Modern Glass Characterization

585 Pages·2015·16.505 MB·English

by  Affatigato, Mario

MODERN GLASS CHARACTERIZATION
Edited by
Mario Affatigato
Copyright © 2015 by The American Ceramic Society and John Wiley & Sons, Inc. All rights reserved.
Published by John Wiley & Sons, Inc., Hoboken, New Jersey.
Published simultaneously in Canada.
No part of this publication may be reproduced, stored in a retrieval system, or transmitted in any form or by any means,
electronic, mechanical, photocopying, recording, scanning, or otherwise, except as permitted under Section 107 or 108 of the
1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment
of the appropriate per-copy fee to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, (978) 750-
8400, fax [phone], or on the web at www.copyright.com. Requests to the Publisher for permission should be addressed
to the Permissions Department, John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, [phone], fax (201) 748-
6008, or online at http://www.wiley.com/go/permission.
Limit of Liability/Disclaimer of Warranty: While the publisher and author have used their best efforts in preparing this book, they
make no representations or warranties with respect to the accuracy or completeness of the contents of this book and
specifically disclaim any implied warranties of merchantability or fitness for a particular purpose. No warranty may be created
or extended by sales representatives or written sales materials. The advice and strategies contained herein may not be suitable
for your situation. You should consult with a professional where appropriate. Neither the publisher nor author shall be liable for
any loss of profit or any other commercial damages, including but not limited to special, incidental, consequential, or other
damages.
For general information on our other products and services or for technical support, please contact our Customer Care
Department within the United States at [phone], outside the United States at [phone] or fax [phone].
Wiley also publishes its books in a variety of electronic formats. Some content that appears in print may not be available in
electronic formats. For more information about Wiley products, visit our web site at www.wiley.com.
Library of Congress Cataloging-in-Publication Data is available.
ISBN: 978-1-118-23086-2
CONTENTS
PREFACE
LIST OF CONTRIBUTORS
1 DENSITY, THERMAL PROPERTIES, AND THE GLASS TRANSITION
TEMPERATURE OF GLASSES
Part I: Introduction to Physical Properties and Their Uses
Part II: Density
1.1 DENSITY: EXPERIMENTAL BACKGROUND AND THEORY
Part III: Thermal Effects with a Focus on the Glass Transition Temperature
1.2 OVERVIEW
1.3 EXPERIMENTAL METHODS AND THEORY
1.4 INSTRUMENTATION USED FOR DETERMINING T AND RELATED
g
THERMAL EVENTS
1.5 ANALYSIS OF DATA AND EXTRACTION OF USEFUL INFORMATION
1.6 CASE STUDIES FROM GLASS SYSTEMS
1.7 CONCLUSION TO THERMAL PROPERTIES
ACKNOWLEDGMENTS
REFERENCES
2 INFRARED SPECTROSCOPY OF GLASSES
2.1 INTRODUCTION
2.2 BACKGROUND AND THEORY
2.3 INSTRUMENTATION
2.4 ANALYSIS OF INFRARED DATA
2.5 CASE STUDIES
2.6 CONCLUSIONS
ACKNOWLEDGMENTS
REFERENCES
3 RAMAN SPECTROSCOPY OF GLASSES
3.1 INTRODUCTION
3.2 BACKGROUND
3.3 INSTRUMENTATION AND DATA ANALYSIS
3.4 CASE STUDIES
3.5 CONCLUSIONS
ACKNOWLEDGMENTS
REFERENCES
4 BRILLOUIN LIGHT SCATTERING
4.1 INTRODUCTION
4.2 BACKGROUND AND THEORY
4.3 INSTRUMENTATION
4.4 DATA ANALYSIS AND INFORMATION CONTENT
4.5 EXAMPLES OF CASE STUDIES
4.6 SUMMARY
REFERENCES
5 NEUTRON DIFFRACTION TECHNIQUES FOR STRUCTURAL STUDIES OF
GLASSES
5.1 INTRODUCTION
5.2 INSTRUMENTATION
5.3 THEORETICAL ASPECTS OF NEUTRON DIFFRACTION ON GLASSES
5.4 THE APPLICATION OF NEUTRON DIFFRACTION TO STUDIES OF GLASS
STRUCTURE
ACKNOWLEDGMENTS
REFERENCES
FURTHER READING
Notes
6 X-RAY DIFFRACTION FROM GLASS
6.1 INTRODUCTION
6.2 BACKGROUND/THEORY
6.3 ANALYSIS OF DATA, EXTRACTION OF USEFUL INFORMATION
6.4 INSTRUMENTATION
6.5 CASE STUDIES
6.6 CONCLUSIONS
ACKNOWLEDGMENTS
REFERENCES
7 XAFS SPECTROSCOPY AND GLASS STRUCTURE
7.1 INTRODUCTION
7.2 THE ORIGINS OF X-RAY ABSORPTION SPECTRA
7.3 XAFS INSTRUMENTATION
7.4 THE PHYSICAL MECHANISM OF XAFS
7.5 EXAFS
7.6 XAFS DATA ANALYSIS
7.7 EXAFS ACCURACY AND LIMITATIONS
7.8 XANES
7.9 XAFS SPECTROSCOPY APPLIED TO GLASS STRUCTURE: SOME
EXAMPLES
7.10 SUMMARY AND CONCLUSIONS
REFERENCES
8 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY OF GLASSES
8.1 INTRODUCTION
8.2 THEORETICAL BACKGROUND
8.3 INSTRUMENTATION
8.4 DATA ANALYSIS AND STRUCTURAL INTERPRETATION
8.5 CASE STUDIES
8.6 CONCLUSIONS
ACKNOWLEDGMENTS
REFERENCES
9 ADVANCED DIPOLAR SOLID STATE NMR SPECTROSCOPY OF GLASSES
9.1 INTRODUCTION
9.2 THEORETICAL ASPECTS
9.3 HETERONUCLEAR EXPERIMENTS
9.4 HOMONUCLEAR EXPERIMENTS
9.5 CASE STUDIES
ACKNOWLEDGMENTS
REFERENCES
10 ATOM PROBE TOMOGRAPHY OF GLASSES
10.1 INTRODUCTION
10.2 BACKGROUND AND THEORY
10.3 INSTRUMENTATION
10.4 ANALYSIS METHODS
10.5 CASE STUDIES
ACKNOWLEDGMENTS
REFERENCES
INDEX
EULA
List of Tables
Chapter 1
Table 1.1
Table 1.2
Table 1.3
Table 1.4
Table 1.5
Chapter 2
Table 2.1
Chapter 4
Table 4.1
Chapter 5
Table 5.1
Table 5.2
Table 5.3
Table 5.4
Table 5.5
Chapter 6
Table 6.1
Chapter 7
Table 7.1
Chapter 8
Table 8.1
Chapter 10
Table 10.1
Table 10.2
List of Illustrations
Chapter 1
Figure 1.1 Schematic of a pycnometer's operation.
Figure 1.2 A Quantachrome® manual pycnometer.
Figure 1.3 Molar volumes of the alkali and alkaline-earth borate glass system [5]. R is
the molar ratio of metal oxide to boron oxide. The error is smaller than the symbols
used.
Figure 1.4 Molar volumes per mole glass former in the lithium borate, lithium silicate,
and lithium germanate glass systems [6]. R is the molar ratio of lithia to silica,
germania, or bora.
Figure 1.5 Packing fractions from a series of alkali and alkaline-earth borate glasses.
R is the molar ratio of alkali oxide to boron oxide [8].
Figure 1.6 The density of alkali and alkaline-earth borates as a function of R, the molar
ratio of modifying oxide to boron oxide [5]. The error is smaller than the symbols.
Figure 1.7 Density of lithium silicate glasses by the sink-float method from Peters et al.
[10] and a comparison of literature values compiled by Bansal and Doremus [11]. J is
the molar ratio of lithium oxide to silicon dioxide.
Figure 1.8 The Qi structural units found in alkali silicate glasses, from left to right they
advance from Q4 to Q0 where the superscript denotes the numbers of bridging oxygens
per Si. A+ represents an alkali ion.
Figure 1.9 The lever rule for lithium silicate glasses.
Figure 1.10 Volume per mol silica from a series of lithium silicate glasses, JLi O.SiO .
2 2
The data are taken from Bansal and Doremus [11]. J is the molar ratio of lithium oxide
to silica.
Figure 1.11 Density of lithium borate glasses as a function of R, the molar ratio of
lithium oxide to boron oxide [12]. Also shown in the figure is the fraction, f , of
2
tetrahedral borons [13].
Figure 1.12 Volumes per mole B O of the cesium borate glass system from Kodama
2 3
[3] The error is less than the symbol size.
Figure 1.13 The triborate and diborate superstructural groups.
Figure 1.14 Molar volumes of the alkali borates using Kodama's data as a function of
R, the molar ratio of alkali oxide to boron oxide [3].
Figure 1.15 Stiffness as a function of composition, R [3].
Figure 1.16 Stiffness as a function of molar volumes for the cesium borate case [3].
Figure 1.17 The DSC head uncovered for sample insertion (from Wikipedia).
Figure 1.18 Representative thermogram from a DSC
Figure 1.19 A schematic of the operation of a DTA.
Figure 1.20 A TA® modulated DSC.
Figure 1.21 A Netzsch® DTA.
Figure 1.22 A Typical DSC thermogram [17]. It is from a lithium borate glass with R =
1.5, where R is the molar ratio of alkali oxide to boron oxide. Note that
endothermic/exothermic directions are reversed from what was given earlier in the
chapter.
Figure 1.23 The T s of barium borosilicate glasses of the form RBaO.B O .KSiO
g 2 3 2
[18].
Figure 1.24 The fraction of four-coordinated borons, N , of barium borosilicate
4
glasses of the form RBaO.B O .KSiO [19].
2 3 2
Figure 1.25 The T s of calcium borosilicate glasses of the form RCaO.B O .KSiO
g 2 3 2
[18].
Figure 1.26 The T s of lithium borosilicate glasses of the form RLiO.B O .KSiO [20].
g 2 3 2
Figure 1.27 (a), Critical cooling rate versus the glass stability parameter K for
LL
several glasses [GeO2 (G), PbO.SiO2 (PS),Na2O.2SiO2 (NS2),
2MgO.2Al2O3.5SiO2 (M2A2S5), Li2O.2SiO2 (LS2), CaO.MgO.2SiO2
(CMS2),CaO.Al2O3.2SiO2 (CAS2), Li2O.2B2O3 (LB2)]. (b), the same K versus
LL
composition in the Li O–B O system [17].
2 2 3
Figure 1.28 (a), Critical cooling rate versus the glass stability parameter K for
3
several glasses [GeO2 (G), PbO.SiO2 (PS),Na2O.2SiO2 (NS2),
2MgO.2Al2O3.5SiO2 (M2A2S5), Li2O.2SiO2 (LS2), CaO.MgO.2SiO2
(CMS2),CaO.Al2O3.2SiO2 (CAS2), Li2O.2B2O3 (LB2)]. (b), Glass stability
parameter K = Th /T versus composition [17].
3 x m
Chapter 2
Figure 2.1 Infrared response of a two-Lorentzian-oscillator model; reflectance
spectrum R(ν) (a), real ϵ (ν) and imaginary ϵ (ν) part of the dielectric function (b), and
1 2
real n(ν) and imaginary k(ν) part of the refractive index (c). The dielectric function ϵ*
(ν) is modeled according to Eq. 2.19 using the parameters: ν = 1080 cm-1, Γ = 55 cm-
1 1
1, Δϵ = 0.65, and ν = 460 cm-1, Γ = 40 cm-1, Δϵ = 0.90. The high frequency
1 2 2 2
dielectric constant is ϵ = 2.15.
∞
Figure 2.2 Comparison of the reflectance spectrum R(ν) (a) with the imaginary part
ϵ (ν) (b) and the energy-loss function Im(−1/ ϵ*(ν)) (c) of the dielectric function ϵ*(ν),
2
for the two-Lorentzian-oscillator model used in Figure. 2.1.
Figure 2.3 Optical layout of the Fourier-transform Bruker Vertex 80v spectrometer.
Infrared radiation from a mid-infrared (MIR) or far-infrared (FIR) source passes
through the variable aperture (APT) to the beam splitter (BMS) of the Michelson-type
interferometer and then directed to the sample and detector (D1, D2) compartments.
(Reprinted with permission from Bruker Optics)
Figure 2.4 (a) Interferograms F(s) (arb. units) measured in specular reflectance at 11°
off-normal from a gold mirror (reference) and a polished slab of vitreous SiO
2
(sample); (b) Single-beam spectra (arb. units) obtained by Fourier-transformation
of interferograms F(s) shown in (a); and (c) Reflectance spectrum of silica glass
in the far- and mid-IR range calculated by (for details
see text).
Figure 2.5 Comparison of results by Kramers–Krönig transformation (KK), Eq. 2.18,
and reflectance fitting by classical dispersion theory (fit), Eq. 2.19, employed for the
analysis of the infrared reflectance spectrum of glass K O.2B O . The experimental
2 2 3
reflectance spectrum (solid line) and the best fit spectrum (circles) are shown in (a).
The results of KK analysis (full lines) and curve-fitting (circles) for the n(ν), k(ν),
ϵ (ν) and ϵ (ν) spectra are shown in (b), (c), (d), and (e), respectively.
1 2
Figure 2.6 (a) Deconvolution of the α(ν) spectrum of glass 0.67CuI-0.33[Cu MoO -
2 4
Cu PO ] (solid black line) into Gaussian component bands according to Eq. 2.41) solid
3 4
grey lines). The simulated spectrum is shown by open circles. Inset, (b) shows the
measured infrared reflectance spectrum (solid line) compared to the best fitting with
Eq. 2.19) open circles).
Figure 2.7 Refractive index n(ν) and extinction coefficient k(ν) spectra of the bulk
glass 0.2AgI-0.8[Ag O-2B O ] obtained by Kramers–Krönig transformation of the
2 2 3
measured reflectance spectrum.
Figure 2.8 Effect of film thickness on the calculated absorbance spectra of free-
standing glass films with composition 0.2AgI-0.8[Ag O-2B O ].
2 2 3
Figure 2.9 Comparison of infrared absorption coefficient spectra of alkaline-earth
borate glasses xMO-(1−x)B O , with metal oxide contents x = 0.33 (a) and x = 0.45
2 3
(b). The spectra were obtained by KK transformation of the measured reflectance
spectra.
Figure 2.10 Relative integrated absorption A = A /A as a function of metal oxide
r 4 3
content in alkaline-earth borate glasses xMO-(1−x)B O . Integrated absorptions A and
2 3 4
A correspond to tetrahedral and triangular borate units, respectively. Lines through
3
data points are drawn to guide the eye.