Marghussian Nano-Glass Ceramics

Processing, Properties and Applications
1. Auflage 2015
ISBN: 978-0-323-35432-5
Verlag: Elsevier Science & Techn.
Format: EPUB
Kopierschutz: 6 - ePub Watermark

E-Book, Englisch, 292 Seiten

Reihe: Micro and Nano Technologies

Nano-Glass Ceramics: Processing, Properties and Applications provides comprehensive coverage of synthesis and processing methods, properties and applications of the most important types of nano-glass ceramics, from a unique material science perspective. Emphasis is placed on the experimental and practical aspects of the subject while covering the theoretical and practical aspects and presenting, numerous examples and details of experimental methods. In the discussing the many varied applications of nano-glass ceramics, consideration is given to both, the fields of applications in which the materials are firmly established and the fields where great promise exists for their future exploitation. The methods of investigation adopted by researchers in the various stages of synthesis, nucleation, processing and characterization of glass ceramics are discussed with a focus on the more novel methods and the state of the art in developing nanostructured glass ceramics. - Comprehensive coverage of nanostructured glass ceramics with a materials science approach. The first book of this kind - Applications-oriented approach, covering current and future applications in numerous fields such as Biomedicine and Electronics - Explains the correlations between synthesis parameters, properties and applications guiding R&D researchers and engineers to choose the right material and increase cost-effectiveness

Prof. Marghussian has 30 years' experience in teaching and researching in the field of glass and glass ceramics. He is the author/co-author of more than 50 research papers on the crystallization of glasses and fabrication of glass ceramics (including nano-glass ceramics) published in international journals (H-Index: 10). These papers cover all essential aspects and applications of glass ceramics (optical, dielectric, magnetic, biomedical, structural, coatings, etc.). Beyond this, Prof. Marghussian is author and co-author ?of 3 books in Persian - one of them on glass structure and properties (including one chapter on glass ceramics) - and he has been Editor-in-Chief of two journals on ceramic science and technology. His research fields also include biomedical application of ceramics. Prof. Marghussian presented at numerous conferences, he has been Director of several national research projects on glass and glass ceramics and supervised more than 50 postgraduate research projects, mainly on glass and especially glass ceramics and nano-glass ceramics.

Autoren/Hrsg.

Marghussian, Vahak

Inhaltsverzeichnis

1;Front Cover;1
2;Nano-Glass Ceramics;4
3;Copyright Page;5
4;Contents;6
5;Preface;8
6;Introduction;10
7;1 Glass Crystallization;12
7.1;1.1 Nucleation in Glass;13
7.1.1;1.1.1 Homogeneous Nucleation;14
7.1.1.1;1.1.1.1 Theoretical Background;14
7.1.1.2;1.1.1.2 Experimental Studies of Homogeneous Nucleation;17
7.1.2;1.1.2 Heterogeneous Nucleation;19
7.1.2.1;1.1.2.1 Theoretical Background;19
7.1.2.1.1;1.1.2.1.1 General Considerations;19
7.1.2.1.2;1.1.2.1.2 Epitaxy in Heterogeneous Nucleation of Glasses;21
7.1.2.1.3;1.1.2.1.3 The Effect of Glass-in-Glass Phase Separation on Heterogeneous Nucleation;25
7.1.2.2;1.1.2.2 Experimental Studies of Heterogeneous Nucleation;26
7.1.2.2.1;1.1.2.2.1 Heterogeneous Nucleation in the Presence of Phase Separation in Glass;27
7.1.2.2.2;1.1.2.2.2 Crystal Nucleation in the Absence of Phase Separation in Glass;34
7.1.2.2.3;1.1.2.2.3 Secondary Crystallization;36
7.1.2.2.4;1.1.2.2.4 Determination of the Optimum Nucleation Temperature and Time;36
7.1.2.2.5;1.1.2.2.5 Determination of the Type and Amount of Effective Nucleating Agents by DTA;40
7.1.2.2.6;1.1.2.2.6 Determination of Crystal Nucleation rates;44
7.1.2.2.6.1;Particle Counting Method;44
7.1.2.2.6.2;Thermal Analysis Methods;46
7.1.3;1.1.3 Nonclassical Theories of Crystal Nucleation in Glass;48
7.1.3.1;1.1.3.1 General Considerations;48
7.1.3.2;1.1.3.2 Phenomenological Models;49
7.1.3.3;1.1.3.3 Density Functional Theory;49
7.2;1.2 Crystal Growth in Glass;50
7.2.1;1.2.1 Theoretical Background;50
7.2.1.1;1.2.1.1 Normal Growth Model;51
7.2.1.2;1.2.1.2 The Screw Dislocation Growth Model;51
7.2.1.3;1.2.1.3 2D Surface-Nucleated Growth;52
7.2.1.3.1;1.2.1.3.1 Jackson’s Model for the Interface;52
7.2.2;1.2.2 Experimental Studies of Crystal Growth in Glass;54
7.3;1.3 Alternative Mechanisms of Glass Crystallization at Low Temperatures;58
7.4;1.4 Overall Glass Crystallization Kinetics;60
7.4.1;1.4.1 Theoretical Background;60
7.4.2;1.4.2 Experimental Studies of the Crystallization Kinetics in Glass;66
7.5;1.5 Concluding Remarks;72
8;2 Optical Properties of Nano-Glass Ceramics;74
8.1;2.1 Theoretical Background of Transparency;74
8.2;2.2 Application of Optical Nano-Glass Ceramics;76
8.2.1;2.2.1 Low Thermal Expansion Glass Ceramics;76
8.2.1.1;2.2.1.1 Structure, Properties, and Application of Stuffed ß-Quartzss Glass Ceramics;76
8.2.1.2;2.2.1.2 Processing of Stuffed ß-Quartzss Glass Ceramics;77
8.2.2;2.2.2 Luminescent Glass Ceramics;83
8.2.2.1;Theoretical Background;83
8.2.2.1.1;Laser Applications;84
8.2.2.1.2;Frequency Up-Conversion;85
8.2.2.1.3;Amplification at 1.3 and 1.5µm;86
8.2.2.1.4;Solar Energy Applications;87
8.2.2.2;Most Common Luminescent Glass Ceramics;87
8.2.2.2.1;2.2.2.1 Transparent Mullite Glass Ceramics;87
8.2.2.2.1.1;Structure, Optical Properties, and Application of Transparent Mullite Glass Ceramics;88
8.2.2.2.1.2;Processing of Mullite Glass Ceramics;91
8.2.2.2.2;2.2.2.2 Spinel Glass Ceramics;93
8.2.2.2.2.1;Properties and Application of Transparent Spinel Glass Ceramics;94
8.2.2.2.2.1.1;Broadband Optical Amplifiers and Tunable Lasers;94
8.2.2.2.2.1.2;Passive Q-switchers;98
8.2.2.2.2.2;Processing of Spinel Glass Ceramics;101
8.2.2.2.3;2.2.2.3 Oxyfluoride Glass Ceramics;103
8.2.2.2.3.1;Processing of Oxyfluoride Glass Ceramics;104
8.2.2.2.3.1.1;General Considerations;104
8.2.2.2.3.2;Properties and Application of Fluorescent Oxyfluoride Glass Ceramics;110
8.2.2.2.3.2.1;Up-Conversion Fluorescent Oxyfluoride Glass Ceramics;110
8.2.2.2.3.2.1.1;Other Host Nano-Crystals;117
8.2.2.2.3.2.2;Down-Conversion Fluorescent Oxyfluoride Glass Ceramics;120
8.2.2.2.3.3;Other Luminescent Glass Ceramics;130
8.2.2.2.3.3.1;Transparent YAG Glass Ceramics;130
8.2.2.2.3.3.2;Transparent Willemite Glass Ceramics;132
8.3;2.3 Concluding Remarks;133
9;3 Ferroelectric and Electro-Optical Properties of Nano-Glass Ceramics;136
9.1;3.1 Theoretical Background;137
9.1.1;Frequency and Temperature Dependence of er;139
9.1.2;Energy Loss;140
9.1.3;The Ferroelectric Effect;140
9.1.4;Electro-Optic Effect;141
9.1.5;Nonlinear Optics;141
9.1.6;Second Harmonic Generation;141
9.1.7;Third Harmonic Generation;142
9.2;3.2 Structure, Properties, and Application of Ferroelectric Nano-Glass Ceramics;142
9.2.1;3.2.1 Titanate-Based Glass Ceramics;144
9.2.1.1;General Processing of Titanate Glass Ceramics;144
9.2.1.2;Processing, Properties, and Application of Major Titanate Glass Ceramics;145
9.2.1.2.1;3.2.1.1 BaTiO3 Glass Ceramics;145
9.2.1.2.2;3.2.1.2 PbTiO3 Glass Ceramics;154
9.2.1.2.3;3.2.1.3 SrTiO3 Glass Ceramics;159
9.2.1.2.4;3.2.1.4 Solid Solution Perovskites;164
9.2.1.2.5;3.2.1.5 Other Titanate Glass Ceramics;168
9.2.1.2.5.1;Bismuth Titanate Glass Ceramics;168
9.2.2;3.2.2 Niobate-Based Glass Ceramics;171
9.2.2.1;3.2.2.1 Niobate Glass Ceramics with TeO2-Based Glasses;172
9.2.2.2;3.2.2.2 Niobate Glass Ceramics with Silicate and Aluminosilicate-Based Glasses;175
9.2.2.2.1;Niobate Glass Ceramics Containing NaNbO3 Nano-Crystals;175
9.2.2.2.2;Niobate Glass Ceramics Containing LiNbO3 Nano-Crystals;179
9.2.2.2.3;Niobate Glass Ceramics Containing KNbO3 Nano-Crystals;180
9.2.2.3;3.2.2.3 Niobate Glass Ceramics with Borate-Based Glasses;184
9.2.3;3.2.3 Other Ferroelectric Nano-Glass Ceramics;187
9.2.3.1;3.2.3.1 Tantalate Nano-Glass ceramics;187
9.2.3.1.1;3.2.3.1.1 Processing and Properties of Nano-Structured LaTaO3;187
9.3;3.3 Concluding Remarks;190
10;4 Magnetic Properties of Nano-Glass Ceramics;192
10.1;4.1 Theoretical Background and Definitions;193
10.1.1;Magnetic Dipoles;193
10.1.2;Magnetic Field Vectors;194
10.1.3;Diamagnetism;195
10.1.4;Paramagnetism;195
10.1.5;Ferromagnetism and Antiferromagnetism;196
10.1.6;Ferrimagnetism;196
10.1.7;Magnetocrystalline Anisotrophy;198
10.1.8;Magnetostriction;198
10.1.9;The Effect of Temperature on Magnetic Behavior;198
10.1.10;Domains and Hysteresis;198
10.1.11;Soft and Hard Magnets;200
10.1.12;Superparamagnetism;201
10.2;4.2 Application of Soft Magnetic Nano-Glass Ceramics;202
10.2.1;4.2.1 Biomedical Applications;202
10.2.1.1;4.2.1.1 Magnetite Glass Ceramics;206
10.2.1.1.1;4.2.1.1.1 Processing of Magnetite Nano-Glass Ceramics;207
10.2.1.1.2;Redox Equilibrium of Iron;212
10.2.1.1.3;4.2.1.1.2 Magnetic Properties of Magnetite Nano-Glass Ceramics;213
10.2.1.2;4.2.1.2 Zinc Ferrite–Based Glass Ceramics;216
10.2.1.2.1;4.2.1.2.1 Processing of Zinc Ferrite–Based Nano-Glass Ceramics;216
10.2.1.2.2;4.2.1.2.2 Magnetic Properties of Zinc Ferrite–Based Nano-Glass Ceramics;218
10.2.2;4.2.2 Other Applications of Soft Magnetic Nano-Glass Ceramics;221
10.2.2.1;4.2.2.1 Lithium Ferrite (LiFe2.5O4)–Based Glass Ceramics;221
10.2.2.2;4.2.2.2 Cobalt Ferrite (CoFe2O4)–Based Glass Ceramics;223
10.2.2.2.1;Magnetic Properties;224
10.3;4.3 Application of Hard Magnetic Nano-Glass Ceramics;224
10.3.1;4.3.1 Barium Hexaferrite (BaFe12O19)–Based Glass Ceramics;225
10.3.2;4.3.2 Strontium Hexaferrite (SrFe12O19)–Based Glass Ceramics;230
10.4;4.4 Concluding Remarks;233
11;5 Biomedical Applications of Nano-Glass Ceramics;236
11.1;5.1 Definitions;238
11.1.1;Biocompatibility;238
11.1.2;Bone Grafting;238
11.1.3;Cellular Differentiation;238
11.1.4;Cellular Proliferation;238
11.1.5;Osteoconduction;238
11.1.6;Osteoinduction;239
11.1.7;Osteogenesis;239
11.1.8;Bioinert Materials;239
11.1.9;Bioactive Materials;239
11.1.10;Resorbable Biomaterials;240
11.2;5.2 Applications;240
11.2.1;5.2.1 Nano-Structured Bioglass-Ceramic Coatings;240
11.2.1.1;5.2.1.1 Enamels;241
11.2.1.2;5.2.1.2 Plasma-Sprayed Coatings;242
11.2.1.3;5.2.1.3 Coatings Produced by Sol-Gel Technique;244
11.2.1.4;5.2.1.4 Coatings Produced by the Magnetron Sputtering Technique;245
11.2.2;5.2.2 Nano-Glass Ceramics in Implantology and Dentistry;246
11.3;5.3 Concluding Remarks;251
12;6 Other Applications of Nano-Glass Ceramics;254
12.1;6.1 Nanoporous Glass Ceramics;254
12.1.1;6.1.1 Fabrication, Properties, and Application of Porous Glass Ceramics;255
12.2;6.2 Tough Nano-Glass Ceramics for Magnetic Memory Disk Substrates;261
12.2.1;6.2.1 Nucleation and Crystallization;261
12.2.2;6.2.2 Mechanical Properties;261
12.3;6.3 Nano-Glass-Ceramic Coatings and Sealants;262
12.3.1;6.3.1 SOFC Sealants;263
12.3.1.1;6.3.1.1 The Glass-Ceramic Materials Employed in SOFC Sealants;263
12.3.2;6.3.2 Glass-Ceramic Coatings as Thermal Barriers;266
12.3.3;6.3.3 Glass-Ceramic Sealants for Solid-State Batteries;269
12.4;6.4 Concluding Remarks;269
13;References;272
14;Index;286

Leseproben

2 Optical Properties of Nano-Glass Ceramics
It is believed that the most important properties of nano-glass ceramics are their optical properties. In this chapter, the structure, processing, properties, and application of the most important nano-glass ceramics are thoroughly discussed, with an emphasis on the experimental and practical aspects of the subject. The luminescent glass ceramics, which have attracted considerable attention, in recent years, such as mullite and spinel glass ceramics doped with transition metal ions, and especially oxyfluoride glass ceramics, containing rare-earth-doped fluoride nano-crystals, have been given extensive coverage. Structure properties and application of more conventional low thermal expansion glass ceramics, such as the stuffed ß-quartzss nano-glass ceramics, and the most recent applications of nano-glass ceramics such as transparent YAG glass ceramics, have also been discussed. Keywords
Optical glass ceramics; mullite glass ceramics; spinel glass ceramics; passive Q-switchers; oxyfluoride glass ceramics; luminescence; up-conversion; down-conversion; YAG glass ceramics Chapter Outline 2.1 Theoretical Background of Transparency 63 2.2 Application of Optical Nano-Glass Ceramics 65 2.2.1 Low Thermal Expansion Glass Ceramics 65 2.2.1.1 Structure, Properties, and Application of Stuffed ß-Quartzss Glass Ceramics 65 2.2.1.2 Processing of Stuffed ß-Quartzss Glass Ceramics 66 2.2.2 Luminescent Glass Ceramics 72 Theoretical Background 72 Most Common Luminescent Glass Ceramics 76 2.2.2.1 Transparent Mullite Glass Ceramics 76 2.2.2.2 Spinel Glass Ceramics 82 2.2.2.3 Oxyfluoride Glass Ceramics 92 2.3 Concluding Remarks 122 The most important optical property of nano-glass ceramics is their transparency, i.e., the ability to transmit light (electromagnetic waves), in certain range of wavelengths according to their specific application. The transparency, however, is not the sole requirement to be fulfilled by these glass ceramics as promising candidates for various current applications, or potential applications in the near future. The great attention that has been attracted in recent years by nano-glass ceramic is mainly because of their ability to combine transparency with other desired properties, such as mechanical, thermal, chemical, and electromagnetic. 2.1 Theoretical Background of Transparency
There are two main mechanisms that may hinder the travel of light through a glass ceramic, which are as follows: 1. The light scattering due to the presence of two (or more) phases, the glass matrix and the dispersed crystalline particles, possessing different refractive indexes. 2. The absorption of light by ionic/atomic species which are present in both the glass matrix and dispersed particles. Effect of the first mechanism, the light scattering, which is the far more effective obstacle for the transmission of light through glass ceramics, can be minimized by (a) trying to achieve closely matched indexes of refraction between the two (or more) phases existing in the glass ceramic and low birefringence in the crystals or (b) by reducing the size of the dispersed crystalline particles to much smaller sizes than the wavelength of the incident light (Beall and Pinckney, 1999). MgZn stuffed ß-quartz solid solution is an example for the criterion (a) in which, despite crystal sizes of up to 10 µm, good transparency can be achieved, whereas the nano-glass ceramics should satisfy the second criterion (small crystallite size). Among several scattering theories, there are two theories which could better describe the mechanism of scattering in nano-glass ceramics. The first theory, known as Rayleigh–Gans model (Kerker, 1969) assumes the existence of widely separated independent scatterers in a glass matrix. In this case, sp, the total turbidity or attenuation due to scattering, is given as p˜(2/3)NVk4a3(n?n)2, where N is the particle number density, V the particle volume, a the particle radius, =(2p/?) (where ? is the wavelength), n the refractive index of the crystal, and ?n the index difference between the crystal and the matrix. For practical purposes, transparency is achieved here with particle radii of <15 nm and a refractive index difference of <0.1 between the glass and the dispersed crystals (Beall and Pinckney, 1999). The other scattering model assumes the existence of small particles that are more closely spaced; the distance between particles should be no smaller than the particle radius but can be up to 6 times the particle radius. In this condition, the turbidity is given by the equation as developed by Hopper (1985): c˜[(23×10-3)k4?3](n?n)2 where =[a+(W/2)] is the mean phase width, in which a and W are the particle radius and the inter-particle spacing, respectively. In this case, improved transparency is allowed with particle sizes <30 nm at larger refractive index differences, up to ?n=0.3 (Beall and Pinckney, 1999). 2.2 Application of Optical Nano-Glass Ceramics
As stated above, nano-glass ceramics as good candidates for various diversified applications are expected to have the capability of combining good transparency with other desired properties regarding the given application. One of the classification methods of these materials is according to the main characteristics (other than transparency) that determine their application. In this way, the transparent nano-glass ceramics can be classified into several groups. In this chapter, the processing, properties, and application of some of the most important transparent nano-glass ceramics are discussed. 2.2.1 Low Thermal Expansion Glass Ceramics
These glass ceramics usually combine the transparency with low thermal expansion and high mechanical strength. Originally developed for use in the high-precision optical applications such as telescope mirror blanks, these glass ceramics have become known and entered the domestic market in applications such as cooker tops, cookware, and as reflectors for digital projectors. The most important materials of this group are stuffed ß-quartzss glass ceramics, the detailed description of the structure and processing of which is discussed in the following sections. 2.2.1.1 Structure, Properties, and Application of Stuffed ß-Quartzss Glass Ceramics Buerger (1954) was the first investigator who recognized that certain aluminosilicate crystals, composed of three-dimensional networks of SiO4 and A1O4 tetrahedra, are similar in structure to crystalline forms of silica. These so-called stuffed derivatives of silica polymorphs may be imagined of as derived from silica networks by replacement of Si4+ by Al3+, accompanied by the filling of structural vacancies by monovalent cations. ß-Eucryptite, LiA1SiO4, and ß-spodumene LiA1Si2O6, which are respectively similar to ß-quartz and keatite structures, are such stuffed derivatives. Monovalent Li+, divalent Mg2+, and, to a smaller extent, divalent Zn2+ ions can also randomly fill the interstitial vacancies in the ß-quartz structure when Al3+ replaces Si4+ producing stuffed ß-quartz solid solutions (ß-quartzss). The aforementioned materials are well known for their very low thermal expansion coefficients over considerable temperature intervals. The two unique properties of these glass ceramics, the ultralow thermal expansion and the ability to be polished similar to a glass, allow these transparent glass ceramics to be very suitable for some optical applications such as mirror blank materials. For such uses, the thermal expansion of the material is very important, since any change in ambient temperature in the neighborhood of the mirror during use may result in a change of focus and lost time on the telescope. On the other hand, since most of the ceramic materials have low thermal conductivities, there is the possibility of large thermal gradient buildup during the dissipation of frictional heat. In order to prevent the distortion of glass bodies, often a long and tedious procedure should be used during the finishing process. The use of ultralow expansion materials would help in minimizing the distortion problems and accelerating the finishing process (Duke and Chase, 1968). As stated previously, the very fine microstructure of these transparent glass ceramics is also an important property. Since glass ceramics are polyphase crystalline assemblages, with significant residual glass, polishing problems could arise due to differential hardness between the phases. It was found that when the grain size was kept smaller than the wavelength of visible light, an optical finish, similar to that possible with glasses, could be obtained with no evidence of relief polishing (Duke and Chase, 1968). Their transparent nature also allows inspection of the mirror blanks for residual stress and...