration ac in the centre of the sphere is

aS = ε S RS =

5a C 2

(4)

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Hence, total acceleration ats of the surface of the sphere is a tS = a C + a S =

7a C 2

(5)

In other words, the centre of gravity of the sphere rotating around the point of attachment to the surface passes only 2/7 of the distance passed by the surface in the full-range motion around the pivot point. So, acceleration of a point on the resonator surface is given by equation a= (2/7) A(2 f)2

(6)

Considering a rigid sphere, the force applied to the particle can be calculated using equation

F=

2 mA 2  f 7

2

(7)

This equation was obtained by solving the motion equation for a ball that dangles on a hinge around the point of contact with the QCM surface and rotating in this motion; factor 2/7 New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

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takes into account the fact that the centre of gravity of the sphere moves at a shorter distance from the pivot point. So, we determined the equations to calculate rupture force. Particle rupture from the surface: If there is only one bond between the particle and the surface, then the perpendicular, tangential and shear forces necessary for bond rupture can be calculated analytically [45, 122]. The critical perpendicular force necessary to break a single bond is equal to the bonding force because the applied force acts along the same straight line as the bonding force. However, if the reaction between the substrate and a molecule getting attached to the surface is reversible, it is necessary to assign the duration of force application before determining the bonding force because a "reversible" bond will break without any applied force if we wait for sufficiently long time. Let Тар be time during which the external force F is applied to the bond. Then the critical force will be defined as a force able to break the bond with the probability 1 – е-1 during time interval Тар. Bond rupture is considered as Poisson process, so we obtain

exp kTap = e 1

(8)

and therefore k = 1/Tap. Substituting kr into equation given in [46], the authors of [45] obtained

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 σ  σ ts   λ    k r = k r0 exp  2k b T  

Using the linear dependence of force on stretch F, we obtain the value of bonding force F or, equivalently, the force necessary to break the bond during observation time Tap. We consider two cases (see Figure 1-B): the force applied to the particle is tangential or shear. The arising bond stretch Т can be calculated for the mechanical equilibrium of the force in x direction and rotation in z direction:

F = T cos φ

(9)

τ=− Ta cos (θ+φ )

(10)

Here  is the rotational moment applied from outside (zero for purely tangential force). The force balance along the у axis is omitted because the resulting nonspecific force will hold the particle to provide balance of forces in the direction perpendicular to the surface. The nonspecific force is symmetrical and thus it does not create rotational moment. Because a/L >> 1, the value of  can be considered to be small, and we may use the approximation cos sin cos sin. Dividing equation 10 by the product of а and equation 9, and transforming, we obtain τ   θ = α1 +  aF  

One can see in Figure 1 that   and  are interconnected geometrically:

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(11)

QCM in the Active Mode Lsin=h+a(1 - cos)

7 (12)

Substituting equation 11 into equation 12 in the approximation of а >> L, we obtain α=

2 L  h  τ   L + a 1 +  aF  

1 τ   1 +  aF  

2 L  h  a

(13)

Then, it follows from equation (9) that F = T cos φ  α T

(14)

Equation 14 gives the relation between bond stretch (T) and the applied tangential or shear body force. This equation is a consequence of the principle of mechanical energy conservation and geometric considerations. If we accept Т to be equal to NCF(1), which is the critical force for bond rupture, then F is the tangential critical force TCF(1) or shear critical force SCF(1) for the detachment of the sphere held by a single bond. So,  is the ratio of the tangential and normal forces necessary for the detachment of the particle. With the tangential force applied to the sphere ( = 0), equation 14 will appear as

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F =T

2L  h a

(15)

Estimations made by the authors of [45] showed that, for the case of the single bond, the force applied in the perpendicular direction must be 20 times larger in value than that in the case of the force directed at a tangent. In the case of the high density of receptors, the forces directed at a tangent can be 56 times more efficient for particle rupture from the surface than the perpendicular forces. The forces applied at an angle of 0 (tangent) to 80 о with respect to the substrate plane are as efficient as the tangential forces. Measurement of the force of bond rupture: The following procedure was used for this purpose. We attach a sphere of the known size and mass to the QCM surface, then we smoothly increase the amplitude of surface oscillations and determine the voltage at which the bond holding the sphere to the surface breaks. The quartz crystal microbalance (QCM) was made of polished quartz plates (AT-cut) at an angle of 35 o, 8.25 mm in diameter. A layer of chromium 10-20 nm thick, and then gold (100-120 nm) shaped as a circle 4 mm in diameter were deposited onto both sides of the central part of the plates. The resonance frequency of QCM was 14.3 MHz. Different types of bonds between the sphere and the surface are to be considered. The bond may be physical, hydrogen, and covalent (chemical). For this purpose, we chose the spheres with different functional groups. To study the physical bond, we used glass beads 5 m in diameter without any additional functional groups and placed them on the surface coated with gold. We chose streptavidin – biotin as the system with hydrogen bond because this system has been thoroughly studied [47, 48] and thus it is widely used as the test system; this bond is the strongest among non-covalent bonds. Calculated and experimental values for

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the energy of this bond are within 15-25 kcal/mol, so it is the strongest known hydrogen bond. We also used this system as test. To prepare the streptavidin – biotin system, biotinized bovine serum albumin was dissolved in the buffer solution (10 mg/10 ml PBS ); 20 m of this solution was deposited on the surface, then the surface was washed and dried in nitrogen flow. After that, 20 l of the solution containing streptavidin-coated microspheres was deposited on the surface (streptavidin gets bound to biotin with hydrogen bonds). The system was left for 3-4 h, then washed with water and dried in nitrogen flow. To obtain a covalent chemical bond, the spheres were attached to the surface through the amine group. In order to prepare amide bonding, at first we treated the surface with the 1 mM solution of 12-mercaptocaprinic acid in ethanol for 24 h. A monolayer is formed on the surface as a result of the reaction of thiol group with gold. The carboxylic group was activated with EDC-NHS for 40 min, then the solution was removed, and spherical particles with the end amino groups were added. After exposure for 1 h, the surface was washed with water, then with ethanol. It is necessary to mention here that the amide bond energy (73-86 kcal/mol) is higher than the energy of the thiol – gold bond (30-35 kcal/mol), so we are able to determine the force of bond rupture just for Au -- S. The structure of the bonds under investigation is shown in Figure 2. Measuring method was chosen relying on the concentration of spheres on the QCM surface. If the degree of surface coating with spheres is close to the monolayer or higher, then, in order to determine rupture force, we may use the method based on measuring the change of the resonance frequency accompanying particle detachment. The measurement scheme for this method is rather simple (Figure 3 (Scheme 1)). The frequency-modulated (FM) signal is supplied to the QCM; the frequency increases linearly. The range of frequency scanning is chosen so that the position of the resonance could be determined.

Figure 2. Schematic structure of bonding between the sphere and the QCM surface: the left image is for hydrogen bonding: S is streptavidin on the surface of the sphere, В is biotinized bovine serum albumin; the right image is for chemical bonding.

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QCM in the Active Mode

1

9

2

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Figure 3. Schematics of experimental set-up for measuring rupture forces.

Usually for a QCM with the resonance frequency of 14-15 MHz this value is 20-30 kHz. With each step we increase the amplitude of alternating voltage supplied to the QCM. Current (I) passing through the QCM and voltage (U) are recorded with the help of the analog-todigital converter (ADC). To increase the dynamic range and to detect the signal, we use the logarithmic amplifier (AD8307). The current transformer (T) is used to measure current. Generator (GSS-40) is controlled and data are collected using the computer (PC) with CVILabWindows software. The second method is applicable for lower concentrations, about 1% of the monolayer. For such a concentration, the frequency change is much lower than that provided by the background temperature non-uniformities of the material, so the presence of the objects on the surface cannot be detected from frequency shift. However, the moment of rupture can be detected as an acoustic signal. What is the physical nature of the generation of rupture signal? The presence of bodies on the QCM surface causes an insignificant distortion of the shape of membrane oscillations shaped as a typical "funnel". In our case, the fact of distortion of oscillation shape is itself principally important because as soon as the body leaves the surface, the shape of oscillations returns to the state of the fundamental mode. A transient process with higher harmonics will arise in the resonator plate; this is the rupture signal. At what harmonics are we to measure the rupture signal? This question will be considered in more detail in the section describing the mathematical model. According to calculations using the model proposed by us [49], if the load is present in the centre (x= 0.5), only symmetrical (even) harmonics will be present. Because these harmonics do not take part in distorting the shape of oscillations, the signal at the second harmonic is completely absent. If the position is shifted to x=0.55, the second and the third harmonics become equal to each other, while after further displacement of the body (x=0.7) the second harmonic dominates. If the bodies are placed in the central part of the QCM, it is better to perform measurements at the 3rd harmonic. A simplified measurement circuit is shown in Figure 3 (scheme 2). To distinguish the acoustic signal, we use the filter tuned to the third harmonic; measurements are made with a selective amplifier (A). The maximal possible voltage in both experimental installations is 10 V and is determined by the generator of signals GSS-80.

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Figure 4 (a). Spectra of rupture forces depending on applied voltage for nonspecific interaction (latex – gold) (3), streptavidin – biotin bond (streptavidin being covalently bound with latex spheres and biotinized bovine serum albumin on gold) (1) and chemical bond (amide bond formed between the thiol layer with the carboxyl end group and latex sphere modified with amines) (2). (b). Shift of the resonance frequency of QCM depending on applied voltage for nonspecific interaction, streptavidin – biotin bond, and the covalent bond [40].

A disadvantage of the first method is possible distortion of the rupture force value because of the mutual influence of the particles on each other. Such an influence should be very small for the concentration about 1%, so the force values obtained using the second method are more precise. Changes of the resonance frequency depending on the amplitude value for the spheres 5 m in diameter for different types of bonds are shown in Figure 4-a. Rupture force spectra are shown in Figure 4-b. The data were obtained in the air for nonspecific interaction, streptavidin – biotin bond, and for amide bond. The rupture force spectrum (Figure 4 b) for nonspecifically adsorbed latex sphere has a peak at about 0.1 V. We discovered that the intensity of the generated acoustic signal is linearly proportional to the number of spheres on the surface. The spectra for streptavidin – biotin system do not have any peaks around this value but instead they contain two peaks at about 6 V in the case of the high surface load (surface coating 1 %) and one peak in the case of lower load (surface coating 0.1-0.2 %). The amide bond does not give any peaks at all. It should be noted that the peaks in the rupture force spectrum are sharp. Repeated scanning in the system streptavidin – biotin immediately after the first scanning gives no peaks around 6 V, only weak peaks below 1 V are observed. This means that the system has not recovered yet. The QCM carrying no spheres does not change frequency with voltage change. Quite contrary, nonspecifically adsorbed particles cause a shift of the resonance frequency between 0 and 1 V, and the shift increases with an increase in voltage applied. Streptavidin – biotin spheres start to cause frequency shift only at a voltage about 6 V. This shift also increases with an increase in applied voltage. The QCM with chemically bound spheres (amide bond) gives a shift at about 6 V and another one at 9 V, though no acoustic signal is observed either at the former voltage value or at the latter one. We explain these changes by a decrease in mass due to the detachment of spheres from the surface; then the spheres roll over the surface

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QCM in the Active Mode

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and later leave it with time. In the case of high amplitude, we observe this to occur within several seconds, while in the case of smaller amplitude the process is slower. Removal of the spheres from the surface explains why we observe the recovery of frequency, while the authors of [50] observed an increase in frequency in the case of a single particle mechanically weakly attached to the surface. Further investigation is necessary in order to understand why we observe frequency shift in the case of chemical bond but do not detect acoustic signal and do not observe detachment of spheres. Our results allow us to suppose that, while both methods allow one to detect the rupture of spheres from the surface, registration of the noise is a more sensitive method than measurement of the shift of resonance frequency. Both these experiments show that we can detect rupture in the case of nonspecific interactions and in the case of interactions in the system streptavidin – biotin. A stronger interaction requires higher voltage (about 60 times higher), and in the present experiments the force is insufficient to break such a bond. The mass of the sphere is equal to 69 pg, so the force (calculated per one sphere) is estimated as 26 N (this value was obtained for the voltage of 6 V). Comparing this value with the force necessary to break one streptavidin – biotin bond (160 pN) [51], we see that about 160 000 bonds are broken simultaneously. According to our stoichiometric estimations, this approximately corresponds to the geometric number of initial streptavidin – biotin bonds between the sphere and the QCM surface, assuming a tightly packed layer of streptavidin on the surface of the sphere. This reasonably corresponds to the "overturn" observed for the blocking degree of streptavidin – biotin interactions approximately equal to 75 % (as shown in Figure 5). Though this is only approximate calculation, it shows that the majority of bonds holding the sphere on the surface are broken simultaneously. This may be the reason why sharp peaks are observed in the rupture force spectrum and why the detectable signal appears during detachment. We carried out a series of experiments in which the positions of streptavidin on the sphere were blocked with biotin, and then the sphere was attached to the surface. Surface blocking is made to decrease the number of bonds and distinguish a single bond because the surface of the sphere is hitched up through a large number of bonds, their exact number depending on the sphere size. We suppose that blocking is a random process, so the fraction of streptavidin positions blocked in the contact region between the microsphere and the surface is the same as the fraction of positions blocked over the whole microsphere. The dependence on the degree of blocking is shown in Figure 5. It is clearly seen that the rupture force decreases linearly with an increase in blocking degree. When more than 75-80 % is blocked, a sharp jump is observed, and this time we measure not the rupture of streptavidin – biotin bonds but the rupture of biotin – blocked streptavidin bonds. In order to broaden the range towards an increase in the force value, we carried out measurements in liquid. The results of measurements in liquid are shown in Figure 6. One can see that the signal for hydrogen bond shifted to lower voltage, and the signal for chemically bound spheres appeared. Assuming identical (surface) density of bonds for nonspecific interaction, streptavidinbiotin system and for chemical bond, and assuming the rupture force to be the same when passing from the air to water, we can obtain the relative scale of rupture force. This is about 1 : 60 : 600 for nonspecific bonding, streptavidin – biotin bond, and chemical bond, respectively, though the data for nonspecific interaction were recorded at lower scanning velocity than for other bonds, so the obtained force value may be somewhat smaller than the actual one. This scaling seems reasonable and demonstrates the dynamic range of the method.

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The published data are: 160 pN for streptavidin – biotin interaction, 1.4 0.3nN for gold – sulphur bond. So, the relations between rupture forces in our experiments are in good agreement with the known data, in spite of the fact that we apply the tangential force while the force applied in AFM measurements is directed normally, and the direct comparison is not quite correct. Below the applications of our method will be considered as described in [5255]. The major application area is sensor, including biological sensors, for example, one can easily identify a molecule, phage, bacterium, or virus on the basis of the rupture force value. The sensitivity of the method allows us to determine the particles down to a single virus [53].

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Figure 5. The shifts of the positions of the first and major peaks in the rupture force spectrum with blocked streptavidin positions on the latex microspheres.

Figure 6. Rupture force spectra in water for the interaction of streptavidin with biotin and for chemical (amide) bond (similarly to Figure 4a.). The diameter of all the spheres is 5 m. New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

QCM in the Active Mode

13

Figure 7. Shift of the QCM resonance frequency depending on voltage applied, for the system: 1 – pure surface, 2- C2H5OH-SiO2.

The dependence of the resonance frequency on amplitude for the system C2H5OH/SiO2 is shown in Figure 7. The surface of silicon dioxide is hydrophilic, and ethanol molecule forms a hydrogen bond. According to [56] moderate or strong hydrogen bonds are formed in this system, their energy being 4-15 kcal/mol or 15-40 kcal/mol. The resulting rupture force value is 25±5 pN; this is an order of magnitude smaller than the rupture force for the covalent bond.

2. A MATHEMATICAL MODEL Copyright © 2013. Nova Science Publishers, Incorporated. All rights reserved.

2.1. Introduction Quartz crystal microbalance (QCM) has been used for a long time to investigate thin film deposition, etching, adsorption of gases. Due to a small temperature coefficient and high mechanical Q factor, the AT-cut QCM is widely used as a sensitive element in gas, chemical and biological sensors [57-62]. At present, researchers show growing interest to methods allowing direct determination of viruses or bacteria. An increase in the frequency of the fundamental mode allows us to improve the sensitivity of QCM and develop simple, efficient and cheap procedures for application in biology and medicine. The so-called AT cut is usually used; such a crystal oscillates in the thickness shear mode (TSM). Since Nomura and Okuhara [63] demonstrated that stable oscillations can also be obtain in a crystal fully submerged into a liquid, QCM had become a useful instrument in electrochemistry (electrochemical quartz crystal microbalance, EQCM) [42, 64-65]. It has also been demonstrated [66, 67] that the QCM can be used as a sensor in biomedical research. If the attached film is thin and sufficiently rigid, a decrease in the frequency is proportional to the added film mass. So, QCM is used as a very sensitive microbalance. The mass of the added layer is calculated using a known Sauerbrey equation [68]: ∆m= - C ∆f / n ,

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where C is a coefficient [ng x Hz-2 x cm-2], n is overtone number. Film thickness can be estimated using equation: d∆m , where is the density of the film under investigation. In many cases, a film is not rigid. A soft (viscoelastic) film does not exactly follow the oscillations of the crystal. Such a damping of crystal oscillations is a measure of film softness D determined as D = Elost/. Here Elost is the dissipated energy, that is, energy lost during one oscillation cycle, E is total energy accumulated in the oscillator. Measuring the frequency of harmonics and applying mathematical modelling we may characterize the deposited film in detail (viscosity, elasticity, thickness and density affect and D). A mathematical description of this model was presented in [69]. The authors of describe the application of this model to analyze the state of surface immobilized single strained biotin-modified probe DNA (b-DNA) coupled via streptavidin to a biotin-doped supported phospholipid bilayer (b-SPB) [70]. QSense company developed an instrument that allows determination of the parameters of viscoelastic films in liquids by means of the simultaneous determination of the damping parameter and the resonance frequency of the quartz crystal. The major advantage of this approach is the possibility to follow the kinetics of changes of structure and mass in surface processes (for example, during biomolecular adsorption) or in thin films. A promising application of the QCM in the determination of viruses and bacteria was proposed [53]. This method has a higher sensitivity than the existing ones. Unlike ordinary QCM technique, here a quartz resonator is not just a sensor but it also plays an active part with respect to the molecules or nanoparticles adsorbed on its surface. Measurements can be carried out both in the air and in the liquid phase. It was shown in [40] that the sensitivity of this method allows one to record the rupture of a single virus. By present, the application possibilities and further development of this method are restrained by the absence of an adequate mathematical description of particle rupture from the surface of QCM oscillating in the shear mode. Advances in these procedures are limited by the relative complicacy of description and representation of the physics of oscillations in ТSM resonators. All the existing description methods can be divided into four groups. The first group methods involve the model of equivalent circuits that represents a resonator as a branched oscillatory circuit and considers the effect of distributed mass load on impedance change [71-73]. The methods of the second group use various 2D and 3D models assigning a priori distribution of displacements [74, 75]. In the methods of the third group, direct equations of motion are solved to calculate the oscillations in the quartz crystal [76,79]. Finally, the methods of the fourth group use the direct 3D finite element modeling (FEM) [80-82] taking into account the crystal anisotropy, piezoelectric effect and metallization of the resonator facings. The above-listed calculation methods are rather complicated; this restricts their application. The effect of a point load on QCM is interesting also because this phenomenon may be involved in the investigation of the behavior of a single nanoparticle on a surface. It should be noted that the effect of a point load may be different; one should distinguish the added point mass and a touch with a needle. The goal was to develop, on the basis of a simple one-dimensional system, a mathematical description of the physical model of processes that take place during the rupture of a single nanoparticle from the surface. The development of such a model will allow us to

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QCM in the Active Mode

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achieve better understanding of the mechanism of nanoparticle interaction with the crystal surface. Though the experimental sensitivity of the QCM procedure is sufficient to detect the rupture of a single nano-sized body like a virus from the membrane [53], the accuracy of calculations according to a full 3D model taking into account the simultaneous influence of anisotropy, piezoelectric effect and electrically conducting electrodes does not describe small perturbations of this kind. We proposed a simple and clear QCM model which is based not on all the possible corrections to the oscillations of a loaded quartz plate calculated on the basis of primary principles but on the introduction of difficultly calculable parameters by taking the experimental values. In order to make the method a working tool for a doctor or a biologist, it is important, for example, not to calculate oscillation frequency but leave it in the free form till an accurate measurement, paying more attention to the parameters of the bodies under investigation. Below we give a detailed description of the approach for two practically important modes of QCM operation: in the free space and in a viscous liquid. The effect of a point load on the oscillations of the quartz crystal microbalance (QCM) is represented with a simple one-dimensional model constructed specially for the determination of the basic physical characteristics of solitary nanoparticles. Due to the analytical form of solution, the model is highly selective and sensitive to small mass load, and quite suitable for the identification of solitary viruses. Thickness shear mode in a quartz crystal microbalance is modeled with longitudinal oscillations of a pair of thin elastic strips, with the free parameters calibrated on the basis of experiment. This approach reduces a complicated three-dimensional problem to a onedimensional one and assesses the effect of distributed and localized mass load on the frequency response of a real QCM. A change of the frequency shift depending on the weigh and position of a point body is demonstrated; the ratios of signal intensities at different harmonics accompanying the rupture of the body from the surface due to inertia in the air and in a viscous liquid are considered. The model is developed for the determination of parameters of solitary biological nano-sized bodies: mass, size, and bond rupture force.

2.2. One-Dimensional Resonator Model Based on Longitudinal Oscillatory Motions in Thin Plates The frequency of the lowest thickness shear mode is [83] 1 f = 2h

 μ    ρ   q 

1/ 2

(16)

where h is plate thickness in Figure 8(a,с), ρq=2.65 g/cm3 is the density of quartz; μ =2.947*1011 dyn/cm2 is [84] the shear elastic constant describing the elastic wave directed along Z, with particle displacement toward the direction of X. For instance, the frequency of f ~ 14 MHz corresponds to the fundamental harmonic in a quartz crystal with h=0.12 mm; the half-wave of transverse oscillations is exactly equal to the plate thickness h. Having picked out two strips with the half-height h/2 directed along the particle displacement on the flat face

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of the resonator, as in Figure 8(d), we will write down the equations of particle motion for each of the strips.

Figure 8 (a, b, c, d). Step-by-step construction of a one-dimensional resonator model in the form of a working pair of thin elastic strips.

It is known that the longitudinal oscillations of thin plates meet the following equation for displacements ux [85]:

E  2u x  2u x = = 0, ρ 1  σ2 x 2 t 2 (17)





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where E is the Young's modulus, σ is the Poisson coefficient, ρ is the density. The x axis is directed along the plate length. To build up a one-dimensional resonator model, one should reduce the bulk density ρ to the linear one ρl per unit length and apportion the harmonic dependence on time t into a separate factor: ux(x, t)= u(x)e -iωt. An ordinary differential equation will be obtained from (17):





1  σ2  2u x + ω2 ρ i u=0, 2 a h / 2 E t

(18)

It is to be supplemented with the boundary conditions (here а is the width of the working strip in Figure 8 (c, d)). It is known that the shear amplitude rapidly falls down to zero in the region unoccupied with the electrodes, at a length of about 8-10% of the electrode diameter [86, 87]. Because of this, at the edges of the working area L displacements may be accepted to be equal to zero: u(0)=u(L)=0. The solution of (18) that meets these boundary conditions is:

u x = Ansinkn x where

kn =

 L

n,ωn =

 L

n

ahE ,n = 1,2,3,4..., An  const 2ρi 1  σ2





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(19)

QCM in the Active Mode

17

One can see in (19) that under the additional (uniform) mass load on the membrane, causing an increase in the linear density ρl, the relative frequency shift ∆f /f is negative and equal to Δρi Δ f = f 2 ρi

,

(20)

According to the generally accepted Sauerbrey equation, the frequency shift in a real 3D resonator with electrode area А caused by the distributed mass load ∆m is equal to [68]

Δf = 

2f 2 Δ m , A ρq μ q

(21)

Uniting thickness h from (16) with (21), we obtain for the frequency shift:

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Δ m / Ah  =  Δρ , Δf 2f 2 Δ m = =  f ρq ρq fA ρ q μ q

(22)

The ratios (22) and (20) will get equal if we demand the bulk effective density of the strip to be twice smaller than the quartz density ρ = ρq/2. With this requirement, the energy balance is also conserved: the mechanical energy of a pair of strips with longitudinal oscillations in Figure 8(d) and the energy of the region cut out in Figure 8(с) are equal to each other. Indeed, the energy of a volume element in a strip is T= ρ·v02/2 , where v0 is particle velocity uniform over the z section. In a real TSM (see Figure 8(a)), the cross distribution of the velocity is non-uniform: v~sin(πz/h) [88], and the energy of a corresponding volume element is T= ρq·v02/4, since the mean sin2(πz/h) value is equal to 1/2. Here v0 is the velocity on the surface. So, one may reduce the shear non-uniform 3D vibrations to uniform longitudinal contradirectional 3D oscillations of a pair of strips as shown schematically in Figure 8(a-d). The following should be done for further calculations. Let us mentally substitute the contradirectional motion of the pair of strips for unidirectional motion having changed the phase of the lower strip by π in (19). The oscillation energy would be unchanged. We will obtain one resonator strip of the same thickness h as the membrane height but with twice smaller density ρ=ρq/2. For the new strip, a response to the uniform mass load ∆m coincides with the frequency response of a real QCM according to the Sauerbrey rule (22). However, we will see further on that due to the transition to a one-dimensional model it is possible to calculate the influence of the point load as well. We leave width a as a free parameter on purpose, to be calibrated from experiment.

2.3. The Effect of a Point Load on a Quartz Crystal Microbalance Now we will obtain a solution within our model not for the distributed resonator load but for the localized (point) one. The domain of application of the load of mass m will be assumed to be so small that the body might be considered to be a point one, for example a

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single nanoparticle. To describe the microscopic bodies, we propose to use the Dirac δfunction [89], which can be represented in our model schematically as a narrow peak of linear density ρl. The main properties of Dirac δ-function, namely integrability with any continuous function F(x) and normalization to the unit area (23), will be used during solving the problem. +x

+x

 F x δx  x dx = F x ,  δx  x dx = 1 , 0

0

x

0

(23)

x

For verification, we will place a single nano-sized body m in point х0 and integrate the expression for density from 0 to L; owing to the second property (23) we will obtain: L

 ρ

l

+ m σ x  x 0 dx = ρl L + m = M + m ,

(24)

0

Here М is the mass of the working strip of the resonator and L is its length. As it should be, integration gives full mass M+m. Therefore, it is correct to represent the new linear density as ρl+ mδ(x-x0), and we may substitute it into equation (18) and try to integrate (18) with the help of the first property (23). Rewriting (18) we obtain:   d 2u m + k 2 1 + δ  x  x 0  u = 0 dx 2 ρ l  

(25)

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Here k=ω[2ρl (1-σ 2)/(ahE)]1/2 is an unknown parameter because frequency ω is changed due to load m. After a single integration of (25) in a small neighborhood ε of point х0, an additional equation will be obtained; it defines a jump of the derivatives u'(x)=du(x)/dx of a continuous function u(x): u ' x 0 + ε   u ' x 0  ε  = k

2

m u x 0 ρ



(26)

Solution will be searched for in the following form: Asin kx , x  x 0 ;   u x  =       φ 0 Bsin kx + , x  x ;  x  L 0 0  

(27)

where φ is some phase shift. Substituting (12) into (10-11) and using the previous boundary conditions u(0)=u(L)=0 we will obtain a connection between amplitudes A and В, and a dispersion equation for the new frequency ω: B = A sin kx 0  / sin kx 0 + φ ;     ctg kx +  ctg kx = kL m M ;       φ /   0     kL + = ; sin φ 0  

(28)

Here ctg means the cotangent function. Two latter equations in (13) being solved together define the above-introduced parameter k, which is proportional to frequency ω, and phase φ. New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

QCM in the Active Mode

19

However, for small m/M gy > gz  ge, which is reversed in comparison with that for O2– (gz > gy > gx  ge). New spin Hamiltonian parameters determined from W-band spectra of a natural citrine (Table 8A in Appendix), together with observed thermal properties and microwave

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82

Rudolf I. Mashkovtsev and Yuanming Pan

power dependence, suggest that Centers #6 and #7 of Mashkovtsev et al. (1978) are probably the O23– type (Pan et al., 2008). However, the g values of Centers #6 and #7 (Table 8A) are significantly higher than that predicted for the isolated O23–. Also, the O23– centers are commonly stabilized by a neighboring trivalent cation (Pan et al., 2012; Botis et al., 2009; Nilges et al., 2008; Bill, 1969), whereas Centers #6 and #7 do not have any detectable 27Al hyperfine structures. Therefore, the proposed structural models for centers #6 and #7 remain tentative. The basic model of the g factors for the ozonide radical predicts the g-minimum axis perpendicular to the molecular plane and the g-maximum along an OO direction (Schlick, 1972). The W-band spectra of a natural citrine (Pan et al., 2008) reveal Center C, which has similar principal g values but a distinctly larger 27Al superhyperfine structure in comparison with Center C of Maschmeyer and Lehmann (1983b). The direction of the g-maximum axis of center C is only 5° away from the O3-O4 edge of the SiO4 tetrahedron. The average g values of centers C and C (Table 8A) are similar to those of the classic ozonide radicals (Che and Tench, 1983; Botis et al., 2008; Schlick, 1972). The orientation of the unique A axis of center C approximately along the Si4–Si0 direction suggests that center C is linked to a substitutional Al3+ ion at the neighboring Si4 site (Pan et al., 2008). It is interesting that another ozonide radical reported by Botis et al. (2008) does not have any detectable 27Al superhyperfine structure, suggesting no Al3+ ion at the immediate neighboring Si sites. Silicon-vacancy hole centers, similar to the oxygen-vacancy electron centers, are common radiation-induced defects in quartz and have long been used in EPR dating and dosimetry (Garrison et al., 1981; Ikeya, 1993). They are also known to give rise to characteristic cathodoluminescence (CL) colors (Botis et al., 2006; Botis et al., 2005; Botis et al., 2008) and have been shown to be useful in defining and tracing paleo-pathways of uranium-bearing fluids in sedimentary basins (Pan et al., 2006; Hu et al., 2008). Further studies of siliconvacancy hole centers in quartz doped with enriched 17O would allow determination of their 17 O hyperfine coupling constants, which are required for confirmation of the proposed structural models. Also, periodic first-principles calculations using the supercell approach (Botis and Pan, 2009; Li and Pan, 2012), versus previous calculations using small clusters (Nilges et al., 2009; Pan et al., 2009), are expected to provide additional insights into the geometries, electronic structures, and formation mechanisms of silicon-vacancy hole centers in quartz. Finally, another family of defects involving small monovalent cations as charge compensators for a missing Si4+ ion is commonly classified as silicon-vacancy hole centers as well (Nuttall and Weil, 1980; Lees et al., 2003) (Table 9A). The best examples of this family include the two hydrogenic [H4O4]+ and [H3O4]0 centers involving four and three protons, respectively (Nuttall and Weil, 1980). The [H4O4]+ center is most likely formed from the neutral diamagnetic “hydrogarnet” defect [H4O4]0 by the loss of an electron. Lees et al. (2003) described a new hydrogarnet-like center [HLi2O4]0 in a gamma-ray-irradiated, synthetic quartz and suggested, on the basis of the principal directions of the g matrix, that hole trapping on the oxygen ion long-bonded to the missing silicon atom. Lees et al. (2003) evaluated the locations of the three monovalent cations by modeling the experimentally determined proton and lithium superhyperfine matrices. Their results showed that the proton position can be assigned with reasonable confidence and is closely associated with O4, adjacent to the main c-axis channel, with an OH bond distance of ~1 Å.

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Nature of Paramagnetic Defects in -Quartz

83

However, the two lithium nuclei could not be assigned with as much confidence and are probably located roughly equidistant from two oxygen anions surrounding the silicon vacancy, close to the tetrahedral edges formed by the four oxygen anions. Lees et al. (2003) recommended further evaluation of the electronic structures and magnetic properties of the [HLi2O4]0 center and other hydrogarnet-like paramagnetic defects in quartz by use of firstprinciples calculations.

APPENDIX. SPIN HAMILTONIAN PARAMETERS OF PARAMAGNETIC DEFECTS IN QUARTZ Table 1A. EPR parameters of aluminum-related centers Center, T, K

g principal values

[AlO4]0 35

gc=2.01810 2.060208 2.008535 2.001948

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0

[AlO4/H] 35

0

[AlO4/Li] 35

gc=2.02450 2.056931 2.008056 2.002495

gc=2.02611 2.061016 2.008259 2.001957

g principal directions θ φ 60.755 124.439 131.641

52.205 59.616 127.38

51.688 116.10 130.52

237.62 305.05 177.48

104.45 347.4 50.78

101.52 168.75 53.998

HF / mT principal values A(27Al) -0.6127 -0.6187 -0.5037 P (27Al) -0.02223 -0.01533 0.03756 A(27Al) -0.9396 -0.9513 -0.8244 P (27Al) -0.0342 0.0102 0.0241 A(1H) -0.063 -0.050 0.129 A(27Al) -0.8105 -0.8140 -0.6907 P (27Al) -0.0263 0.0017 0.0246 A(7Li)

HF principal directions θ φ

References

92.17 135.23 45.29

119.07 211.26 206.92

60.12 60.24 44.69

89.244 340.07 214.76

127.23 132.87 65.566

198.96 64.105 129.16

93.27 3.46 91.13

51.19 70.32 141.25

104.7 162.9 81.53

249.7 38.46 337.5

60.312 37.500 110.73

23.883 Nuttall and 245.90 Weil (1981c) 306.34

69.38 39.18 58.36

37.50 280.01 140.91

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Nuttall and Weil (1981a)

Nuttall and Weil (1981c)

84

Rudolf I. Mashkovtsev and Yuanming Pan Table 1A. (Continued)

Center, T, K

g principal values

gc=2.01854 [AlO4/Na]0 2.044143 35 2.008591 2.002668

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[AlO4/Li]q 15

[AlO4]+ 35 S=1

2.055681 2.008643 2.002240

gc=2.02258 2.04722 2.01017 2.00291

g principal directions θ φ

HF principal directions θ φ 105.1 249.6 164.7 80.17 92.69 340.3

126.74 113.41 45.90

110.19 72.41 27.31

305.22 28.53 260.64

49.56 131.88 111.44

331.24 111.07 221.68

86.21 170.1 99.13

333.69 41.38 244.31

85.49 8.29 83.04

64.07 186.74 333.52

40.46 111 123

209.84 146 251

49 58 122.1

219 96 162.8

70.1 107 154

186.2 102 229

33 104 60

306 14 96

44.999 90 45.001

270 0 90

141.57

90

58.56 127.96 53.75

131.62 90 138.38

HF / mT principal values -0.032 -0.024 0.028 A(27Al) 97.85 -0.7455 168.99 -0.8705 234.19 -0.8742 P (27Al) 0.0247 -0.0035 -0.0212 A(23Na) 0.01910 -0.01085 -0.02250 P(23Na) 0.0242 0.0053 -0.0295 A(27Al) 240.51 -0.6395 302.02 -0.7483 357.14 -0.7507 P (27Al) 0.0274 -0.0034 -0.0241 A(7Li) 0.0322 -0.0195 -0.0232 P(7Li) 0.0025 -0.0003 -0.0023 D 270 -46.891 0 17.236 90 29.655 A(29Si) 0.455

New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

References

Dickson and Weil (1990)

Walsby et al. (2003)

Nuttall and Weil, 1981b

Nature of Paramagnetic Defects in -Quartz Center, T, K

[AlO4/Ag]0 I

20

[AlO4/Ag]0 II

20

g principal values

g principal directions θ φ

HF / mT principal values 0.474 0.486 A(27Al) -0.805 -0.815 -0.877 P (27Al) 0.0278 0.0119 -0.0397

85

HF principal directions θ φ 90 0 51.57 90 53.57 90 143.57

90 0 90

59.96 90 149.96

90 0 90

References

gc=2.1216 2.2667

111.5

242.6

2.1020 2.0074 gc=2.1610

155.1 101.6

31.7 147.9

Davis et al. (1978)

2.2749

57.1

68.5

Davis et al.

2.1141 2.0061

145.9 97.7

51.5 153.4

(1978)

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Table 2A. EPR parameters of germanium-related centers Center T, K [GeO4]-I 15

[GeO4]-II 15

[GeO4]-av or Ge(B) 220 [GeO4]-III 293

g principal values gc=1.99797 2.0017 2.0004 1.9934 gc=1.99394 2.0001 2.0007 1.9929 gc=1.99696 2.0001 1.9981 1.9970 gc=1.9955 2.0011 1.9950 1.9939 gc=1.9951

g principal directions θ φ 45.60 16.93 74.10 270.74 131.29 346.25 90 0 110.96 270 159.04 90 93.67 270 90 0 176.32 90 113 52 47

50 340 116

HFS/ mT principal values A(73Ge) -27.374 -27.617 -29.119 A(73Ge) -29.630 -27.977 -27.791 A(73Ge) -28.989 -28.264 -27.831 A(29Si) 1.054 0.818 0.818 A(73Ge)

HFS principal directions θ φ

References

132.82 47.75 72.94

344.71 17.40 271.22

Isoya et al. (1978)

90 59.79 30.20

0 90 270

Isoya et al. (1978)

105.25 90.0 15.25

90 0 90

Isoya et al. (1978)

66 59 41

83 337 204

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Feigl and Anderson(1970)

86

Rudolf I. Mashkovtsev and Yuanming Pan Table 2A. (Continued)

Center T, K

g principal values

[GeO4]-IV 293

2.0010 1.9942 1.9935 gc=1.9976 2.0009 1.9952 1.9943 gc=1.99480 2.00091 1.99726 1.99292

[Ge(E2)/H]0293

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[GeO4/H2Li+]0 293

0

[GeO4/Li] 293

A

[GeO4/Li]0C 293

[GeO4/Na]0A 293

gc=1.9926 2.0014 1.9997 1.9913 gc=1.9995 2.0000 1.9973 1.9962 gc=1.993083 1.991581 1.999807 2.001152

g principal directions θ φ 114 49 53 339 47 114 131 49 68

208 167 277

114.06 52.07 69.03 331.92 32.85 98.32

66 90 24

270 0 90

26 90 64

90 0 270

156.7 90 113.3

270 0 90

HFS/ mT principal values 28.7 24.1 24.1 A(1H) 0.1 -0.03 -0.05 A(73Ge) -21.291 -21.437 -23.928 A(1H) 8.5893 8.3717 8.3153 A(7Li1) -0.04599 -0.03740 0.05960 A(7Li2) 0.0398 -0.0433 -0.0672 A(73Ge) -28.206 -29.569 -27.869 A(73Ge) -30.876 -29.438 -29.532 A(73Ge) -29.105 -27.465 -27.251 A(23Na) 0.0965 0.0617 0.0532 P(23Na) -0.0093

HFS principal directions θ φ 113 50 145 178 65 129 130 57 57

203 145 260

148.87 104.87 63.34

282.26 166.18 248.52

114.99 99.04 26.79

112.99 18.74 90.38

108.45 124.78 40.72

195.55 298.94 262.75

108.03 21.08 79.45

355.55 27.94 269.03

67 90 23

270 0 90

26 90 64

90 0 270

90 61 23

0 90 270

90 14 76

0 270 90

120.4

90

New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

References

Feigl and Anderson(1970) Feigl and Anderson(1970)

Weil (1971a)

Weil (1971b)

Weil (1971b)

Dickson et al. (1991)

Nature of Paramagnetic Defects in -Quartz Center T, K

g principal values

[GeO4/Na]0C 293

gc=2.00026 1.99630 1.99728 2.00059

[GeO4/Ag]0 293

gc=1.99249 2.0084 2.0000 1.9884

g principal directions θ φ

74.1 90 15.9

116.7 90 153.3

90 0 270

270 0 90

HFS/ mT principal values 0.0014 0.0079 A(73Ge) -31.305 -29.769 -29.697 A(23Na) 0.089 0.064 0.060 P(23Na) 0.0133 -0.0057 -0.0075 A(107Ag) 25.859 25.938 27.076 A(109Ag) 29.858 29.941 31.261

HFS principal directions θ φ 90 0 30.4 90 171 90 98.8

270 0 90

17.2 90 72.8

270 0 90

114.2 90 155.8

270 0 90

40.3 49.7 90

270 90 0

38.8 51.2 90

270 90 0

87

References

Dickson et al. (1991)

Laman and Weil (1977)

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Table 3A. EPR parameters of titanium-related centers Center T, K -

[TiO4] I’ 20

[TiO4/H]0A 20

[TiO4/H]0B 20

g principal values gc=1.9831 1.9910 1.9224 1.9242 gc=1.96957 1.9856 1.9310 1.9151

g principal directions θ φ 19.9 90 109.9 90 90 0 151.1 75.2 82.8 358.5 62.1 92.3

gc=1.90568 1.990 86.6 87.7 1.914 118.6 175.8

HFS/ mT principal values A(47Ti) -0.400 2.148 2.152 A(1H) 0.937 0.456 0.434 A(47Ti) 2.176 0.418 0.191 A(1H) 0.914 0.511

HFS principal directions θ φ 158.6 68.6 90

270 270 0

72.1 140.5 123.8

354.4 61.4 276.9

118.2 84.8 28.8

270.5 357.7 258.2

113.52 52.21

345.22 55.50

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References

Isoya and Weil (1979)

Rinneberg and Weil (1972)

Rinneberg

88

Rudolf I. Mashkovtsev and Yuanming Pan Table 3A. (Continued)

Center T, K

g principal values 1.903

[TiO4/Li]0A 35

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[TiO4/Li]0B 35

[TiO4/Na]0A 35

g principal directions θ φ 28.9 183.9

gc=1.97068 1.97887 20.6 1.93094 90 1.91193 69.4

1.98022 1.92977 1.91022

270 0 90

108.6 270 90 0 161.4 90

gc=1.96271 1.89841 106.4 278.7 1.95160 70.6 194.7 1.97046 154.1 151.2

HFS/ mT principal values 0.476 A(47Ti) 1.930 0.471 0.225 A(7Li) 0.2691 0.1286 0.1103 A(47Ti) 2.6003 0.6261 0.6218 A(49Ti) 2.6025 0.6173 0.6157 A(7Li) 0.161 0.001 -0.003 A(49Ti) 2.686 0.727 0.680 A(23Na) 0.160 0.088 0.084 A(49Ti) 3.082 1.220 0.865

HFS principal directions θ φ 46.98 279.17 12.50 83.29 79.49

301.09 179.07 87.82

90 36.3 53.7

0 270 90

112.8 90 157.2

270 180 270

112.9 157.1 90

270 90 0

90 103.3 166.7

0 270 90

21.5 90 68.5

270 0 90

103.7 126.9 40.2

356.3 255.8 283.1

70.6 19.6 92.7

94.2 282.9 5.2

References and Weil (1972)

Isoya et al. (1988)

Bailey and Weil (1992a)

Bailey and Weil (1992b)

Table 4A. EPR parameters of ferric-related centers Center T, K

g principal values -

[FeO4]

gc=2.00412 2.00357

g principal directions θ φ 90

0

FS/HFS/ mT principal values D 48.9397

FS/HFS principal directions θ φ 90

0

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References

Nature of Paramagnetic Defects in -Quartz Center T, K

g principal values

293

2.00384 2.00532

0

[FeO4/H] 20

a

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0

[FeO4/Li] 20

0

a

[FeO4/Li] 20

b

gc=2.005230 2.00402 2.00494 2.00567

gc=2.00408 2.00426 2.00418 2.00360

gc=2.00407 2.00537 2.00404 2.00303

g principal directions θ φ 25.7 90 115.7 90

115.9 114.1 143.2

90 155.4 65.4

98.8 171.1 90.7

17.5 274.9 147.9

180 90 90

143.8 319.3 53.6

89

FS/HFS/ mT principal values 8.4268 -57.3665 B4m 0.01629 -0.05274 0.15341 0 0 D 207.2335 82.5052 -289.738 A(1H) -0.1641 -0.1392 0.3247 B4m 0.0157 -0.0592 0.1409 0.0792 0.0510 D 226.5253 -49.9481 -176.577 B4m 0.0183 -0.0442 0.136 0 0 A(7Li) 0.1306 -0.0214 -0.0340 D 179.2085 -11.7146 -167.490

FS/HFS principal directions θ φ 89.3 90 0.7 90

0.06530 0.1474

0.02109 -0.0423

References Mombourquette et al. (1986)

0 0 -0.14795 -0.10312

111.0 125.0 42.6

261.4 7 326.7

69.1 145.2 63.6

98.2 41.5 357.3

Mombourquette et al. (1989)

0.00357 -0.0867 0.1131 0.1457

60.3 90 29.7

270 0 90

Halliburton et al. (1989)

0 0 0.1356 0.0143

90 150.7 119.3

180 270 270

70.8 30.0 112.1

121.9 354.7 40.0

New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

Minge et al. (1989b)

90

Rudolf I. Mashkovtsev and Yuanming Pan Table 4A. (Continued)

Center T, K

g principal values

gc=2.0036 [FeO4/Na] a 2.0045 20 2.0043 2.0029 0

g principal directions θ φ

60.7 118.4 136.9

110.9 38.6 164.0

FS/HFS/ mT FS/HFS principal directions principal values θ φ -0.08557 0.03847 -0.02398 -0.0677 -0.03818 D 158.5947 120.6 258.3 -2.1267 78.3 175.4 -156.471 33.2 283.8 B4m 0.0196 -0.0417 -0.0528 0.1245 0.1345 0.1138 -0.0207 -0.0196 -0.0371

References

Minge et al. (1990)

Table 5A. EPR parameters of phosphorus centers

Copyright © 2013. Nova Science Publishers, Incorporated. All rights reserved.

Center T, K 0

[PO4] 293

AV’

[PO4]0E’ 120

[PO4]0G’ 120

[PO4]0G’ 40

g principal values gc=2.0007 2.0010 2.0025 2.0003 gc=2.0012 2.0013 2.0034 1.9991 gc=1.9998 2.0012 2.0032 1.9991 gc=1.9999 2.0012 2.0032 1.9991

g principal directions θ φ 90 117.1 152.9

0 90 270

76.2 46.1 45.9

270.5 11.1 169.9

90 114.9 155.1

0 270 90

90 115.5 154.6

0 270 0

HFS/ mT principal values A(31P) 113.902 112.099 105.779 A(31P) 115.972 102.514 101.222 A(31P) 122.893 108.686 107.484 A(31P) 122.796 108.528 107.345

HFS principal directions θ φ 90 84.5 174.5

0 90 270

80.6 46.8 44.7

26.9 7.8 169.3

90 115.1 154.9

0 270 90

90 115.2 154.6

0 270 90

New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

References

Uchida et al. (1979)

Nature of Paramagnetic Defects in -Quartz

91

Table 6A. EPR parameters of E' centers Center T, K E'1 293

E'1 293

E'2(I) 293

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E'2(II) 293

E'3 293

E'4 293

E'9 293

g principal values gc=2.0006 2.00179 2.00053 2.00030 gc=2.0006 2.00172 2.00051 2.00027 gc=2.0009 2.0020 2.0007 2.0005

gc=2.00098 2.00161 2.00051 1.99994

gc=2.00081 2.0017 2.0007 2.0005 gc=2.00106 2.00154 2.00064 2.00059

gc=2.00095 2.00183 2.00079 2.00067

g principal directions θ φ 114.1 134.5 125.4

227.7 344.4 118.7

111.2 139.6 57.4

229.4 346.5 305.0

59.9 67.2 140.7

28.4 132.5 73.3

45.7 129.1 109.8

63.6 153.6 91.0 46.3 120.6 120.8

114 152 105

72.2 109.8 2.7

HFS/ mT principal values Ac(29Si)=40.36 45.32 39.08 39.07 Ac(29Si)=40.15 45.4000 38.9001 38.9000 Ac(29Si)=42.5 45.857 40.539 40.490 Ac(1H)=0.04 0.16 -0.01 -0.02 Ac(29Si)=46.4 49.6016 43.3413 43.2862 Ac(1H)=0.01 0.0249 -0.0096 -0.0112

HFS principal directions θ φ 114.1 128.3 132.1

229.7 340.4 115.9

Jani et al. (1983)

113.0 28.2 74.6

230.0 192.3 313.3

Perlson and Weil (2008)

58.8 132.9 121.1

87.7 143.4 19.1

Perlson and Weil (2008)

54.2 136.8 69.2

34.9 74.7 140.8

48.8 132.8 71.2

70.7 106.4 178.1

44.9 83.2 134.2

10.6 107.5 24.2

86.6 64.0 176.1 66.2 10.7 121.4

213 359 117

References

Perlson and Weil (2008)

Perlson and Weil (2008) Ac(29Si1)=15.57 17.528 15.357 15.334 Ac(29Si2)=37.56 39.727 34.814 34.778 A(1H) 1.886 0.065 -0.005 Ac(29Si)=39.34 43.94 37.46 37.42

71.9 73.1 154.8

44.4 140.1 90.5

43.9 100.6 131.9

86.1 7.4 107.1

53.3 80.1 141.5

70.9 168.4 91.1

119.7 150 92

214.7 30 124

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Isoya et al. (1981)

Mashkovtsev and Pan (2012b)

92

Rudolf I. Mashkovtsev and Yuanming Pan Table 7A. EPR parameters of E'' centers (triplet approximation)

Center T, K

g principal directions θ φ 136.3 67.3 125.0

162.1 226.2 299.2

132 62 125

184 245 313

130 95 40

67 333 57

114.1

304.1

D/ mT principal values Dc=1.10 2.542 -1.254 -1.288 Dc=1.79 1.793 -0.894 -0.899 Dc=0.66 3.783 -1.883 -1.899 Dc=1.0 6.322

D principal directions θ φ

E''6

gc=2.0009 2.00133 2.00077 2.00056 gc=2.0010 2.00142 2.00063 2.00061 gc=2.0007 2.00135 2.00078 2.00034 gc=2.0007 2.00144

293

2.00106

85.2

32.0

-3.118

128.0

12.2

155.3

111.5

134.8

61.1

61.3

-3.204 Dc=0.38 0.794

124.9

E''7

2.00044 gc=2.0008 2.00151

48.5

61.7

293

2.00079

90.8

331.8

-0.394

48.1

279.2

151.1

63.3

350.3

119.9

237.8

-0.399 Dc=0.71 1.318

109.8

E''8

2.00045 gc=2.0009 2.00178

132.2

235.6

293

2.00097

103.2

335.6

-0.656

56

287

33.2

266.5

175

126.0

243.5

-0.662 Dc=2.227 2.664

61

E''9

2.00060 gc=2.0008 2.00166

136.1

240.9

293

2.00056

61.1

177.2

-1.324

86.8

327.6

2.00034

49.6

295.3

-1.339

133.7

54.6

E''2 293

E''3 293

E''4 293

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g principal values

References

130.9 123 51

238.2 113 180

Mashkovtsev and Pan (2011)

138.1 127.3 106.4

225.7 13.6 116.6

127.6 129.2 118.5

265.7 34.6 150.9

Mashkovtsev and Pan (2011)

123.1

251.6

Mashkovtsev and Pan (2012a)

Not published

Mashkovtsev and Pan (2012a)

Mashkovtsev and Pan (2012a)

Mashkovtsev and Pan (2012a)

Table 8A. EPR parameters of silicon-vacancy hole centers Center T, K

g principal values

#1 O2110

gc=2.025 2.02945 2.00765 2.00210

g principal directions θ

φ

26.0 64.0 88.0

266.2 91.2 0.3

HFS/ mT principal values A(27Al) -0.025 -0.026 -0.027

HFS principal directions θ φ 80.0 63.2 28.9

New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

References

Nilges et al. (2009)

Nature of Paramagnetic Defects in -Quartz Center T, K

g principal directions θ

φ

gc=2.030

B O2293

2.03505 2.00773 2.00234

22.1 71.1 78.6

172.6 319.3 5.32

B' O2293

2.03555 2.00771 2.00231

22.5 69.5 80.9

165.5 319.5 52.9

2.04953 2.00701 2.00206

73.6 50.1 44.4

248.9 353.0 141.5

2.05175 2.00682 2.00213

76.4 51.7 41.5

244.1 345.1 138.2

G O2293

2.03102 2.00809 2.00238

46.8 84.2 43.7

0.7 265.2 169.2

G' O2293

2.02925 2.00809 2.00238

46.8 84.2 43.7

0.7 265.2 169.2

57.6 69.5 39.7 76.0 22.1 73.0

36.7 293.1 176.5 141.1 13.6 235.4

gc=2.008

D O2115

E O2115

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g principal values

#6 O2377 #7 O2377

-

HFS/ mT principal values A(29Si) 0.420 0.441 0.444 A(27Al) -0.222 -0.292 -0.300 A(27Al) -0.27 -0.35 -0.36 A(27Al) -0.038 -0.140 -0.146 -0.020 -0.092 -0.101 A(27Al) -0.41 -0.51 -0.54 A(27Al) -0.41 -0.51 -0.54

HFS principal directions θ φ

93

References

65.5 66.9 34.8

262.5 3.7 131.5

65 42 58

156 36 263

Pan et al. (2008)

62 107 33

156 237 300

Pan et al. (2008)

73 77 20

28 122 248

Pan et al. (2009)

51 38 92

302 128 214

Pan et al. (2009)

52 39 80

307 146 44

Nilges et al. (2008)

52 39 80

307 146 44

Pan et al. (2008)

gc=2.018 2.06807 2.00732 2.00187 2.05960 2.00759 2.00179

C* O3 293

2.0183 2.0090 2.0033

26.7 90 63.3

270 0 90

C' O3293

2.01698 2.00823 2.00248

30.7 75.2 63.7

274.9 158.6 61.1

X** O3293

2.0177 2.0076 2.0029

39.6 89. 50.3

269.8 0.4 90.8

Pan et al. (2008) Pan et al. (2008) A(27Al) 0.15 0.12 0.12 A(27Al) -0.10 -0.21 -0.22

33

90

Maschmeyer and Lehmann (1983)

53 57 52

309 191 72

Pan et al. (2008)

New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

Botis et al., (2008)

94

Rudolf I. Mashkovtsev and Yuanming Pan Table 9A. EPR parameters of miscellaneous centers

Center T, K

g principal values

[SiO4/Li]0 35

gc=1.999282 1.998795 2.000534 2.001462

[SiO4/Ag]0 20

[SiO4/Cu]0

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77

gc=1.99726 1.99978 1.99864 1.99244

1.998 2.000 2.000

g principal directions θ φ 154.7 90 115.3

88.1 28.3 118.1

60 150 90

270 0 90

357.4 263.8 268.5

90 90 0

Cu2+ 77

2.420 2.130 2.021

65 28 80

90 245 355

Ni+ 77

2.787 2.111 2.088 gc=2.0628 2.1351 2.0047 1.9962 gc=2.0369 2.0911 2.0103 2.0002 gc=2.002174

70 58 40

90 347 210

135.5 60.5 123.2

263.3 322 30.2

127.1 55.8 124.5

267.1 326.2 28.4

[H3O4]0 25

[H4O4]+ 25

HFS/ mT principal values A(29Si) 44.56 40.44 40.12 A(7Li) 0.1489 0.0928 0.0881 A(107Ag) 39.220 39.341 40.87 A(29Si) 11.904 11.999 14.230 A(65Cu) 122.08 122.14 128.75 A(29Si) 16.97 16.97 20.00 A(63Cu) 2.31 7.57 11.48

HFS principal directions θ φ 90 66.3 23.7

0 90 270

90 115.1 154.9

0 270 90

124.9 34.9 90.1

270.3 270.1 180.2

114.0 24.0 90.1

270.2 270.1 180.2

60 150 90

90 90 0

60 150 90

90 90 0

65 28 80

90 245 355

References

Bailey and Weil (1991)

Davis and Weil (1978)

Amanis and Kliava (1977)

Solntsev et al. (1974)

Solntsev et al. (1974)

Nuttall and Weil (1980)

A(1H)

New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

Nature of Paramagnetic Defects in -Quartz Center T, K

g principal values

H0 80

2.002266 2.002228 2.002095

0

[HLi2O4] 100

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A 77

Al…O- - P 300 #5 293

O-- O40 S=1

2.034377 2.009657 2.002674

2.03408 2.00925 2.00346

g principal directions θ φ 132.8 270 90 0 137.2 90

115.1 128.4 131.3

0 109.1 21

70.6 182.3 316.3

HFS/ mT principal values 51.9483 51.7505 51.6981 A(29Si) -0.068 -0.130 -0.134 A(1H) 0.5619 -0.2145 -0.3035 A(7Li1) -0.2437 -0.1676 0.0340 A(7Li2 ) -0.0752 -0.0395 0.0472

95

HFS principal directions θ φ 65.4 270 155.4 270 90 0 116.2 90 26.2

270 0 90

142.1 55.7 104.0

112.8 141.3 221.5

11.4 29.6 97.7

98.4 116.5 192.6

136.3 66.3 56.0

195.9 133.5 240.7

98.4 266.4 112.1

2.0105 2.0149 2.0172 2.0229 2.0123 2.0010

148.9 96.1 131.6 90 90 0

10.6 110.9 204.5 0 90

2.16671 2.00229 1.99299

48.3 111.3 130.7

198.1 267.7 158.2

References

Isoya et al., (1983)

Lees et al. (2003)

Maschmeyer et al. (1980)

A(31P)=4.5 A(27Al) 0.099 0.142 0.135

120.0 118.5 136.3

-14.2 237.5 113.5

Maschmeyer and Lehmann (1983a) Mashkovtsev et al. (1978)

D -6.225 3.093 3.132

112.6 22.6 90

90 90 0

Isoya et al., (1982)

ACKNOWLEDGMENT R.I.M. acknowledges support from the Russian Foundation for Basic Research (Grant 1005-00178).

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REFERENCES . Aliabadi, R., Amraei, R., Ranjbar, A. H., Rafieian, S., and Nasirimoghadam, S. 2010 ESR response of powder samples of clear fused quartz material to high doses of 10 MeV electrons: possible applications for industrial radiation processing Nuclear Instruments and Methods in Physics Research Section B-Beam Interactions with Materials and Atoms 268 2411-4. Allan, D. C. and Teter, M. P. 1990 Local density approximation total energy calculations for silica and titania structure and defects Journal of the American Ceramic Society 73 324750. Amanis, I. K. and Kliava, J. G. 1977 Modèles des centre paramagnétiques formés par les atomes de cuirve et d'argent dans le quartz Physica Status Solidi A 41 385-92. Anand, S. V., Pandian, M. S., Ravikumar, R., and Rao, P. S. 2012 EPR characteristics of quartz from tungsten deposits at Degana and Balda, Rajasthan, India. Radiation Effects and Defects in Solids 167 163-9. Azzoni, C. B., Meinardi, F. and Paleari, A. 1994 Traped-hole centers in neutron-irradiated synthetic quartz Physical Review B 49 9182-5. Bahadur, H. 2003 Radiation-induced modifications of point defects in quartz crystals and their application in radiation dosimetry Radiation Measurements 36 493-7. Bailey, P. and Weil, J. A. 1991 EPR study of the [SiO4/Li]0 center in alpha-quartz Journal of the Chemical Society-Faraday Transactions 87 3143-6. Bailey, P. and Weil, J. A. 1992a EPR of [TiO4/Li]B0 and related centers in X-irradiated alphaquartz Journal of Physics and Chemistry of Solids 53 601-10. Bailey, P. and Weil, J. A. 1992b The EPR spectral parameters and dynamic properties of the center [TiO4/Na]A0 in X-irradiated alpha-quartz Journal of Physics and Chemistry of Solids 53 309-18. Baker, J. M., Jenkins, A. A. and Ward, R. C. C. 1991 Electron magnetic-resonance in lithiumoxide from a center containing Fe3+ Journal of Physics-Condensed Matter 3 8467-77. Balatsky, A. V., Nishijima, M. and Manassen, Y. 2012 Electron spin resonance-scanning tunneling microscopy Advances in Physics 61 117-52. Beerten, K. and Stesmans, A. 2005 Single quartz grain electron spin resonance (ESR) dating of a contemporary desert surface deposit, Eastern Desert, Egypt Quaternary Science Reviews 24 223-31. Beerten, K. and Stesmans, A. 2006 Some properties of Ti-related paramagnetic centres relevant for electron spin resonance dating of single sedimentary quartz grains Applied Radiation and Isotopes 64 594-602. Beurlen, H., Müller, A., Silva, D., and Da Silva, M. R. R. 2011 Petrogenetic significance of LA-ICP-MS trace-element data on quartz from the Borborema Pegmatite Province, northeast Brazil Mineralogical Magazine 75 2703-19. Bill, H. 1969 Investigation on colour centres in alkaline earth fluorides Helvetica Physica Acta 42 771–97. Blöchl, P. E. 2000 First-principles calculations of defects in oxygen-deficient silica exposed to hydrogen Physical Review B 62 6158-79.

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Boero, M., Oshiyama, A. and Silvestrelli, P. L. 2003 E' centers in alpha quartz in the absence of oxygen vacancies: A first-principles molecular-dynamics study Physical Review Letters 91 206401. Boero, M., Oshiyama, A. and Silvestrelli, P. L. 2004 E' centers in silicon dioxide: Firstprinciples molecular dynamics studies Modern Physics Letters B 18 707-24. Boero, M., Pasquarello, A., Sarnthein, J., and Car, R. 1997 Structure and hyperfine parameters of E'(1) centers in alpha-quartz and in vitreous SiO2 Physical Review Letters 78 887-90. Bossoli, R. B., Jani, M. G. and Halliburton, L. E. 1982 Radiation-induced E'' centers in crystalline SiO2 Solid State Communications 44 213-7. Botis, S., Nokhrin, S. M., Pan, Y. M., Xu, Y. K., Bonli, T., and Sopuck, V. 2005 Natural radiation-induced damage in quartz. I. Correlations between cathodoluminence colors and paramagnetic defects Canadian Mineralogist 43 1565-80. Botis, S., Pan, Y. M., Bonli, T., Xu, Y. K., Zhang, A. M., Nokhrin, S., and Sopuck, V. 2006 Natural radiation-induced damage in quartz. II. Distribution and implications for uranium mineralization in the Athabasca basin, Saskatchewan, Canada Canadian Mineralogist 44 1387-402. Botis, S. M., Adriaens, D. A. and Pan, Y. M. 2009 Ab initio calculations on the O23--Y3+ center in CaF2 and SrF2: its electronic structure and hyperfine constants Physics and Chemistry of Minerals 36 1-7. Botis, S. M., Pan, Y., Nokhrin, S., and Nilges, M. J. 2008 Natural radiation-induced damage in quartz. III. A new ozonide radical in drusy quartz from the Athabasca Basin, Saskatchewan Canadian Mineralogist 46 125-38. Botis, S. M. and Pan, Y. M. 2009 Theoretical calculations of [AlO4/M+]0 defects in quartz and crystal-chemical controls on the uptake of Al Mineralogical Magazine 73 537-50. Botis, S. M. and Pan, Y. M. 2011 Modeling of [AlO4/Li+]+ paramagnetic defects in alphaquartz Canadian Journal of Physics 89 809-16. Breiter, K. and Müller, A. 2009 Evolution of rare-metal granitic magmas documented by quartz chemistry European Journal of Mineralogy 21 335-46. Buscarino, G., Agnello, S. and Gelardi, F. M. 2006 Characterization of E'δ and triplet point defects in oxygen-deficient amorphous silicon dioxide Physical Review B 73 045208.1-8. Buscarino, G., Agnello, S. and Gelardi, F. M. 2009a Structural modifications induced by electron irradiation in SiO2 glass: Local densification measurements EPL 87 26007.1-5. Buscarino, G., Agnello, S., Gelardi, F. M., and Boscaino, R. 2009b Polyamorphic transformation induced by electron irradiation in a-SiO2 glass Physical Review B 80 094202.1-11. Carbonaro, C. M., Fiorentini, V. and Bernardini, F. 2001 Proof of the thermodynamical stability of the E' center in SiO2 Physical Review Letters 86 3064-7. Chadi, D. J. 2003 Negative-U property of the oxygen vacancy defect in SiO2 and its implication for the E '(1) center in alpha-quartz Applied Physics Letters 83 437-9. Che, M. and Tench, A. J. 1983 Caracterization and reactivity of molecular-oxygen species on oxide surfaces Advances in Catalysis 32 1-148. Claridge, R. F., Kryliouk, O. M., Weil, J. A., and Williams, J. A. 2008 Paramagnetic Ge-Li centres in alpha quartz revisited: The D-Li( GeO4/Li (0)(D)) centre Canadian Journal of Physics 86 1303-11.

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Cortezão, S. U., Pontuschka, W. M., Da Rocha, M. S. F., and Blak, A. R. 2003 Depolarisation currents (TSDC) and paramagnetic resonance (EPR) of iron in amethyst Journal of Physics and Chemistry of Solids 64 1151-5. Cox, R. T. 1976 ESR of an S=2 centre in amethyst quartz and its possible identification as the d4 ion Fe4+ Journal of Physics C: Solid State Physics 9 3355-61. Cox, R. T. 1977 Optical absorption of the d4 ion Fe4+ in pleochroic amethyst quartz Journal of Physics C: Solid State Physics 10 4631-43. Cressey, G., Henderson, C. M. B. and Vanderlaan, G. 1993 Use of L-edge X-ray-absorption spectroscopy to characterize multiple valence states of 3d transition-metals - a new probe for mineralogical and geochemical research Physics and Chemistry of Minerals 20 111-9. Davis, P. H., Huang, C. Y. and Weil, J. A 1978 Paramagnetic aluminum-silver centers in alpha-quartz Journal of the Physics and Chemistry of Solids 39 897-9. Davis, P. H. and Weil, J. A. 1978 Silver atom center in alpha-quartz Journal of the Physics and Chemistry of Solids 39 775-80. Dedushenko, S. K., Makhina, I. B., Mar'in, A. A., Mukhanov, V. A., and Perfiliev, Y. D. 2004 What oxidation state of iron determines the amethyst colour? Hyperfine Interactions 156 417-22. Devine, R. A. B. and Hübner, K. 1989 Radiation-induced defects in dense phases of crystalline and amorphous SiO2 Physical Review B 40 7281-3. Di Benedetto, F., D'Acapito, F., Fornaciai, G., Innocenti, M., Montegrossi, G., Pardi, L. A., Tesi, S., and Romanelli, M. 2010 A Fe K-edge XAS study of amethyst Physics and Chemistry of Minerals 37 283-9. Dickson, R. S. and Weil, J. A. 1990 The magnetic properties of the oxygen-hole aluminumcenters in crystalline SiO2 .4. AlO4/Na+ Canadian Journal of Physics 68 63042. Dickson, R. S., Weil, J. A. and Davis, P. H. 1991 The paramagnetic germanium sodium impurity centers (GeO4/Na)A0 and (GeO4/Na)C0 in alpha-quartz Canadian Journal of Physics 69 761-79. Duttine, M., Villeneuve, G., Bechtel, F., and Demazeau, G. 2002 Electron paramagnetic resonance characterization of natural quartz from different sources Comptes Rendus Geoscience 334 949-55. Duval, M., Moreno, D., Shao, Q. F., Voinchet, P., Falgueres, C., Bahain, J. J., Garcia, T., Garcia, J., and Martinez, K. 2011 ESR dating of the Early Pleistocene archaeological site at Vallparadis (Terrassa, Cataluna, Spain) Trabajos De Prehistoria 68 7-24. Edwards, A. H., Fowler, W. B. and Feigl, F. J. 1988 Asymmtrical relaxation of simple E' centers in silicon dioxide isomorphs Physical Review B 37 9000-5. Fedin, M., Gromov, I. and Schweiger, A. 2006 Sensitivity optimization in amplitudemodulated CW-EPR experiment Journal of Magnetic Resonance 182 293-7. Feigl, F. J. and Anderson, J. H. 1970 Defects in crystalline quartz: electron paramagnetic resonance of E' vacancy centers associated with germanium impurities Journal of Physics and Chemistry of Solids 31 575-96. Feigl, F. J,. Fowler, W. B. and Yip, K. L. 1974 Oxygen vacancy model for the E′1 center in SiO2 Solid State Communications 14 225-9. Feng, P. B., Wang, Y., Rong, X., Su, J. H., Ju, C. Y., and Du, J. F. 2012 Characterization of the electronic structure of E'2 defect in quartz by pulsed EPR spectroscopy Physics Letters A 376 2195-9.

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Fujita, H. and Hashimoto, T. 2007 Effects of annealing temperatures on some radiationinduced phenomena in natural quartz Radiation Measurements 42 156-62. Garrison, E. G., Rowlett, R. M., Cowan, D. L., and Holroyd, L. V. 1981 Electron-spinresonance dating of ancient flints Nature 290 44-5. Gillen, R. and Robertson, J. 2012 Hybrid functional calculations of the Al impurity in alpha quartz: Hole localization and electron paramagnetic resonance parameters Physical Review B 85 014117.1-6. Giordano, L., Sushko, P. V., Pacchioni, G., and Shluger, A. L. 2007 Optical and EPR properties of point defects at a crystalline silica surface: Ab initio embedded-cluster calculations Physical Review B 75 024109.1-9. Griscom, D. L. 2011a On the natures of radiation-induced point defects in GeO2-SiO2 glasses: reevaluation of a 26-year-old ESR and optical data set Optical Materials Express 1 40012. Griscom, D. L. 2011b Trapped-electron centers in pure and doped glassy silica: A review and synthesis Journal of Non-Crystalline Solids 357 1945-62. Halliburton, L. E., Hantehzadeh, M. R., Minge, J., Mombourquette, M. J., and Weil, J. A. 1989 EPR study of Fe3+ in alpha-quartz - a reexamination of the lithium-compensated center Physical Review B 40 2076-81. Han, D., West, D., Li, X. B., Xie, S. Y., Sun, H. B., and Zhang, S. B. 2010 Impurity doping in SiO2: Formation energies and defect levels from first-principles calculations Physical Review B 82 155132.1-7. Harbridge, J. R., Rinard, G. A., Quine, R. W., Eaton, S. S., and Eaton, G. R. 2002 Enhanced signal intensities obtained by out-of-phase rapid-passage EPR for samples with long electron spin relaxation times Journal of Magnetic Resonance 156 41-51. Hattori, W., Katsura, M. and Yamanaka, C. 2006 Optically induced conversion of Ge centers in quartz Japanese Journal of Applied Physics Part 1-Regular Papers Brief Communications and Review Papers 45 8760-2. Howarth, D. F., Mombourquette, M. J. and Weil, J. A. 1997 The magnetic properties of the oxygen-hole aluminum centres in crystalline SiO2 .5. O-17-enriched AlO4/Li(+) and dynamics thereof Canadian Journal of Physics 75 99-115. Hu, B. Q., Pan, Y. M., Botis, S., Rogers, B., Kotzer, T., and Yeo, G. 2008 Radiation-induced defects in drusy quartz, Athabasca basin, Canada: a new aid to exploration of uranium deposits Economic Geology 103 1571-80. Ikeya, M. 1993 New Applications of Electron Paramagnetic Resonance: ESR Dating, Dosimetry, and Spectroscopy (Singapore: World Scientific). Isoya, J., Tennant, W. C., Uchida, Y., and Weil, J. A. 1982 Biradical center in alpha-quartz Journal of Magnetic Resonance 49 489-97. Isoya, J., Tennant, W. C. and Weil, J. A. 1988 Electron-paramagnetic-res of the TiO4/Li center in crystalline quartz Journal of Magnetic Resonance 79 90-8. Isoya, J. and Weil, J. A. 1979 Uncompensated titanium(3+) center in alpha-quartz Physica Status Solidi (A) 52 K193-K6. Isoya, J., Weil, J. A. and Claridge, R. F. C. 1978 The dynamic interchange and relation between germanium centers in alpha-quartz. The Journal of Chemical Physics 69 487684. Isoya, J., Weil, J. A. and Davis, P. H. 1983 Electron-paramagnetic-res of atomic-hydrogen H1 and H-2 in alpha-quartz Journal of Physics and Chemistry of Solids 44 335-43.

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Isoya, J., Weil, J. A. and Halliburton, L. E. 1981 Electron-paramagnetic-res and ab initio SCF-MO studies of the Si-H-Si system in the E'4 center of alpha-quartz Journal of Chemical Physics 74 5436-48. Jani, M. G., Bossoli, R. B. and Halliburton, L. E.1983 Further characterization of the E'1 center in crystalline SiO2 Physical Review B 27 2285-93. Jani, M. G. and Halliburton, L. E. 1984 Point-defects in neutron-irradiated quartz Journal of Applied Physics 56 942-6. Khamidova, L. G., Ivannikov, A. I., Kondrashov, A. E., Tikounov, D. D., Skvortsov, V. G., Stepanenko, V. F., and Hoshi, M. 2001 Possibility of using porcelain samples of highvoltage line insulators for radiation dose reconstruction by EPR spectroscopy Applied Radiation and Isotopes 55 843-8. Koshchug, D. G., Gazeev, V. M., Gurbanov, A. G., Shabalin, R. V., and Vyatkin, S. V. 2005 EPR dating and evolution of the Elbrus volcano Applied Magnetic Resonance 28 331-42. Känzig, W. and Cohen, M. H. 1959 Paramagnetic resonance of oxygen in alkali halides Physics Review Letters 3 509-10. Lægsgaard, J. 2002 Triplet states at an O vacancy in alpha-quartz Physical Review B 66 024107.1-9. Laino, T., Donadio, D. and Kuo, I. F. W. 2007 Migration of positively charged defects in alpha-quartz Physical Review B 76 195210.1-9. Laman, F. C. and Weil, J. A. 1977 Silver-compensated germanium center in α-quartz Journal of Physics and Chemistry of Solids 38 949-56. Lee, H. K. and Yang, J. S. 2007 ESR dating of the eupchon fault, south Korea Quaternary Geochronology 2 392-7. Lees, N. S., Walsby, C. J., Williams, J. A. S., Weil, J. A., and Claridge, R. F. C. 2003 EPR of a hydrogen/double-lithium centre in alpha-quartz Physics and Chemistry of Minerals 30 131-41. Le Page, Y., Calvert, L. D. and Gabe, E. J. 1980 Parameter variation in low-quartz between 94 and 298K Journal of Physics and Chemistry of Solids 41 721-5. Li, Z. and Pan, Y. 2012 Quartz, Deposits, Mineralogy and Analytics ed. J. Götze and R. Möckel (Berlin: Springer-Verlag) pp 161-75. Lin, M., Yin, G. M., Ding, Y. Q., Cui, Y., Chen, K. S., Wu, C. P., and Xu, L. J. 2006 Reliability study on ESR dating of the aluminum center in quartz Radiation Measurements 41 1045-9. Lu, Z. Y., Nicklaw, C. J., Fleetwood, D. M., Schrimpf, R. D., and Pantelides, S. T. 2002 Structure, properties, and dynamics of oxygen vacancies in amorphous SiO2 Physical Review Letters 89 285505.1-4. Lunsford, J. H. 1973 ESR of adsorbed oxygen species Catalysis Reviews 8 135-56. Lutoev, V. P. 2005 Application of the ESR method in geological correlation problems Applied Magnetic Resonance 28 311-30. Maschmeyer, D. and Lehmann, G. 1983a A trapped-hole center causing rose coloration of natural quartz Zeitschrift für Kristallographie 163 181-96. Maschmeyer, D. and Lehmann, G. 1983b New hole-centers in natural quartz Physics and Chemistry of Minerals 10 84-8. Maschmeyer, D., Niemann, K., Hake, H., Lehmann, G., and Räuber, A. 1980 Two modified smoky quartz centers in natural citrine Physics and Chemistry of Minerals 6 145-56.

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Mashkovtsev, R. I., Howarth, D. F. and Weil, J. A. 2007 Biradical states of oxygen-vacancy defects in alpha-quartz Physical Review B 76 214114.1-11. Mashkovtsev, R. I. and Pan, Y. 2011 Biradical states of oxygen- vacancy defects in alphaquartz: centers E''(2) and E''(4) Physics and Chemistry of Minerals 38 647-54. Mashkovtsev, R. I. and Pan, Y. 2012a Stable states of E″ defects in α-quartz EPL 98 56005.15. Mashkovtsev, R. I. and Pan, Y. M. 2012b Five new E' centers and their Si-29 hyperfine structures in electron-irradiated alpha-quartz Physics and Chemistry of Minerals 39 7985. Mashkovtsev, R. I., Shcherbakova, M. Y. and Solntsev, V. P. 1978 Rengenografia i spectroskopia mineralov, ed. V. S. Sobolev (Novosibirsk: Nauka) pp 79-86. McQueen, K. G., Pwa, A. and van Moort, J. C. 2001 Geochemical and electron paramagnetic characteristics of quartz from a multi-stage vein environment, Cowarra gold deposit, New South Wales Journal of Geochemical Exploration 72 211-21. Minge, J., Mombourquette, M. J. and Weil, J. A. 1989a Dynamic interchange between [FeO4/Na]0 configurations in alpha-quartz Physical Review B 40 6523-8. Minge, J., Mombourquette, M. J. and Weil, J. A. 1990 EPR study of Fe3+ in alpha-quartz - the sodium-compensated center Physical Review B 42 33-6. Minge, J., Weil, J. A. and McGavin, D. G. 1989b EPR study of Fe3+ in alpha-quartz characterization of a new type of cation-compensated center Physical Review B 40 64908. Mitchell, D. G., Quine, R. W., Tseitlin, M., Meyer, V., Eaton, S. S., and Eaton, G. R. 2011 Comparison of continuous wave, spin echo, and rapid scan EPR of irradiated fused quartz Radiation Measurements 46 993-6. Mombourquette, M. J., Minge, J., Hantehzadeh, M. R., Weil, J. A., and Halliburton, L. E. 1989 EPR study of Fe3+ in alpha-quartz - hydrogen-compensated center Physical Review B 39 4004-8. Mombourquette, M. J., Tennant, W. C. and Weil, J. A. 1986 EPR study Fe3+ in alpha-quartz a reexamination of the so-called I-center Journal of Chemical Physics 85 68-79. Mombourquette, M. J. and Weil, J. A. 1985 Ab initio self-consistent-field molecular-orbital calculaions on AlO4 centers in alpha-quartz Canadian Journal of Physics 63 1282-93. Mysovsky, A. S., Sushko, P. V., Mukhopadhyay, S., Edwards, A. H., and Shluger, A. L. 2004 Calibration of embedded-cluster method for defect studies in amorphous silica Physical Review B 69 085202.1-10. Nilges, M. J., Pan, Y. M. and Mashkovtsev, R. I. 2008 Radiation-damage-induced defects in quartz. I. Single-crystal W-band EPR study of hole centers in an electron-irradiated quartz Physics and Chemistry of Minerals 35 103-15. Nilges, M. J., Pan, Y. M. and Mashkovtsev, R. I. 2009 Radiation-induced defects in quartz. III. Single-crystal EPR, ENDOR and ESEEM study of a peroxy radical Physics and Chemistry of Minerals 36 61-73. Nuttall, R. H. D. and Weil, J. A. 1980 Two hydrogenic trapped-hole species in alpha-quartz Solid State Communications 33 99-102. Nuttall, R. H. D. and Weil, J. A. 1981a The magnetic properties of the oxygen-hole aluminum centers in crystalline SiO2 .1. [AlO4]0 Canadian Journal of Physics 59 1696-708. Nuttall, R. H. D. and Weil, J. A. 1981b The magnetic properties of the oxygen-hole aluminum centers in crystalline SiO2 .3. [AlO4]+ Canadian Journal of Physics 59 1886-92.

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Nuttall, R. H. D. and Weil, J. A. 1981c The magnetic properties of the oxygen-hole aluminum centers in crystalline SiO2 .2. AlO4-H+ and AlO4-Li+ Canadian Journal of Physics 59 1709-18. Pacchioni, G., Frigoli, F., Ricci, D., and Weil, J. A. 2001 Theoretical description of hole localization in a quartz Al center: The importance of exact electron exchange Physical Review B 63 054102.1-11. Pan, Y., Mao, M., Botis, S. M., Mashkovtsev, R. I., and Shatskiy, A. F. 2012 Single-crystal EPR study of three radiation-induced defects (Al-O23-, Ti3+ and W5+) in stishovite Physics and Chemistry of Minerals 39 (to be published; online DOI 10.1007/s00269-012-0517-9). Pan, Y. M., Botis, S. and Nokhrin, S. 2006 Applications of Natural Radiation-Induced Paramagnetic Defects in Quartz to Exploration in Sedimentary Basins Journal of China University of Geosciences 17 258-71. Pan, Y. M., Nilges, M. J. and Mashkovtsev, R. I. 2008 Radiation-induced defects in quartz. II. Single-crystal W-band EPR study of a natural citrine quartz Physics and Chemistry of Minerals 35 387-97. Pan, Y. M., Nilges, M. J. and Mashkovtsev, R. I. 2009 Radiation-induced defects in quartz: a multifrequency EPR study and DFT modelling of new peroxy radicals Mineralogical Magazine 73 519-35. Pantelides, S. T., Lu, Z. Y., Nicklaw, C., Bakos, T., Rashkeev, S. N., Fleetwood, D. M., and Schrimpf, R. D. 2008 The E' center and oxygen vacancies in SiO2 Journal of NonCrystalline Solids 354 217-23. Perlson, B. D. and Weil, J. A. 2008 Electron paramagnetic resonance studies of the E' centers in alpha-quartz Canadian Journal of Physics 86 871-81. Poolton, N. R. J., Smith, G. M., Riedi, P. C., Bulur, E., Botter-Jensen, L., Murray, A. S., and Adrian, M. 2000 Luminescence sensitivity changes in natural quartz induced by high temperature annealing: a high frequency EPR and OSL study Journal of Physics DApplied Physics 33 1007-17. Ranieri, V., Darracq, S., Cambon, M., Haines, J., Cambon, O., Largeteau, A., and Demazeau, G. 2011 Hydrothermal growth and structural studies of Si1-xGexO2 single crystals Inorganic Chemistry 50 4632-9. Ranjbar, A. H., Aliabadi, R., Amraei, R., Tabasi, M., and Mirjalily, G. 2009 ESR response of bulk samples of clear fused quartz (CFQ) material to high doses from 10 MeV electrons: Its possible application for radiation processing and medical sterilization Applied Radiation and Isotopes 67 1023-6. Rinneberg, H. and Weil, J. A. 1972 EPR studies of Ti3+-H+ centers in X-irradiated alphaquartz Journal of Chemical Physics 56 2019-28. Romanelli, M., Di Benedetto, F., Bartali, L., Innocenti, M., Fornaciai, G., Montegrossi, G., Pardi, L. A., Zoleo, A., and Capacci, F. 2012 ESEEM of industrial quartz powders: insights into crystal chemistry of Al defects Physics and Chemistry of Minerals 39 47990. Rudra, J. K. and Fowler, W. B. 1987 Oxygen vacancy and the E'1 center in crystalline SiO2 Physical Review B 35 8223-30. Rugar, D., Budakian, R., Mamin, H. J., and Chui, B. W. 2004 Single spin detection by magnetic resonance force microscopy Nature 430 329-32. Schlick, S. 1972 ESR spectrum of O3- trapped in a single crystal of potassium chlorate The Journal of Chemical Physics 56 654-61.

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Schofield, P. F., Henderson, C. M. B., Cressey, G., and Vanderlaan, G. 1995 2P X-rayabsorption spectroscopy in the earth-sciences Journal of Synchrotron Radiation 2 93-8. Silsbee, R. H. 1961 Electron spin resonance in neutron-irradiated quartz Journal of Applied Physics 32 1459-62. SivaRamaiah, G., Lin, J. R. and Pan, Y. M. 2011 Electron paramagnetic resonance spectroscopy of Fe3+ ions in amethyst: thermodynamic potentials and magnetic susceptibility Physics and Chemistry of Minerals 38 159-67. SivaRamaiah, G. and Pan, Y. M. 2012 Thermodynamic and magnetic properties of surface Fe3+ species on quartz: effects of gamma-ray irradiation and implications for aerosolradiation interactions Physics and Chemistry of Minerals 39 515-23. Snyder, K. C. and Fowler, W. B. 1993 Oxygen vacancy in alpha-quartz - a possible bistable and metastable defect Physical Review B 48 13238-43. Solntsev, V. P., Mashkovtsev, R. I. and Shcherbakova, M. Y. 1974 Copper and nickel centers in alpha-quartz Soviet Physics Solid State 16 1192-3. Solntsev, V. P., Mashkovtsev, R. I. and Shcherbakova, M. Y. 1977 Electron paramagnetic resonance of the radiation centers in quartz Journal of Structural Chemistry 18 578-83. Suhovoy, E., Mishra, V., Shklyar, M., Shtirberg, L., and Blank, A. 2010 Direct microimaging of point defects in bulk SiO2, applied to vacancy diffusion and clustering EPL 90 26009. To, J., Sokol, A. A., French, S. A., Kaltsoyannis, N., and Catlow, C. R. A. 2005 Hole localization in [AlO4]0 defects in silica materials Journal of Chemical Physics 122 144704. Toyoda, S. 2005 Formation and decay of the E'1 center and its precursor in natural quartz: basics and applications Applied Radiation and Isotopes 62 325-30. Toyoda, S. 2011 The E'1 center in natural quartz: Its formation and applications to dating and provenance researches Geochronometria 38 242-8. Toyoda, S. and Hattori, W. 2000 Formation and decay of the E'1 center and of its precursor Applied Radiation and Isotopes 52 1351-6. Toyoda, S., Rink, W. J., Yonezawa, C., Matsue, H., and Kagami, T. 2001 In situ production of alpha particles and alpha recoil particles in quartz applied to ESR studies of oxygen vacancies Quaternary Science Reviews 20 1057-61. Uchida, Y., Isoya, J. and Weil, J. A. 1979 The dynamic interchange among three states of phosphorus(4+) in alpha-quartz Journal of Physical Chemistry 83 3462-7. Uchino, T. and Yoko, T. 2006 Density functional theory of structural transformations of oxygen-deficient centers in amorphous silica during hole trapping: Structure and formation mechanism of the E'γ center Physical Review B 74 125203.1-11. Usami, T., Toyoda, S., Bahadur, H., Srivastava, A. K., and Nishido, H. 2009 Characterization of the E'1 center in quartz: Role of aluminum hole centers and oxygen vacancies Physica B-Condensed Matter 404 3819-23. Walsby, C. J., Lees, N. S., Claridge, R. F. C., and Weil, J. A. 2003 The magnetic properties of oxygen-hole aluminum centres in crystalline SiO2. VI: A stable AlO4/Li centre Canadian Journal of Physics 81 583-98. Weeks, R. A. 1956 Paramagnetic resonance of lattice defects in irradiated quartz Journal of Applied Physics 27 1376-81. Weeks, R. A. 1963 Paramagnetic spectra of E'2 centers in crystalline quartz Physical Review 130 570-6.

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Weeks, R. A. and Abraham, M. M. 1965 Spin-one states of defects in quartz Bulletin of the American Physical Society 10 374. Weeks, R. A., Magruder, R. H. and Stesmans, A. 2008 Review of some experiments in the 50 year saga of the E' center and suggestions for future research Journal of Non-Crystalline Solids 354 208-16. Weil, J. A. 1971a Germanium-hydrogen-lithium center in alpha-quartz Journal of Chemical Physics 55 4685-98. Weil, J. A. 1971b The analysis of large hyperfine splitting in paramagnetic resonance spectroscopy Journal of Magnetic Resonance 4 394-9. Weil, J. A. 1975 The aluminum centers in alpha-quartz Radiation Effects 26 261-5. Weil, J. A. 1984 A review of electron-spin spectroscopy and its application to the study of paramagnetic defects in crystalline quartz Physics and Chemistry of Minerals 10 149-65. Weil, J. A. 1993 A review of the EPR spectroscopy of the point-defects in alpha-quartz - the decade 1982-1992 Physics and Chemistry of SiO2 and the Si-SiO2 Interface 2 ed. C. R. Helms and B. E. Deal (Plenum Press, New York) pp 131-44. Weil, J. A. 1994 EPR of iron centers in silicon dioxide Applied Magnetic Resonance 6 1-16. Weil, J. A. 2000 A demi-century of magnetic defects in alpha-quartz Defects in SiO2 and Related Dielectrics: Science and Technology ed. G. Pacchioni, L. Skuja and D. L. Griscom (Kluwer Academic, Dordrecht, Netherlands) pp 197-212. Weil, J. A. and Bolton, J. R. 2007 Electron Paramagnetic Resonance (New York: Wiley). Woda, C. and Wagner, G. A. 2007 Non-monotonic dose dependence of the Ge- and Ticentres in quartz Radiation Measurements 42 1441-52. Zhao, J. D., Zhou, S. Z., He, Y. Q., Ye, Y. G., and Liu, S. Y. 2006 ESR dating of glacial tills and glaciations in the Urumqi River headwaters, Tianshan Mountains, China Quaternary International 144 61-7. .

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Chapter 3

VEINED QUARTZ OF THE URALS: STRUCTURE, MINERALOGY, AND TECHNOLOGICAL PROPERTIES V. N. Anfilogov1, S. K. Kuznetsov2, R. S. Nasirov1, M. A. Igumentseva1, M. V. Shtenberg, P. Argishev1 and A. Lebedev1 1

Institute of Mineralogy of Ural Branch of Russian Academy of Sciences, Miass, Russia 2 Institute of Geolog of Komi Scientific Center of Ural Branch of Russian Academy of Sciences, Siktikvkar, Russia

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ABSTRACT There are three major groups of the Ural quartz deposits: the Circumpolar group, the Middle Ural group and the South Ural one. The Circumpolar group is represented by the typical hydrothermal veined deposits. One of the big Circumpolar quartz deposit is “Jelannoie” one. It is located in the monomineralic quartzy sandstone. The quartz vein may be to 100 meters thick. Rutile, turmaline, zircon and sericite are the major accessory minerals. The chief deleterious constituent in quartz is water, which is located in the gasliquid inclusions. The effective method for H2O elimination is described. High quality quartz glass may be produced after primary quartz enriching. The Middle Ural is represented by giant quartz body “Mounain Chrustalnaia” . Quartz body has a size 380X140X160 m. The content of quartz is 98.89%. Quartz deposit was formed on the big massive of quartz-diorite and granite contact. The main accessory minerals are microcline, muscovite, kaolin, hydrogoethite and pyrite. Quartz has a giant crystalline structure. There is a specific enriching technology for this quartz deposit. The South Ural group of quartz deposits is represented by a large body quartz vein, disposed in East part of the Ufaleisky gneiss-migmatite complex. The length of quartz vein area is 50 km. There are more than 3000 quartz veins on this area. Granulated quartz is prevalent for this group of deposits. Field spars, micas, rutile, sphene, ilmenite and carbonates are the main accessory minerals. Concentration of impurities in granulated quartz is as the IOTA STD. There is standard technology of quartz enriching for these deposits.

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INTRODUCTION Three main provinces concentrating major quartz vein deposits are distinguished in the Urals: Subpolar, Central, and South Urals. The Gora Khrustal’naya (Crystal Mount), the largest quartz deposit in the Urals, has been known since 1734. For a long time, the main attention of the researchers was directed to the search and study of piezoquartz deposits. In the Urals, piezoquartz was extracted in the Astaf’evskii deposit in the South Urals and Zhelannoe deposit in the Subpolar Urals. The Kyshtym mining and processing enterprise is an exclusive Russian producer of quartz concentrate suitable for the production of the purest quartz glass since 1966. The vein quartz from the Zhelannoe deposit is used for the synthesis of piezoquartz crystals. The most intense studies of geology and mineralogy of quartz deposits in the South and Middle Urals were conducted in the mid-1980s [4, 15]. The quartz vein deposits from Subpolar Urals are described in the paper of S.K. Kuznetsov [13]. To date, new data have been accumulated and are presented in the given review.

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SUBPOLAR URALS The Subpolar Urals concentrates the large quartz vein deposits in the Urals which systematic study began in 1920-s. A huge amount of works are dedicated to this problem. A review of studies of quartz from the Subpolar Urals is given in the works [26, 27]. The main studies were focused in crystal-bearing veins which were the important source for piezoquartz for a long time. The active study of vein quartz as a possible material for production of quartz glass has been started since the 1970-s. The quartz vein deposits are confined to the core of megaanticlinorium composed of the Riphean metamorphic rocks and felsic and mafic igneous rocks [2]. The schematic geological map of the region is shown on Figure 1 [2]. The quartz veins of the Subpolar Urals are distinct in bedding, morphology, structure, and mineral composition. They occur within the rocks of different genesis, age, and degree of metamorphism. The important role in location of quartz veins belongs to the disjunctive faults whose formation is governed by many factors. The quartz veins fill the concordant fractures and those crosscutting the schistosity of the host rocks. A.E. Karyakin [5] distinguished the following types of quartz veins: 1. near-longitudinal or N-E-trending veins in concordant shear fractures (concordant veins) with western and northwestern dip at an angle of 25-85º; 2. near-longitudinal veins in the crosscutting shear fractures (crosscutting veins) with eastern dip at the angle of 0-75º; 3. near-latitudinal or N-W-trending veins in the transverse tension cracks (transverse veins) with southern and southwestern dip at the angle 60-90º.

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Figure 1. Schematic geological map of the axial zone of the Subpolar Ural. 1. Carbonates. 2. Quartzite, shale and conglomerate. 3. Polymict sandstone, tufogenic sandstone, quartz-sericite shales. 4. Quartzchlorite sales with marble lenses and effusive rocks in upper part. 5. Quartz-chlorite and other shale, quartzite, arkoses and conglomerates. 6. Quartzite, arkoses conglomerate and shale. 7. Non-articulated micaceous shale and gneiss. 8. Fieldspathic quartzite,marbl lenses, gneiss, micaceous- garnet and amphibole sale. 9. Peridotite, gabbro, diorite. 10. Caledone granitiode. 11. Ultrabasite, gabbro, quartz diorite. 12. Granitoide. 13 Fructures.

The quartz veins in fractures concordant to the rock schistosity are dominant in the region and the veins in the crosscutting fractures occasionally occur. The Proterozoic shales are mostly saturated with unevenly distributed veins. Probably, this is related to the large N-E-trending faults, accompanying fractures, and zones of intense rock schistosity. The intrusive plutons and lenses and interlayers of conglomerates and quartzites contain lesser amount of quartz veins in contrast to shales. The quartz veins are also abundant in the Early Proterozoic Nyarta complex but in the lesser amount than in its shale framework. The veins are very unevenly developed in the Ordovician rocks. The Lower Proterozoic strongly foliated gravelstones, quartzites, and siltstones host numerous quartz veins. Massive varieties of these rocks contain significantly lesser amount of veins. The Middle to Upper Ordovician quartz-chlorite-mica and phyllite shales, marbles, and limestones are also saturated with quartz veins.

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Morphology and structure of quartz veins: Diverse morphology of quartz veins in the Subpolar Urals depends on morphology of host fractures which is caused by physicomechanical properties of rocks and character of tectonic stresses. The veins of lens, platy or complicate morphology are most abundant (Figure 2). The lens veins are developed in all rocks but are most typical of plastic quartz-mica and quartzchlorite-mica shales.

Figure 2. Forms of quartz veins. a, b – lens-shaped, lenticular-broken; c , d – winding; e – platy g – complicated. 1. Enclosed rock. 3. Veined quartz.

The platy veins are widespread in relatively hard rocks (quartzites, granites, and, occasionally, plastic shales). They occur both in concordant and crosscutting fractures. These veins are characterized by consistent thickness and absence of significant swells and pinches. The vein thickness widely ranges from millimeters up to several tens of meters. The thickest veins are typical of massive hard rocks, particularly, quartzites. They are located in areas of fractures which divide the rocks into the large blocks. The transportation of blocks after tectonic movements resulted in formation of the giant vein-hosting cavities. The extension of veins along the strike and the dip is different. Some veins are abruptly pinched out whereas other veins are traced for many tens of meters. The contacts of veins with host rocks are sharp or gradual. The rocks near concordant veins are intensely foliated and the contacts are disrupted. The slickenlines are observed in

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the vein selvages. The wall rocks are often muscovitized, chloritized, and epidotized. The width of zones of altered rocks varies from several centimeters up to several meters. The widest halos are observed near the pockets with rock crystals and fractures which served the pass ways for crystal-forming fluids. The internal vein structure depends on the orientation of quartz individuals, change of their morphology and size, transparence, distribution of mineral inclusions, occurrence of factures and cavities, and other peculiarities. The quartz individuals may be chaotically or orderly oriented. Locally, they grow transversely to fracture walls forming the columnar vein structure. The quartz grains in near-selvage areas are much smaller then in the central vein parts. The minor minerals form pockets, bands or zones oriented along the vein axes. Mineral composition: To date, about 150 minerals have been established in quartz veins of the Subpolar Urals. Reasonably complete mineral catalogues were composed in different years by A.E. Karyakin and V.A. Smirnova, V.V. Bukanov, and P.P. Yukhtanov [2, 8, 29]. In addition to quartz, the most abundant minerals are muscovite, chlorite, calcite, feldspars (albite, microcline, oligoclase, and orthoclase), titanite, apatite, hematite, ilmenite, pyrrhotite, and pyrite. The composition of crosscutting veins free of crystal-bearing pockets is usually very simple. They contain quartz with subordinate sericite developing along the cracks. The crystal-bearing veins are distinct in extremely wide mineral diversity. Tens of minerals occur in the pockets along with rock crystals and as inclusions in quartz. These are axinite, rutile, tourmaline, titanite, calcite, chlorite, muscovite, and anatase. Most minerals of these veins (chlorite, muscovite, rutile, titanite, calcite, tourmaline, ilmenite, hematite, monazite, etc.) were formed after the main mass of quartz but before its crystals. They occur in fractures crosscutting the milky white quartz or as inclusions in rock crystals. Calcite, hematite, and goethite crystallized simultaneously with the rock crystals that is established by compromise growth surfaces. Apophyllite, zeolites, probably brookite, anatase, late generations of chlorite, calcite, sericite, and pyrite deposited later. These minerals grow on the rock crystals. Mineral composition of quartz veins is obviously related to the composition of host rocks that was previously shown for the crystal-bearing veins [6]. Muscovite, albite, chlorite, biotite, titanite, rutile, and calcite are typical of veins in granites and granodiorites; chlorite and calcite are characteristic of dolerites; chlorite, muscovite, calcite, biotite, titanite, pyrite, pyrrhotite, and sphalerite are distinctive of quartz-chlorite-mica shales; and muscovite, rutile, and tourmaline occur in quartzitic sandstones. Our data also indicate that mineral composition both of the crystal-bearing and other types of veins significantly depends on composition of host rocks. Veins in gneisses and granitogneisses of the Nyarta Formation usually contain muscovite, biotite, and ilmenite with abundant feldspars (microcline and oligoclase), calcite, and apatite. Veins in limestones bear a lot of calcite, veins in dolerites, gabbro, granodiorites, and granites contain chlorite, calcite, and locally feldspars, and those in quartzitic sandstones have muscovite and hematite. Veins in quartz-chlorite-mica shales from the Puiva, Moroya, and other formations are characterized by most diverse mineral composition. They contain pyrite, pyrrhotite, galena, sphalerite and other sulfides along with chlorite, calcite, and muscovite. Type and properties of vein quartz: The vein quartz from the Subpolar Urals is widely diverse. Several types of quartz may be macroscopically distinguished. Traditional types include vein quartz and quartz crystals. The classification may be also based on textural-

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structural peculiarities, properties, and genesis. For the sake of convenience of review and description, we distinguish allotriomorphic-granular (properly vein) and euhedral quartz. The allotriomorphic-granular quartz may be subdivided on giant-, coarse-, medium-, and smallgrained quartz and euhedral one includes rock crystals, smoky quartz, citrine, and amethyst. Quartz contains numerous variously oriented open and sealed fractures with scales of muscovite and fluid inclusions. Locally, one or several parallel fractures obliquely or almost orthogonal crosscutting each other are dominant. Strongly foliated and milonitized quartz also occurs. Transparent lens, rectangular or complex areas up to several centimeters across are often located between fractures. The giant- and coarse-grained quartz from crosscutting veins is commonly characterized by weak plastic deformations. In thin sections, quartz exhibits even, cloudy, and wavy extinction and deformation bands. No blocking was observed. Quartz near the fractures and fragmentation zones is mostly plastically deformed. In many concordant veins, coarse- to giant-grained milky white and transparent quartz is granulated. This is evident from the position of the small grains, their morphology, structure, interrelations with larger grains, and other macro- and microfeatures typical of similar quartz [4, 10, 26]. The coarse- to giant-grained strongly deformed quartz underwent granulation. Single newly formed grains within the large individuals are usually confined to one or several variously directed and intersecting deformation bands or are chaotically located forming the chains and aggregates Figure 3. Locally, one can establish the structures suggesting the relation between granulation and quartz blocking. The size of newly formed isometric quartz with even or step boundaries is 0.1-2 mm. In contrast to the primary quartz, it shows slight or no plastic deformations, Figure 4.

Figure 3. The beginning stage of coarse- and giant-grained quartz. Quartz veins are in muscovitechlorite-quartz shale (a); in gneiss (b); in quartzite sandstone – river Parnuc (c); river Balbaniu: thin sections. X10. New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

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Figure 4. Granulated quartz with relicts of isometric grains. Quartz veins in muscovite-chlorite quartz sale (a, b, c): in granite (d): thin sections. X10.

Significant areas of coarse- to giant-grained quartz in salbands or pinching out of veins are often granulated. The main volume of veins is composed of giant-grained massive quartz alternating by small-grained quartz toward the salbands and pinching out. The contacts of such veins with host rocks are always disrupted and the side surfaces contain numerous slickenlines. Zhelannoe quartz vein deposit: The Zhelannoe deposit is the largest quartz vein deposit in the Subpolar Urals and is located in its mountain part. It is hosted in monomineral quartzitic sandstones and includes Western and Eastern mineralized zones distinct in vein size, morphology and tipomorphism of minerals [14, 25]. Each zone contains several tens of large compound vein bodies composed of quartz and underlying vein sericitolites. The quartz veins up to 100 m thick are made up of giant-crystalline milky white quartz. Some vein areas features numerous aggregates of transparent recrystallized quartz up to several centimeters across. In most cases, the rock crystals are superimposed on the veins. The cavities or pockets with transparent quartz crystals may occur both inside veins (intraveined) and in salbands along the contact of milky white quartz with sericitolites or quartzitic sandstones. The quartz crystals from sericitolites are radiationally colored whereas those from the intravein pockets and at the contact with quartzitic sandstones are colorless but take a color at artificial lighting. The crystals from the Eastern zone are sharply rhombohedral and citrinecolored whilst in the Western zone they are prismatic and smoky. The geological structure of the Zhelannoe deposit is shown on Figure 5. Only milky white quartz is presently being extracted from the deposit as a working mixture for monocrystal synthesis. It can not be used for optical glasses because of the abundant fluid inclusions. Many researchers note that, by a series of parameters, the milky

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white quartz from the Zhelannoe deposit compares well to transparent varieties or, in some cases, excels them.

Figure 5. Geological map of “Gelannoe” deposit. 1- phyllitoid shale with marble lenses; 2 – basaltic porphytite; 3 – conglomerate; 4 – interbedding of sandstone and aleurolite shale; 5 – coarse-gained sandstone and conglomerate; 6 – quartz sandstone; 7 – aleurolite interlayer; 8 - aleurolite and sandstone; 9 – aqleurolite; 10 – West qurtz-vein zone (З); East quartz zone (B); 11 – quartz-vein joint; 12 – mountain quartz crystal socket; 13 - fracture, which is companied by acid leaching; 14 - quartz vein controlling fracture; 15 – zone of intensive jointing; 17 – adit; 18 - sample of quartzitic sandstone.

New Developments in Quartz Research: Varieties, Crystal Chemistry and Uses in Technology : Varieties, Crystal Chemistry and Uses in

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Table 1. Optical transmission and content of trace elements in vein quartz and enriched concentrates from the Western zone of the Zhelannoe deposit Main quartz types Milky white quartz concentrate Transparent areas in milky white quartz concentrate Rock crystal concentrate

Amount of sample 10 1 1 4 1 39 1 1

Т, % 40 – 60

80

Content of trace elements, n x 10-4 wt % Al Na K Li Fe Ca 9.55 19.45 4.5 0.88 2.13 4.76 17.9 4.8 3.8 0.68 24.3 2.7 18 5.9 1.97 0.81 0.19 0.57

Ti 0.65 7.86 0.45

Mg 0.84 0.6 0.06

Mn 0.4 0.1 0.03

Cu 0.04 – 0.01

Cr