Silica Glass and Its Application PDF

GLASS SCIENCE AND TECHNOLOGY
Volume 1. J. Stanek, Electric Melting of Glass

Volume 2. C. R. Bamford, Colour Generation and Control in Glass
Volume 3. H. Rawson, Properties and Applications of Glass
Volume 4. J. Hlavac, The Technology of Glass and Ceramics:
An Introduction
Volume 5. I. Fanderlik, Optical Properties of Glass
Volume 6. K. L. Loewenstein, The Manufacturing Technology
of Continuous Glass Fibres
Volume 7. M. B. Volf, Chemical Approach to Glass
Volume 8. Z. Strnad, Glass-Ceramic Materials
Volume 9. M. B. Volf, Mathematical Approach to Glass
Volume 10. M. B. Volf, Technical Approach to Glass
Volume 1 1 . 1 . Fanderlik, Silica Glass and Its Application
Glass Science and Technology 11
Silica Glass
and its Application
edited by
IVAN FANDERLIK
State Glass Research Institute, Hradec Krälovo, Czechoslovakia
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Amsterdam - Oxford - New York - Tokyo 1991
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Library of Congress Cataloging-in-Publication Data

Kfemenne sklo. English.
Silica glass and its application / edited by IvanFanderlik.
p. cm. -- (Glass science and technology; 11)
Translation of: Kfemenne sklo
Includes bibliographical references.
ISBN 0-444-98755-X
1. Glass. 2. Silica. I. Fanderlik, Ivan. II. Title.
III. Series: Glass science and technology; v. 11.
TP857.K74 1990 90-3013
666'. l-dc20 CIP
ISBN 0-444-98755-X (vol. 11)

ISBN 0-444-41577-7 (series)
© SNTL - Publishers of Technical Literature, Prague, 1991

Translation © ing. Karel Nemecek, CSc, 1991
All rights reserved. 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 or otherwise,
without prior written permision of the publishers.
Printed in Czechoslovakia
PREFACE
In terms of chemical composition, silica glass is the simplest amorphous substance

which has been commercially utilized in many fields of application in a number of
industrial branches, thanks to its physico-chemical properties.
No special monograph devoted solely to silica glass has so far been published.
Most of the information available had therefore to be gathered from a variety of
specialized literature.
The present publication thus fills a gap in the literature on glass. It deals with the
quartz raw materials suitable for the manufacture of clear, opaque and synthetic
silica glasses, various manufacturing processes, the physico-chemical properties of
silica glasses and their utilization in technological practice.
The monograph provides detailed information on the properties and use of silica
glass to workers in the glass industry, including those in research and development,
as well as to people in the fields of electronics, electrical engineering, communication
technology, optics and the chemical, power engineering and metallurgical industries,
and in a number of other industrial fields. It may also be useful to students of technical
schools and universities in supplementing information on the properties and appli
cations of silica glasses.
The team of authors thanks Ing. Zdenek Habrman, CSc, Ing. Vitezslav Kf est'an
and Ing. Petr Pavlas for their participation in the formulation of some parts of the
book.
The authors
5
Team of authors:
Ing. Josef Broukal, CSc,

State Glass Research Institute, Hradec Kralove, Czechoslovakia
Frantisek Dubsky,
Ing. Ivan Fanderlik, CSc,
Ing. Josef Jeräbek,
Institute of Mineral Raw Materials, Kutnä Hora, Czechoslovakia
Ing. Rudolf Zrustek,
Crystalex, Novy Bor, Czechoslovakia
LIST OF SYMBOLS AND UNITS
a activity (fugacity of gases)

a exponential coefficient of absorption, coefficient of thermal conductivity
a0 lattice constant (nm, μιη)

A Madelung's constant
b constant
b0 lattice constant (nm, μιη)
B photoelasticity constant (10~ 12 Pa"*)
c concentration of absorbing centres
c speed of light in vacuo (m s~l)
c0 lattice constant (nm, μιη)
Ci concentration of O H groups in silica glass (ppm)
cp specific heat (J g~ l K~l)
cp mean specific heat (J g~ * K~l)
C molar heat (J mol ~* K " l )
D{ (Ei) internal optical density (extinction)
e elementary electron charge
E modulus of elasticity in tension (Young's modulus) (MPa)
E activation energy (kJ m o l " x )
Ee electron energy (eV)
Er energy of the rotational motion of electrons (eV)
Ev energy of the vibrational motion of electrons (eV)
J] oscillator force
fm atomic dispersion factor of irradiated atom m
F free energy (Helmholtz function)
AFr change in free energy (of Helmholtz function) (J mol" l )
G modulus of elasticity in torsion (MPa)
h Planck's constant (6.6256 · 10" 34 ) (J s)
H enthalpy (J mol" x )
H° enthalpy in standard state (J mol" *)
AH change in enthalpy
/ experimental intensity of coherent dispersion
k equilibrium constant of reaction
10
km effective number of diffracting electrons in atom m
/ internuclear distance between two neighbouring ions
/ glass thickness
m electron mass
rri number of boundary surfaces
ηλ refractive index of glass for wavelength λ
n' refractive index of air (ri ~ 1)
n0 refractive index for ordinary ray (ordinarius)
nF - n c ,
n¥> — nc> m e a n d i s p e r s i o n
η
π» Ηγ» ng refractive indices
ne refractive index for extraordinary ray (extraordinarius)
JVA Avogadro number = 6.022 · 10 2 6 (k mol~ *)
N{ number or particles (molecules) in unit volume
p gas pressure (MPa)
p compressive or tensile stress (MPa)
q constant (0.0345 nm)
r speed of ultrasound (m s~ *), distance from centre
rA, r B atomic or ionic radii (for the case of single bond)
r AB interatomic distance between atoms A and B
rSi_0 separation of Si—O atoms
r Si _ Si separation of Si—Si atoms
R ratio of total number of oxygen to total number of silicon atoms
R gas constant = 8.314 33 (J mol~ x K " x )
R path difference
s degree of ionicity of a covalent bond
s, p, d, f electron configuration in Paschen's symbols
S entropy (J m o l " 1 K " 1 )
S overlap integral
S° entropy in standard state (J m o l " x K'1)
t temperature (°C), time (s, min)
ig transformation temperature
t2 second-order transformation point
At thermal endurance (resistance to thermal shock)
T temperature (K)
U potential energy
v phase speed of light in glass (m s" \)
dV elementary volume
W interaction energy
x A , x B electronegativities of atoms A and B
Δχ Α _ Β difference in electronegativities of atoms A and B
11
X mean number of non-bridging oxygen atoms in polyhedron
Y mean number of bridging oxygen atoms in polyhedron
Z mean number of all oxygen atoms in polyhedron (mean coordination
number)
Zm atomic number of atom m
ZX,Z2 charge numbers of ions
a coefficient of longitudinal thermal expansion (°C~ *), angle of the Si—O—Si
bond, absorption coefficient
a attenuation of ultrasound absorption (dB c m - 1 )
ß constant (0.09)
y surface tension (mN m~ *)
tan δ loss factor
Av porosity of quartz (%)
ε, ε' molar exponential absorption coefficient
ε permittivity
ε0 permittivity of vacuum
η viscosity (dPa s)
η0 viscosity at T -> oo (dPa s)
Θ angle (degree)
<9 m limit angle (degree)
Θ\ refraction angle of radiant flux (degree)
Θ1 angle of incidence of radiant flux (degree)
Θ2 refraction angle of radiant flux (degree)
λ wavelength (nm, μηι)
Aef effective thermal conductivity (W m " l K " *)
Ak thermal conductivity d u e t o conduction (W m " x K " l )
As thermal conductivity due to radiation (W m~ l K'1)
μ Poisson's ratio
v light wave frequency
ve, vd Abbe number
vt electron frequency
π bond due to overlapping of orbits perpendicular to the line connecting the
nuclei of two atoms
π Ludolf number
ρ coefficient of reflectance, density (kg m " 3 ) , resistivity (Ω)
ρά coefficient of scattered reflectance
ρρ surface electrical resistance (Ω)
ρτ coefficient of direct reflectance
ρ0 mean number of electrons in unit volume
σ bond due to overlapping orbits along the line connecting the nuclei of two
bound atoms, apparent density (kg m" 3 )
12
τ coefficient of transmission
τά coefficient of scattered transmittance
Tj coefficient of internal transmission
τΓ coefficient of direct transmittance
Φ total incident radiant flux
Φα absorbed radiant flux
Φβύ scattered reflected radiant flux
Φη mirror-reflected radiant flux
ΦτΓ directly traversing radiant flux
Φτά scattered traversing radiant flux
Φτ potential
Â> ^ B wave function (orbit) of atoms A and B
^hybrid wave hybridization function
Ψ3ζ wave function of 3s electrons
Ψ3ρ wave function of 3p electrons
13
1 SIGNIFICANCE AND CLASSIFICATION
OF SILICA GLASSES
Silica glass is finding ever-broader fields of application in various branches

of industry and research by virtue of its extraordinary physico-chemical properties,
such as resistance to thermal shock, spectral transmittance from the near ultraviolet
to the near infrared spectrum regions, chemical durability, electrical properties, high
resistance to deformation on heating, high chemical purity and consequent high
resistance to radioactive radiation. These properties are specific to silica glass and
are not exhibited by any other amorphous materials. Only Vycor glass shows
properties which approach those of silica glass.
Silica glass is manufactured by melting, i.e. the phase transformation of natural
crystalline quartz or quartz sand, pyrolysis or hydrolysis of SiCl4, or melting of Si0 2
gel or a number of other synthetic silicon compounds. Except for special cases of
preparation, the melting and working temperatures are mostly in the range of 1750
to 2000 °C, and depending on the method of manufacture and the purity of the raw
materials, the melted glass contains 99.5 to 99.9% Si0 2 .
The three basic types are
— clear silica glass melted from natural crystalline quartz raw materials,
— clear silica glass melted from synthetic silicon compounds,
— opaque (non-transparent) silica glass melted from sand.
According to Bruckner [ l ] , clear silica glass can be divided into the following
groups according to its terms of manufacture and properties:
Type I — clear silica glass made by melting natural quartz (rock crystal or vein
quartz) in electric furnaces, in vacuo or in an inert gaseous atmosphere. The glass
melted in this way contains up to 5 ppm of OH groups, but is characterized by its
relatively high concentration of Al (30 to 200 ppm) or Na (4 to 10 ppm). The cor
responding types of commercially manufactured silica glasses include Infrasil
(Heraeus), IR-Vitreosil (Thermal Syndicate), G.E. 105, 201, 204 (General Electric),
the Czechoslovak silica glass Silquartz (Sklotas, C.C., Novy Bor Works), Trasil
(Jablonec Glassworks, C.C., Desna in Jizerske Mountains), Infralux (Heraeus), Pur-
sil 453, Pursil Ultra and Pursil Optique (Quartz et Silice) and KI (USSR).
Type II — clear silica glass made by melting crushed natural rock crystal which
is introduced into a burner flame. As a result of the flame melting, the melted silica
glass contains about 250 to 400 ppm of OH groups. The corresponding types of
commercial glasses include Herasil (Heraeus), Homosil (Heraeus), Optosil (Heraeus),
15
O.G. Vitreosil (Thermal Syndicate), O.H. Vitreosil (Thermal Syndicate), Ultrasil
(Heraeus), G.E. 104 (General Electric), O H F (Heraeus), Q l , Q2, Q3 and Q4 (Schott
and Gen. Jena), KU-1, KU-2, KV and KV-R (USSR).
Type III — synthetic clear silica glass made by hydrolysis of SiCl4 vapours intro
duced into the flame of an oxygen-hydrogen burner. This glass is virtually free of
impurities, but contains up to 1000 ppm of OH groups and up to 100 ppm of Cl.
Among the corresponding types of commercial glasses are Suprasil (Heraeus),
Spectrosil (Thermal Syndicate), Corning 7940 (Corning Glass Works) and Type 151
(General Electric).
Type IV — synthetic clear silica glass made by pyrolysis of SiCl4 vapours blown
into a plasma burner flame in the presence of oxygen. The silica glass made in this
way contains only about 0.4 ppm of OH groups, but about 200 ppm of Cl. The cor
responding types of commercially produced glasses include Suprasil W (Heraeus),
Spectrosil WF (Thermal Syndicate) and Corning 7943 (Corning Glass Works).
The other types include special clear silica glasses with adjusted spectral t r a d
mittance in the ultraviolet region of the spectrum, such as M 62, M 84 (Heraeus) and
Germisil (Quartz et Silice). They are used in the manufacture of mercury discharge
lamps which do not produce ozone. Mention should also be made of the manufacture
of clear silica glass tubes with a toughened surface to raise the deformation tem
perature, of variously doped clear silica glasses for special purposes, etc. In addition
to the basic manufacturing methods, there are further modifications of the com
mercial technologies, such as the melting of Si0 2 gel prepared from sol by various
processes that are dealt with in more detail in Chapter 3.
The above types of clear silica glasses show some differences in physico-chemical
properties, as a result of the differences in melting technology and purity of the
initial raw materials. For specific technical applications, there is thus a wide choice
of special products.
Opaque (non-transparent) silica glass is made in electric resistance furnaces by
melting from silica sand.
It should be stressed that manufacturing technologies, particularly those for clear
silica glass, are subject to continuous development so as to allow for the manufacture
of glasses of the maximum possible purity (e.g. for the production of fibre optics) and
with superior physico-chemical properties; another aim is to achieve the highest
possible technological efficiency and to reduce power consumption. These questions
are dealt with in the appropriate chapters of the present volume; for deeper study
of the individual subjects, the reader is referred to the literature listed at the end
of each main chapter.
16
2 RAW MATERIALS FOR SILICA GLASS MANUFACTURE
2.1 INTRODUCTION
Clear silica glass is manufactured from natural or synthetic raw materials,
while opaque types are made from natural raw materials (sands). According to the
required purity of the glasses being manufactured it is necessary, particularly in the
case of clear silica glasses, to use quartz raw materials of suitable purity, i.e. to carry
out refining.
The present Chapter deals with natural and synthetic quartz raw materials from
the standpoint of their structure, properties and phase transformation in the course
of heating, as well as from that of the genetic conditions of the formation of natural
types of quartz, quartz deposits, sand deposits, and the respective evaluation methods.
An account of the refining methods is given in Section 3.3.
2.2 NATURAL RAW MATERIALS

2.2.1 The structure and properties of crystalline silica
Crystalline silicic oxide (silica), Si0 2 , is one of the most abundant minerals
of the Earth's crust, and occurs in various modifications and species. A comprehensive
tabular classification of the modifications and types of silica, according to Dinger
and Jebsen-Marwedel [3], is shown in the scheme on p. 18.
According to Blankenburg [2] and Florke [4], silica has 13 modifications, and
according to Sosman [14] it has 25 condensed phases. Below, we present a survey
of the most significant phases of silica, together with the respective crystallographic
systems:
— low-temperature /J-quartz (trigonal, trigonally trapezohedral),
— high-temperature α-quartz (hexagonal, hexagonally trapezohedral),
— low-temperature /J-cristobalite (tetragonal, pseudocubic),
— high-temperature α-cristobalite (cubic),
— low-temperature y-tridymite (structure not determined),
— medium-temperature ß-tridymite (hexagonal),
— high-temperature α-tridymite (hexagonal),
— coesite (monoclinic),
— melanophlogopite (cubic),
— keatite (tetragonal),
17
Modifications and types of silica oxide 13]
quartz high tempera-| tridymite silica

cristobalite glass
tu re quartz
I
Si0 2
crystalline fine crystalline amorphous
higMempera- cristobalite tridymite

quartz hure quartz
chalcedon
clear coloured with characteristic
mineral
(transparent) (inclusions) texture
—r~i— 1 1
i mostly grey,
turbid coloured laminar mineral
rock transparent opaque
I 1 _L _L
crystal J cornelian, agate, flinty
hornstone,
smoky quartz sapphire quartz fibrous quartz flint chrysoprasej onyx, shale,
morion cat's eye drop-shaped quartz and others plasma/ sardonyx lydite
citrine tiger's eye porphyric quartz heliotrope, and and
amethyst ferrian quartz granite quartz jasper others others
rose quartz milk quartz and others and others
and others and others .j
i—
compact hyd rated
I I anhydrous
tertiary and sand opal sintered, tuff and
boulder stones soil formations
quartz
milk opal, sintered quartz, natural silica glass,]
fire opal, sintered pearl, silica glass
hyalite, quartz tuff
glassy opal, and others
precious opal
and others
— fasriges Si0 2 (rhombohedral),
— stishovite (tetragonal),
— opal Si0 2 + H 2 0 (amorphous),
— lechatelierite (amorphous, natural silica glass).
From the point of view of the individual species, silica can be divided into the
following groups, according to Blankenberg [2] and Rost and Kocar [5]:
Quartz — rock crystal, smoky quartz, morion, citrine, amethyst, rose quartz, milk
quartz, cat's eye, falcon's eye, tiger's eye, ferrian quartz, auriferous quartz, prase,
aventurine, star quartz, porphyric quartz, fibrous quartz, etc.
Finely crystalline quartz — chalcedon, enhydros, agate, onyx, sardonyx, Chrysopras,
plasma, heliotrope, carneol, jade, annular agate, kasholong, flint, hornfels, lydite,
limnoquartzite, etc.
Opal — hyalite, geysirite, wax opal, milk opal, wood opal, precious opal, fire opal,
kasholong, fiorite, menilite, kieselguhr, etc.
Table 1
Group classification of the structure of silicate anions
Group Type Number of shared oxygen atoms
I separate tetrahedra 0
II tetrahedron couples 1
III simple rings 2
trinomial rings
tetranomial rings
hexanomial rings
IV double rings alternately 2 and 3
V infinite chains 2
VI double infinite chains alternately 2 and 3
VII infinite layers 3
VIII infinite double layers alternately 3 and 4
IX spatial networks 4
Silica, Si0 2 , does not produce any separate molecules ( 0 = S i = 0 ) because double
bonds do not form. To avoid the formation of a structural entity with an unsaturated
electron cloud at the silicon atom in the case of a single bond, the [ S i 0 4 ] 4 ~ tetrahedra
join to produce a polymer with various spatial arrangements (Table 1). In this way
there arises a giant, three-dimensional, very strong lattice of a structural arrangement
which fuses only at very high temperatures. As a result of the alternative possibilities
of structural arrangement, there exist a number of crystalline modifications and
species (types) of crystalline silica.
Expressed in Paschen's symbols, the electron configuration of the oxygen atom
corresponds to is 2 2s2 2p 4 . In agreement with Hund's rule, one of the 2p orbits
19
(e.g. 2px) is occupied by two electrons with antiparallel spins, while the other two
orbits contain one electron each with parallel spins. This corresponds to a lower
energy level of the atom, as shown in Fig. 1.
1s 2s 2p
t Fig. 1 — States of electrons in the oxygen atom
The last 2p-orbits are responsible for the valency of oxygen and the two non-pair
electrons, 2py and 2pz, form the bond with the outer electrons of silicon.
The electron configuration of the silicon atom is Is2 2s2 2p6 3s2 3p2. The individual
electrons are distributed in the orbits as shown in Fig. 2.
τ^ iltfl·
1s 2s 2p 3s 3p
II tl f I
1 I
I I
Fig. 2 — States of electron in the silicon atom
In the excited state, the electron configuration of the silicon atom in Paschen's
symbols is Is2 2s2 2p6 3s 3p^ 3p^ 3p^, as demonstrated in Fig. 3.
1s 2s 2p 3s 3p
HD 0 h 11111 n i Q] \\\\J\\
Fig. 3 — States of electrons in the silicon atom (excited state)
Silicon is capable of forming four bonds in the latter case, and if the energy of bond
formation is high enough to excite the atom, tetravalency will prevail. Silicon is
actually tetravalent in most chemical compounds.
If one considers an ionic bond with a tetrahedral arrangement of four oxygen atoms
around one silicon atom, and takes into account the radii of the Si 4+ and O 2 - ions,
this tetrahedral arrangement will be the most closely packed one.
In the instance of a covalent bond, this arrangement likewise corresponds to four
oxygen valencies directed towards the four corners of a regular tetrahedron occupied
by four oxygen atoms. With substances having a purely ionic bond, a region of zero
fclectron density would have to arise between the Si 4+ cation and the O 2 - anion;
as no such region has been found in the case of the Si—O bond (cf. Fig. 9), it may be
assumed covalent as well as ionic in character.
The subject of the two types of bonds in relation to the [Si0 4 ] 4 ~ tetrahedron is
briefly dealt with below.
20
2.2.1.1 I o n i c m o d e l of t h e [ S i 0 4 ] 4 elementary tetrahedron
To assess quantitatively the conditions for the formation of ions, one has
to consider in particular the ionization energy (the energy required for breaking one
electron from an atom in its basic state), the electron affinity (the energy released
when a free atom accepts one electron, thus creating a negatively charged ion), the
ionic bond energy, the deformation and the polarizing effect of ions. The formation
of an ionic bond is further affected by the electrostatic attraction between the two ions.
In a crystal, each ion is surrounded on all sides by ions of opposite charge, so that
multidirectional interaction occurs. This leads to further changes in energy.
The potential energy in a crystal can be calculated from the equation
NAAZ1Z2e2
U = - (1)
4πε0/
where U is the potential energy,
NA is Avogadro' number, 6.022 · 10 26 (kmol~ *),
Z 1? Z 2 are the charge numbers of the ions,
e is the elementary charge,
ε0 is the permittivity of vacuum,
/ is the internuclear distance between two neighbouring ions,
A is Madelung's constant
Madelung's constant takes into account the structural interactions, and its value
depends on the type of crystal structure. However, with a crystalline structure, it is
further necessary to consider the mutual repulsion of cations and anions resulting
JL
attraction
Fig. 4 — Energy of the crystalline structure,

in terms of intermolecular distance between ions
21
from their negatively charged electron envelope. For this case Born and Meyer
derived the exponential function b e~i/q, so that equation (1) may be written in the
form
where b and q are constants.

A graphical representation of this relationship is shown in Fig. 4.
For the minimum on the curve (Fig. 4) it holds that
dU NAAZlZ2e2 b
2 - - e"1'* = 0 (3)
dl 4πε 0 /
Using equation (3), constant b can be eliminated from equation (2), and Born-Meyer's
equation acquires its final form
_ _ Ν,ΛΖ,Ζ^ / _ A
U
4πε0ί V //
For most crystalline substances, the constant q has the value 0.0345 nm.
In a crystalline structure, the ions therefore take up certain equilibrium positions
for which the potential energy of the system is at its minimum. When approaching
each other, the ions become subject to repulsive forces acting against their mutual
compression. This is why, according to this theory, ions are regarded as incom
pressible spheres of certain dimensions, defining the ranges of their energy effects
in the crystalline structure. The values of the radii of the individual ions were deter
mined by Pauling [7] for the coordination number 6.
The process of arranging the cations and anions in a structure involves defor
mation of the electron envelopes by the effect of their electric fields. This deformation
depends on the size of their charge and on the volume.
The polarizing effect of a cation results from the influence of the adjacent boundary
orbits in the electron envelope of the anion; it is directly proportional to the cation
charge and inversely proportional to its volume. The structure of the outer electron
layer also has a considerable influence on the polarizing effect of a cation. Similarly,
an anion will also deform a cation by repulsing its electron envelope by its negative
charge. However, the deformability of cations is much smaller than that of anions.
According to Pauling [7], for coordination number 6 the ionic radii of the Si4 +
and O 2 - ions are 0.041 nm and 0.140 nm, respectively. Goldschmidt and Zachariasen
specify the range of 0.039 to 0.044 nm for the Si 4 + ions and 0.132 to 0.140 nm for the
O 2 - ion. To convert the ionic radius from coordination 6 to 4 (which is the case
of the [ S i 0 4 ] 4 ~ tetrahedron) use is made of a coefficient of 0.922 given by Pauling [7],
so that the Si—O distance in the tetrahedron, calculated from ionic radii, should
be 0.167 nm. This distance between the two ions varies in the respective modifications
22
of silica and in the more complex silicates, and its value is around 0.162 + 0.005 nm.
The distance between two neighbouring oxygen ions, O—O, situated in the tetra
hedron, likewise shows a variation from 0.262 nm to 0.267 nm in the diverse silica
modifications and silicates. Figure 5 shows a schematic diagram of the ionic model
of the [ S i 0 4 ] 4 " elementary tetrahedron, according to Pryanishnikov [8].
/
/
I
I
Νχ Λ / Fig. 5 - Schematic diagram of an ionic model of the
[Si0 4 ] 4 _ elementary tetrahedron
The following criteria can therefore be established for the ionic bond in a crystal
on the basis of Pauling's rules:
— a coordination polyhedron of anions is formed around each cation, where the
cation-anion distance corresponds roughly to the sum of radii and the coordination
number is defined by the ratio of their radii;
— in stable structures, the total strength of the valency bond of each cation in
the coordination polyhedron is divided uniformly among all the surrounding anions.
On the other hand, the valency of each anion is saturated by all the neighbouring
cations; the number of bonds into which the respective valency of the elements is
divided, depends solely on the coordination;
— the strongly charged cations tend to stay apart, with the result that the anionic
multihedra coordinated around the cation tend to join preferentially by sharing
their apices;
— in crystals containing various cations, those with the higher valency and a lower
coordination number tend to occupy the multihedron points alone;
— the number of crystallographically different components in a crystal should be
as low as possible.
For coordination 4 (using the conversion coefficient of 0.922), the ionic radii will,
therefore, be
Si 4 + 0.038 nm,
O 2' 0.129 nm.
According to Pauling [7], the value of the ratio 0.038/0.129 = 0.29 allows us to
assume that the structure of silica has actually the coordination 4, if the partial
deformability of the O 2 " ions is taken into account.
23
We have so far only considered the ionic model of the [ S i 0 4 ] 4 " tetrahedron.
However, between the crystals with a purely ionic bond and those with a purely
covalent one, there is a continuous series with transient types of bonds. On the basis
of electronegativities Pauling [7] established to what degree a bond can be considered
ionic and covalent. As regards the Si—O bond, he came to the conclusion that it is
only 50% ionic. This is why the covalent bond also has to be considered in the account.
2.2.1.2 C o v a l e n t m o d e l of t h e [ S i 0 4 ] 4 " e l e m e n t a r y t e t r a h e d r o n
Neither the form nor the energy of the covalent bond can be explained on
the basis of classical bond theories. Various quantum mechanical theories have
therefore been developed to assess the suitability of the diverse theoretical approaches
employed, by comparison with experimental data [6].
Among the respective theories, mention should be made of the valence bond theory,
the covalent radii theory, the covalent bond ionicity theory, the directional character
of the covalent bond theory and, in particular, of the hybridization theory.
The valence bond theory was worked out by Slater and Pauling [9, 12]. On the
basis of calculations carried out for the hydrogen molecule, they concluded that as
two atoms approach within a certain distance of each other, an electron can pass
from one nucleus to the other until the probabilities that each electron occurs in the
region of one or the other nucleus become equal. The two electrons then belong
jointly to the two nuclei, and a covalent bond has been formed. However, according
to Pauli's principle, the two electrons in the molecule (or equally in the atom) should
differ by at least one quantum number. In the hydrogen molecule, they differ in the
spin quantum number, thus having antiparallel spins. In that instance, a reduction
in energy and an increase in stability result when hydrogen atoms come close together.
It was further found that atoms in a molecule or in an atomic crystal may be
ascribed certain covalence radii. The sum of the covalence radii of two atoms equals,
approximately, the internuclear distance of these atoms in compounds. In the case
of a single bond, this radius amounts to 0.117 nm and 0.074 nm for a silicon and an
oxygen atom, respectively.
In the bond of two different atoms, e.g. Si and O, it is further necessary to consider
the polarity of the covalent bond. In this case the electron pair is not bound to the
two atoms by the same force, being shifted towards that showing greater attraction.
This effect raises the electron charge density and produces polarity.
The ability of a covalently bound atom to attract an electron pair is called electro
negativity. According to Gazo [6], silicon and oxygen have respectively electro
negativities of 1.8 and 3.5. If the difference in electronegativity values, xA — xB, for the
two atoms is up to 1.7, the bond is covalent by 50% and ionic by 50% (according to
Pauling [7]). If the value of the difference exceeds 1.7, the bond is prevailingly ionic.
24
As already mentioned above, it may be assumed that both the ionic and covalent
characters are partially involved in every bond. Pauling has, therefore, derived an
equation for the degree of ionicity of the covalent bond between atoms A and B
having electronegativities xA and xB:
s= 1 _ e -' / 4 <* A -* B ) 2 , (5)
where the electronegativities of atoms A and B, respectively.

On the basis of electronegativity calculations, Lakatos,Bohus and Medgyesi [46],
Jatkar and Jyengar [47] and others found that the ionicity degree of the Si—O bond
varies between 35 and 50%, which is in reasonable agreement with the ionicity degree
established by Pauling (50%).
This bond exhibits a certain polarity, influenced above all by the difference in
electronegativity of the two bound atoms. The higher this difference, the more polar
the bond and, consequently, the higher the bond ionicity.
The results obtained from studies of the spatial arrangement of covalently bound
atoms indicate that the mutual arrangement of covalent bonds in space is additionally
affected by the angular distribution of the atomic orbits. This finding is in agreement
with Schrödinger's wave equation, which describes the probability density of the
occurrence of electrons. The bond strength is determined by a factor called the
atomic orbit overlap degree or overlap integral S, which can be calculated from the
following equation after Mulliken [6, 17]:
S=|VA!PBdV (6)
where ΨΑ, ΨΒ are the wave functions (orbits) of atoms A and B between which the
bond is formed and dV is the elementary volume.
The higher the S value, the stronger the bond.
However, the directional arrangement of the bonds has been found to differ from
that predicted from the participation of the simple s, p and d orbits of the central
atom. The bond strengths also disagree with the participation of these so-called pure
atomic orbits.
It was the hybridization theory which succeeded in explaining these discrepancies.
For a detailed study of the distribution of electrons in atoms, particularly with
regard to De Broglie theory and Schrödinger's wave equation, the reader is referred
to [72, 44, 45].
The principle of hybridization is that suitable linear combinations of the original
atomic functions (orbits) produce new ones, called the hybrid orbits. They may arise
when atomic orbits with suitably similar energies combine, while in the direction
of their orientation (given by the hybridization type) the hybrid orbits always show
25
a higher electron cloud density than the pure atomic orbits. This is in agreement with
Schrödinger's wave equation.
This allows for stronger overlapping with the orbits of other atoms and, con
sequently, for the formation of stronger bonds.
For its bond formation, oxygen utilizes particularly the non-pair 2py and 2pz
electrons, always one for each silicon atom. Silicon, on the other hand, uses only
the 3s non-pair valency electron and three 3p valency electrons. Theoretically, these
four orbits with non-pair electrons in the silicon atom should not be equivalent in the
excited state. In contradiction to this, however, many factors and symptoms indicate
a full equivalence of all the four bonds, as will be shown below.
On the basis of wave mechanics, it may be assumed that the system will attain
its minimum energy when the four orbits (three p and one s) combine, i.e. hybridize.
sp - hybridization
b)
sp - hybridization
Fig. 6 — Electron configuration

of the Si—O—Si bond:
(a) sp-hybridization;
(b) sp 2 -hybridization;
sp - hybridization (c) sp 3 -hybridization
26
In the case of the structure of the [ S i 0 4 ] 4 ~ tetrahedra, the possible hybridizations
are sp 3 , sp 2 and sp, as demonstrated in Fig. 6 according to Lazarev [13] and Balta [10]
(the points represent the σ-bonds, and in planar symmetry the d7C bonds forming
between the non-shared electron pairs of the oxygen 2p orbits and the silicon d orbits).
The distribution of electrons around the silicon atom in the valency state can be
described by the wave equation according to Pryanishnikov [8]:
hybrid = . ^ , + 7 3 ^ (7)
where iPhybrid is the hybridization wave function,

W3s is the wave function of the 3s electrons,
Ψ3ρ is the wave function of the 3p electrons.
An analysis of the peaks exhibited by the hybrid functions revealed that they were
uniformly distributed in space and directed along the diagonals of a regular tetra
hedron with a valency angle Θ ~ 109° 28' of the Si—O bond (cf. Fig. 7). The strength
of these hybrid bonds is greater than that of the s and p bonds.
The sp hybridization:
The s and p orbits are located along one straight line, thus having a diagonal
orientation (cf. Fig. 6(a)) and making an angle of 180°.
The sp2 hybridization:
The orbits lie in a single plane (cf. Fig. 6(b)), making an angle of 120°.
The sp3 hybridization:
A linear combination of one s orbit and three p orbits is capable of creating

four sp 3 hybrid orbits, showing a tetrahedral orientation and including an angle
of 109° 28'(cf. Fig. 6(c)).
From Mulliken' overlap integral S (equation 6), the maximum overlap (S ~ 0.8)
should be achieved with sp hybridization, which means that the sp bonds should be
stronger than the sp 2 and the sp 3 bonds. In the case of sp 3 hybridization, four simple
equivalent σ bonds are formed and, subsequently, also the [ S i 0 4 ] 4 _ tetrahedra,
mutually bound into a spatial lattice via the common silicon atom. The σ bond is
produced by the overlapping of orbits situated on the line connecting the nuclei
of the two bound atoms and, in most instances, involves the overlapping of ss, sp
and pp orbits. It is further formed by the overlapping of s and p orbits with the hybrid
ones, or by mutual overlapping of hybrid orbits.
The covalent model of the [ S i 0 4 ] 4 ~ structure is, therefore, based on a localized
structure effected by sp 3 hybridization of silicon orbits with 2py or 2pz oxygen orbits.
Measurements have shown that the angle of the Si—O—Si bond varies with the
27
different tetrahedra of the polyhedron, according to the respective form of silica
(and for various silicates) over the range of 143° to 180° (for vitreous Si0 2 , from 120°
to 180°), as listed in the table (Table 2) compiled by Pryanishnikov [8] on the basis
of data from various authors.
Table 2
The Si—O distance and the Si—O—Si bond angle for various Si0 2 modifications
Modification Si—O distance Si—O—Si bond angle

(nm) (°)
(according to various authors)
Low-temperature 0.1603 + 0.0003 147

jS-quartz 0.1611 ± 0.0002 143.9 ± 0.2
0.1596 to 0.1617 144 ± 0.2
High-temperature 0.162 146

a-quartz 155
Low-temperature 0.162 147

1
/?-cristobalite 0.159 150
High-temperature 0.154 180

a-cristobalite 0.158 to 0.169 152
Amorphous Si0 2 0.162 180

0.158 146
142
0.160 143 ± 17
0.162 120 to 180
The angle between the Si—O bonds in the elementary tetrahedron is, therefore,
stable (109° 28'), whereas the angle of the Si—O—Si bond between the individual
tetrahedra in the polyhedron varies over the ranges given above.
In considering the covalent model of [ S i 0 4 ] 4 ~ and taking into account the changes
in the angle of the Si—O—Si bond and the Si—O separation distance, one must
include the effect of the 2py and 2pz non-pair electrons, a's well as that of the 2p x
electrons and the 2s orbits resulting from their hybridization (formation of short
bonds). These are produced by more than just one pair of electrons. In that instance,
the oxygen may form bonds in sp 3 hybridization (four σ bonds), in sp 2 , p hybridi
zation (three σ bonds and one π bond) and in sp, p 2 hybridization (two σ bonds and
two π bonds). The π bond arises due to overlapping of orbits situated perpendicular
to the line connecting the nuclei of the two atoms, i.e. by the overlapping of pp, pd
and dd orbits. The σ bond exhibits a rotational symmetry with respect to the bond
axis; the π bond does not show any such symmetry.
28
According to Pryanishnikov, it is further necessary to consider the so-called
siloxan bond, including the participation of the donor—acceptor bond. The former
is effected by dislocated electrons of unshared electron pairs of oxygen, which lead
to a decrease of the effective charges of both atoms. This bond generally results in
the creation of closed circular structural formations (in the case of a smaller number
of structural units) or of chain-like formations (of a higher number of structural
units).
In the case of silicon, five additional 3d orbits should therefore be considered,
besides the s and p orbits [8]. Although less stable than the 3s and 3p orbits, one or
two of them may be utilized to create a bond with the 3s and 3p orbits. From the
standpoint of energy content, they are close to the 3p orbits.
According to Lazarev [13], considerable overlapping of d orbits with respect to
the σ bond can be expected. Effective overlapping of silicon d orbits with oxygen
p orbits requires that their nodal planes and the σ bonds be identical, and correspond
to the maximum electron density of the d orbits. If the atoms at the apices of the
tetrahedra are sufficiently electronegative, the (d7t - ρπ) bonds are strengthened.
The mechanism of bond formation between an oxygen atom and two neighbouring
silicon atoms (Si—O—Si) can, therefore, be explained in the following way. With the
various forms and modifications of silica, the angle of the Si—O—Si bond varies
over the range of 120° to 180°, i.e. in the space between the sp2 and the sp orbits of
the oxygen atom. As we already know, sp2 hybridization joins two p orbits with one
s orbit. In the_given case, 2p r 2pz and 2s orbits hybridize, producing three new atomic
orbits s + >/2p, lying in one plane at an angle of 120 degrees. The two unshared elec
trons of the 2px orbit remain vacant and may form a dislocated π bond with the free
d orbits of the silicon atoms (dx2_y2 or dz2). In the case of linear sp hybridization,
p and s orbits of two equivalent hybrid orbits s + p combine; the latter are distributed
on opposite sides at an angle of 180 degrees, while the electrons of the 2px and 2py
orbits remain available for the creation of π bonds with the silicon atom orbits
(dJC2_);2 and dz2). The possible weakening of the σ bonds is balanced by strength
ening of the άπ bond.
With the [Si0 4 ] 4 " tetrahedron, it may therefore be assumed that the angle
between the Si—O bonds is affected by sp3 hybridization of the 3s and 3p orbits
Fig. 7 — Schematic diagram of the covalent model of the

[ S i 0 4 ] 4 _ elementary tetrahedron
29
of the silicon atom, and that the various sizes of the Si—O—Si bond are influenced
by a complex case of sp" hybridization in which the hybrid orbits are not equivalent.
For the various modifications, the degree of participation of the respective types of
hybridization and, consequently, the corresponding strengths of the (d7C — ρπ) bonds,
vary; this also affects the differences in the Si—O—Si bond angles and those in the
Si—O separation distances. The covalent model of the elementary [Si0 4 ] 4 _ tetra
hedron according to Pryanishnikov [8] is shown in Fig. 7.
2.2.1.3 Characteristics of the Si—O bond
The results of studies by Slater [18], Weber and Cromer [19], Bratcev [20],
Bragg [21] and others indicate that the Si—O separation distance in the various
modifications of silica and in the diverse types of silicates may be taken to vary in
Fig. 8 — Electron density

of low-temperature
ß-quartz
Q1 i
30
the range of 0.154 nm to 0.170 nm, while the mean value specified for quartz is
0.162 ± 0.005 nm (cf. Table 2).
These values can be calculated from the equation
*AB = rA + rB - βΔχ Α _ Β (8)
where rAB is the interatomic distance between atoms A and B,

rA, rB are the atomic or ionic radii (for the case of the single bond),
β is a constant (0.09),
ΔχΑΒ is the difference in the electronegativities of the two atoms.
Brill, Hermann and Peters [22, 23] studied the structure of low-temperature
/J-quartz by means of X-ray techniques. The electron densities according to Brill
are given in Fig. 8.
In relation to the typical electron distribution in ionic crystals, the values established
by Brill indicate a marked prevalence of covalent bonds in the low-temperature
modification of /J-quartz. The results of studies by a number of other authors, e.g.
Golutvin [24] and Pauling [7], likewise indicate a significant share of covalence in
the Si—O bond, of approximately 30 to 50%.
2.2.1.4 C r y s t a l l i n e m o d i f i c a t i o n s of q u a r t z a n d p h a s e t r a n s f o r m a t i o n s
Figure 9 shows a phase diagram of the stable modifications of quartz under

atmospheric pressure, according to Fenner [16]. The diagram has been brought up
to date and adjusted by a number of authors according to more recent research
results, as dealt with in Section 3.2.
The structure and phase transformations of the main modifications of quartz are
the subject of a separate paragraph below.
Low-temperature ß-quartz and high-temperature en-quartz
The structure of low-temperature /?-quartz, according to Bragg and Gibbs [25],

is shown in Fig. 10.
In low-temperature jß-quartz, the Si and O atoms are arranged in two spatial groups,
i.e. that of the right-hand quartz (designated D* by Schoenflies [33] and P 3X 21
by the International Union [34], and left-hand quartz (Df or P 3 2 21). The tetra-
hedra are distributed on different levels, along spirals rotated to the right (right-hand
quartz) and to the left (left-hand quartz) around a trigonal axis. According to Sosman
[14], low-temperature ß-quartz is stable over the temperature range from —273
to + 573 °C (Fenner quotes a temperature of 575 °C). According to Wyckoff s classi-
31
fication [26], the corresponding positions of atoms for the P 3l 21 spatial group
are as follows:
Si(a) — ü, ü, 1/3; u, 0, 0; 0, u, 2/3
O(c) — x, y, z; y — x, x, z + 1/3; y, x — y, z + 2/3;
x - y, y, z; y, x, 2/3 - z; x, y - x, 1/3 - z
(u = 0.465; x = 0.415; y - 0.272; z = 0.120).
a
to a-cristobalite
ß> -cristobalite
/d-tridymite —
^-tridymite
ΜΌ
Fig. 9 — Phase diagram of stable modifications of crystalline Si0 2
O Si
O 0 Fig. 10 — The structure of low-temperature /?-quartz
32
The elementary cell contains 3 SiO2,a0 = 0.4890-0.4913 nm,c0 = 0.539-0.5409 nm,
the Si—O separation distance is 0.160-0.162 nm, that of O—O being 0.262-0.267 nm,
and the angle between the Si—O bonds in the tetrahedron is 108°8'-110°3'. The
Si—Si distance apart is 0.304 nm and the angle of the Si—O—Si bond in the poly
hedron is 143-147°. The density is 2500-2656 kgm" 3 and the refractive indices at
20 °C for λ = 589.3 nm are n e = 1.55336, n0 = 1.54425.
At 573-575 °C, low-temperature /J-quartz converts to the high-temperature
α-quartz. The structure of high-temperature α-quartz, according to Wyckoff [53],
Si
O O Si
O 0 O 0
Fig. II - The structure of high-temperature α-quartz Fig. 12 - The structure of low-temperature

/f-cristobalite
In high-temperature α-quartz, the Si and O atoms are arranged in spatial groups,

i.e. right-hand quartz (D£; P 62 22) and left-hand quartz (D^; P 64 22) and, according
to Wyckoff, the positions of the atoms corresponding to the P62 22 spatial group
are the following:
(Si(c) - 1/2, 1/2, 1/3; 1/2, 0, 0; 0, 1/2, 2/3
0(j) — u, ü, 5/6; Π, u, 5/6; u, 2u, 1/2; ü, 2ü, 1/2; 2u, u, 1/6; 2ü, ü, 1/6.
The elementary cell contains 3 Si0 2 , a0 = 0.501 nm, c0 = 0.547 nm, the Si—O
distance apart is 0.162 nm, the O—O separation distance is 0.255 nm, the Si—Si
separation 0.3034 nm, the Si—O—Si bond angle is 146-155° and the density at 585 °C
2100-2518 kg m" 3. The refractive indices at 585 °C for λ = 589.3 nm are ne = 1.5405,
n0 = 1.5329.
Low-temperature ß-cristobalite and high-temperature a-cristobalite

The structure of low-temperature /?-cristobalite, according to Barth [32], is shown
in Fig. 12.
33
The spatial arrangement (spatial group) is again of the left-hand type (D*; P 4 ^ 2 )
and right-hand type (D®; P 43 2t2). In the former case, the arrangement of atoms
according to Wyckhoff is as follows:
Si(a) - u, u, 0; ü, ü, 1/2; 1/2 - u, u + 1/2, 1/4; u + 1/2, 1/2 - u, 3/4
O(b) - x, y, z; x, y, z + 1/2; 1/2 - y, x + 1/2, z + 1/4;
y + 1/2, 1/2 - x, z + 3/4; y, x, z; y, x, 1/2 - z;
1/2 - x, y + 1/2, 1/4 - z; x + 1/2, 1/2 - y, 3/4 - z
(u = 0.30; x = 0.245; y = 0.10; z = 0.175).
The elementary cell contains 4 Si0 2 , a0 = 0.4973 nm, CQ = 0.6930 nm, the separ
ation distances are Si—O 0.159 nm, O—O 0.258-0.263 nm and Si—Si 0.306 nm, with
the Si—O—Si bond angle 150°. The density at 20 °C is 2320-2330 kg m" 3 and the
refractive index at 20 °C ne = 1.484 and n0 = 1.487.
The metastable form of low-temperature ß-cristobalite occurs over the tem
perature range from — 273 to 272 °C.
The phase transformation of /J-cristobalite into α-cristobalite takes place at
218-272 °C, depending on the grain size, the conversion temperature duration and
the presence of structural impurities, as demonstrated experimentally by Sinelnikov
[27], Flörke [28] and others [29, 30].
Sl Sl
^ Fig. 13 - The structure O Fig. 14 - The structure of
O 0 of high-temperature α-cristobalite O 0 high-temperature a-tridymite
The structural transformation of j8-cristobalite into α-cristobalite and vice-versa

proceeds rapidly, without disturbing the Si—O bond; the conversion brings about
only a change in the Si—O—Si angle and involves a thermal effect, of 1298 ± 84
(J mol~x) [31]. The transformation results in a change of volume, by 3.7%.
The structure of high-temperature α-cristobalite, according to Wyckoff [54], is
shown in Fig. 13.
34
The spatial group of high-temperature α-cristobalite is O^; F d 3m. According to
Wyckoff, this spatial group exhibits the following distribution of atoms:
Si(8f) - 0,0,0; 1/2,1/2,0; 1/2,0,1/2; 0,1/2,1/2; 1/4,1/4,1/4; 1/4, 3/4, 3/4;
3/4, 1/4, 3/4; 3/4, 3/4, 1/4
0(16b) - 1/8, 1/8, 1/8; 5/8, 5/8, 1/8; 5/8, 1/8, 5/8; 1/8, 5/8, 5/8; 1/8, 7/8, 7/8;
5/8, 3/8, 7/8; 5/8, 7/8, 3/8; 1/8, 3/8, 3/8; 7/8, 1/8, 7/8; 3/8, 5/8, 7/8;
3/8, 1/8, 3/8; 7/8, 5/8, 3/8; 7/8, 7/8, 1/8; 3/8, 3/8, 1/8; 3/8, 7/8, 5/8;
7/8, 3/8, 5/8.
In contrast to this, Barth [32] considers the spatial group T 4 ; P 2 a 3.
According to Barth [32], the elementary cell contains 8 Si0 2 , a0 = 0.711-0.713 nm,
the Si—O separation distance is 0.154 nm, the Si—Si distance apart 0.308 nm, the
Si—O—Si bond angle 180°. The density at 290 °C is 2200 kg m" 3 , the refractive
index nm = 1.486.
According to Sosman [14], the metastable form of high-temperature a-cristo-
balite occurs over the temperature range 272-1470 °C, the stable form over the
temperature range 1470-1723 °C.
Low-temperature y-tridymite, medium-temperature ß-tridymite and high-temperature

CL-tridymite
The elementary modification of tridymite is the stable form of high-temperature

α-tridymite, occurring over the temperature range 867-1470 °C. Its structure, ac
cording to Gibbs [55], is shown in Fig. 14.
The elementary cell consists of 4 Si0 2 , a0 = 0.503 nm, c0 = 0.822 nm and the
density is 2260 kg m" 3 . It is optically monoaxial-positive.
On cooling high-temperature α-tridymite, it is converted at 163 °C to the meta
stable form of medium-temperature jS-tridymite, which has so far been the form of
quartz least extensively studied. Its structure is probably hexagonal-monoaxial.
Further cooling, below 117 °C, yields a metastable form of low-temperature
y-tridymite. The parameters of the elementary cell of low-temperature y-tridymite
are a0 = 1.842 nm, b0 = 0.502 nm, c0 = 2.578 nm, the density being 2260 kg m" 3 .
The refractive index, which depends significantly on structural arrangement and
defects, is np = 1.468-1.479, ng = 1.473-1.483.
The phase transformations of the basic tridymite modifications can therefore be
summarized as follows:
high-temperature α-tridymite „ medium-temperature

1 1 7 °C
/^-tridymite ^ low-temperature y-tridymite.
35
Table 3
Modifications of Si0 2 [14]
Modification Temperature Form Notes

range n - stable
(°c) m - metastable
Crystalline modifications of Si0 2
Low-temperature quartz - 2 7 3 to +573 s atm. pressure

High-temperature quartz 573 to 867 s atm. pressure
Tridymite S-I - 2 7 3 to +64 m atm. pressure

Tridymite S-II 64 to 117 m atm. pressure
Tridymite S-III 117 to 163 m atm. pressure
Tridymite S-IV 163 to 210 m atm. pressure
Tridymite S-V 210 to 475 m atm. pressure
Tridymite S-VI 475 to 867 m atm. pressure ,
867 to 1470 s atm. pressure
Tridymite M-I - 2 7 3 to +117 m atm. pressure

Tridymite M-II 117 to 163 m atm. pressure
Tridymite M-III above 163 m atm. pressure
Low-temperature cristobalite - 2 7 3 to +272 m atm. pressure

272 u» 1470 m atm. pressure
High-temperature cristobalite 1470 to 1723 s atm. pressure
Si0 2 —W (silica W| Monotropic form, chain structure at

atm. pressure, lightest modification of Si0 2
Coesite 300 to 1700 Negative thermal expansion, pressure
15to40 10 5 kPa
Stishovite 1200 to 1400 Rutile structure, the heaviest form of S i 0 2
Amorphous modifications of Si0 2
Liquid Si0 2 above 1723 s atm. pressure

Vitreous Si0 2 - 2 7 3 to 1723 m formed by rapid cooling
of liquid Si0 2
Supra-piezo-vitreous Si0 2 m
Compact vitreous Si0 2 m
Si0 2 —M (silica M) produced by the effect
of fast neutrons on SiO z
under atmospheric pressure
36
However, according to Sosman [14], further modifications of tridymite occur, as
shown in Table 3.
Whereas the transformations between tridymite, quartz and cristobalite are rela
tively slow, the temperature conversions of the low-temperature, medium-tempera
ture and high-temperature modifications are very fast. The conversions of quartz
modifications differing in their structure are called polymorphous transformations.
In contrast to the conversions occurring within the individual structural modifi
cations, the polymorphous conversions are characterized by transformation of the
crystalline structure.
Af
200 L
U- cristobalite
tridymite —-j
JA
/ I c quartz
.-*=t-teo-^ ■s
20 h *■
_«o~o-:*-4
_--o—o—o-
^ °S^ silica Fig. 15 — Thermal expansion
-200 200 400 600 800 1000 9 l a s s of the stable modifications
t CO of SiO,
37
It has been observed that, at a heat treatment temperature of 1350 °C and higher,
the conversion of quartz to cristobahte is nucleated by the presence of mineralizers;
the rate of the so-called cristobalitization depends on the grain size of the quartz, as
the process proceeds in the solid phase from the grain surface towards the interior.
The cristobahte to tridymite conversion proceeds simultaneously throughout the
grain volume, and the mineralizers weaken the Si—O bonds.
According to Blankenburg [2], there are differences, as illustrated in Fig. 15, in the
temperature dependence of thermal expansion of the individual Si0 2 modifications.
The lowest expansivity is exhibited by silica glass. A change in volume takes place
at 573 °C during the heating of low-temperature /?-quartz; similarly, changes in
volume occur at 200-250 °C when the high-temperature modification of a-cristo-
balite is cooled and converted to low-temperature jß-cristobalite.
Formation of the Si02 melt

According to the more recent findings described in Section 3.2, the phase conversion
of high-temperature α-quartz to an amorphous phase occurs already at 1400-1450 °C
(in the presence of alkalis); however, α-cristobalite, whose melting temperature is
1723 °C, is formed at the same time. The structure of the melt stable at temperatures
above 1723 °C does not show any great difference from the crystalline structure from
which it has formed by phase transformation. However, it is characterized by non-
uniform distribution of the [ S i 0 4 ] 4 ~ tetrahedra, showing various values of the
Si—O—Si bond angles from 120° to 180° and corresponding variations of the Si—O
interatomic distances.
In a melt of quartz, the relatively strong Si—O covalent bonds are responsible for
its high viscosity; the proportion of sp-hybrid bonds increases with increasing energy
of the system, and the angle of the Si—O—Si bond increases correspondingly (up
to 180°). The S i 0 2 melt represents a highly viscous liquid, close to the typical defect-
free Bernal liquid. According to Bernal [48, 49], this type of liquid is homogeneous,
coherent and assumed to contain essentially non-uniform groupings of molecules.
They are not assumed to contain any crystalline regions, nor cavities of sizes which
could accommodate another molecule.
A further characteristic of the liquid is that the non-uniformity of arrangement
is a result of a very low concentration of atoms showing a small deviation from the
normal coordination number. In this way the model considerably resembles the
structure of a crystal, and it may be assumed that the anions are mobile only in the
anionic region and the cations only in the cationic region of the structure. Below the
melting point of the crystal, this type of liquid is highly viscous, thus being easily
overcooled into an amorphous state.
At temperatures higher than 1723 °C, i.e. those at which the liquid phase of S i 0 2
has formed, a number of physico-chemical processes take place that are particularly
significant in the manufacture of silica glass. This subject was dealt with in detail
38
particularly by Shick [35], Toropov, Barzakovskii, Bondarev and Udalov [36, 37],
and surveyed by Pryanishnikov [8].
Shick [35] published the high-temperature thermodynamic data of liquid Si0 2
listed in Table 4.
Table 4
Thermodynamic data on Si0 2 at high temperatures [35]
TJO ΓΓΟ
Temperature TJO
n
T
TJO
-"2000 CP AH 298
nT — n2gs
(K) (Jmor1) ( J m o r 1 K"1) (Jmol" 1 )
(JmoP1)
2000 121 459 0 90.69 - 9 0 0 999

2500 166 802 45 343 90.69 - 8 8 9 498
3000 212 145 90 686 90.69 - 8 8 1 1.83
Vaporization of Si0 2 was dealt with by Bezborodov and Pryanishnikov [38], who
showed that in a neutral atmosphere the vaporization process proceeds according
to the equation
Si0 2(iJ) - SiO(g) + l/2 0 2(g) (9)
where s is the solid state,

1 is the liquid state,
g is the gaseous state.
Brewer and Mastick [39] determined the following gas pressures above an Si0 2
melt at various temperatures:
1840 K 0.411 Pa
1933 K 0.757 Pa
1951 K 0.711 Pa
Porter, Chupka and Ingram [40] measured the following gas pressures in a neutral
atmosphere above a cristobalite melt at 1800 K and 1900 K:
1800 K 1900 K
Si0 2 0.0016 Pa 0.0101 Pa
SiO 0.689 Pa 3.445 Pa
02 0.0053 Pa 0.0083 Pa
O - 0.0223 Pa
The heat of vaporization amounts to 569 · 103 + 33 · 103 J mol" 1 .
Brewer and Mastick [39] specified a value of 510· 103 J mol" 1 , Ruff and Kon-
schak [50] tfie value 481 · 103 J mol" 1 . For SiO, Bergman and Medvedev [41]
specify the value 360 · 103 J mol" V
39
Bergman and Medvedev [41] calculated the thermodynamic properties of liquid
and gaseous Si0 2 by the method published by Gercberg [51], on the assumption
that the Si0 2 molecule has a linear form with an interatomic distance of 0.1554 nm.
The results of the calculations are listed in Table 5.
Shick's calculation results [35] are listed in Table 6.
Table 5
Si0 2 / SiO 20
Temperature
(K) Hr — H0 ΦΤ HT — H 0
(JmoP1 K'1) (JmoP1) ( J m o l " 1 KP 1 ) (JmoP1)
2000 104.552 126 676 278.477 108 698

2400 117.318 174 548 288.499 133 333
2800 128.845 214 741 296.296 158 052
3000 304.719 182 838
Φτ is the potential of mechanical displacement (geochemical interpretation)
Table 6
# 0 — #0 IJO TJO
Temperature H° - tf0° S°
T n - ^298
(K) (Jmol^K-1) (Jmol^K-1) (Jmol" 1 ) (JmoP'K-1)
(JmoP1)
298 45.22 35.71 10 643 0 228.8
500 52.54 41.16 20 578 9 935
1000 59.03 48.82 48 818 38 175
1500 60.71 52.63 78 942 68 299
1800 54.01 97 217 86 575 328.9 j
1900 54.39 103 334 92 692 332.3
2000 61.42 54.68 109 359 98 716 335.2
2500 61.67 56.10 140 258 129 615 349.1
3000 61.92 57.02 171 073 160 430 359.9
Shick [35] further calculated the thermal effects of the reaction

SiO2(0 - SiO(g) + l/2 0 2(g) (10)
for temperatures of 2000 to 3000 K. The results are plotted in Fig. 16.
For reaction (10) he found the equation
AFT = -RT In k = -RT In îilÛ^M (H)
40
where AFT is the change in free energy (Helmholtz's function),
a is the activity (fugacity) of the gases,
k is the equilibrium constant of the reaction.
Table 7 lists the changes in free energy of reactions taking place between 1500
and 4000 K.
CO
o
τ—
CO
(D
GO
O
E
Fig. 16 - Changes in free energy of the reactions

1 - Si0 2 ( s ) - ► SiO(g) + l/20 2 ( g ) ;
2 - SiO 20) -^ SiO(g) + 1/20«,,;
3 - Si0 2(I) -^ Si0 2 ( g ,; 4 - i/2o 2 ( g ) - o»;
1400 2200 3000 3800 5 - Si0 2 ( s ) -* SiO(g) 6 - Si 2 0 2 ( g ) -i►2SiO(g,
- ΠΚ)
Table 7
Changes in free energy during heating of Si0 2 [35]
Reaction Temperature interval Δ7Γ°

(K) (Jmol - 1 )
Si0 2 ( s ) ■-* SiO(g) + i 0 2 ( g ) 1800-2000 756 973-243.29 7 1

Si0 2(1) -* SiO (l) + J O i t t ) 2000-4000 724 316-226.92 T
SiOM -> SiO(gl 1800-2000 324 603-146.12 7
δ
'2θ 2 «) -* 2SiO (g) 1500-3000 219 807-139.84 7 1
io*w
S
- o» 2000-4000 256 852-67.45 7 !
>0 2 ,|, -* S i 02, g , 2000-4000 532 561-150.72 7
Si«) + Olg) - Si0
<B> 1700-2950 - 1 6 3 084-42.58 7
SiO(8l - Si(g> + l 0 2 ( g l 3000 540 097-68.29 7
The values shown in Table 7 allow the equilibrium constant k to be calculated

and the partial pressure of the gaseous components to be determined for various
temperatures in a neutral atmosphere. The results are plotted in Fig. 17.
Above the surface of melted Si0 2 at temperatures of 2000 to 3000 K (i.e. in the
gaseous phase) one finds SiO, 0 2 , Si0 2 , O and Si 2 0 2 . The boiling temperature of
41
Si0 2 under a pressure of 1.01 · 105 Pa was determined by thermodynamic calculations
to be 3070 K, i.e. about 2800 °C. For the given temperature, the partial pressures
of the individual gases are as follows:
Psio 6.28 · 104 Pa
Po2 2.63 · 104 Pa
Po 7.49 · 103 Pa
Psi02 5.88-103 Pa
Psi2o2 1.01 · 101 Pa
Ptotal 1.01 · 105 Pa
in
o
CO
1Λ -
p
1.0 /
f
0.6 -
0.2
j ^
1 1700 1800 1900 2000
^ T (K)
Fig. 18 - Partial pressure of SiO and CO:
' ~ Pco'■>2 ~ Psio (f° r t n e reaction
l/2Si0 2 2 ( s ) + l/2Si(1) - S i O J
Fig. 17 - Partial pressures of the reaction

products of the decomposition of Si0 2 in
a neutral atmosphere: 1 — piotal; 2 — psio;
fioV 1 ) 3
- Po2',4 - p0\5 ~ Psio2;6 -Psu()2
Various technologies are used in the melting of silica glasses, so that in addition
to the neutral atmosphere, it is also necessary to consider the presence of H2, CO,
SiO, Si, C, W, Mo and others.
The reactions of Si0 2 with Si and C are the following:
SiO 2(s,l) 2 SiO(g) (12)

Si(s,l)
SiO 2(s,l) "(s) SiO(g) + co((g)
Figure 18 shows a plot of partial pressures of SiO and CO.
The effect of hydrogen and silicon on the reaction Si0 2 + H2 -+ SiO + H 2 0(a)
and Si0 2 + Si -► 2 SiO(b) is illustrated in Fig. 19, following Shick [35].
42
Table 8
Changes in free energy due to reaction of Si0 2 with various substances [52, 35]
Reaction Δ7° ( J m o l - 1 )
(1) SiO 20) + C(s) - SiO(g) + CO (g) 669 888-326.6 7

(2) SiO 20) + 3 C(s) -* SiC(s) + 2CO ( g ) 598 712-333.3 7
(3) Si0 2(S)1) + Si(1) -► 2SiO (g) 610 101-305.6 7
( 4 ) 2 S i 0 2 ( . t l ) + SiC w -► 3 SiO(g) + CO (g) 1434 816-711.8 7
(5) SiO 20) + CO (g) -> SiO(g) + C0 2 ( g ) 478 969-178.4 7
(6) SiO 20) + H 2(g) -► SiO(g) + H 2 0 ( g ) 510 789-20^.2 7
(7) Si0 2(1) + H 2(g) -► SiO(g) + H 2 0 ( g ) 510 789-205.2 7
(8) SiO 20) + i M o ( s ) -► SiO(g) + i M o 0 3 ( g ) 611273-130.3 7
(9) SiO 20) + i W w ~* sio (g) + iwo 3 ( g ) 644 767-234.5 7
(6) - a t p H , o = 1.01-10 5 Pa (7) — at pH2o = constant

10 2 r
m
o
-2
in
o P 10
0.06
CO
r-
O
σ 0.04 a
a.
* -R
0,02 h 10 6
10~8
1900 30 40 50 60
γ·10 5 (Κ" 1 )
Fig. 19 — Partial pressures of SiO during the Fig. 20 — Partial pressure of SiO, 0 2 , Si0 2
reactions of SiO, and N 2 during decomposition of Si0 2 in an
1 - Si0 2 ( s ) + H12 ( g ) - SiO(g) + H 2 0 ,(g)' oxidizing atmosphere (air), at
2 - Si0 2 ( s ) + Si, 2 SiO,, p= 1 . 0 1 1 0 5 P a : i - A o t a I ; 2 - ^ 2 ;
3
~ Ρο2Ί 4 - Po\ 5 ~ Psio2; 6 - Psio5
7 — #j i 0 (in neutral atmosphere)
The partial pressures of SiO, 0 2 , Si0 2 and N 2 during decomposition of Si0 2

in a medium of air under pressure of 1.01 · 105 Pa are plotted in Fig. 20, after Shick [35].
Geld and Esin [52] carried out approximate thermodynamic calculations whose
results are summarized in Table 8, together with the results obtained by Shick [35]
and others authors.
Geld and Esin [52] demonstrated that in vacuum melting, Si plays the major role
in terms of reducing capability, which is poorer for both C and SiC.
43
According to Borisov and Yudin [43], the reaction
SiO20) + 2SiC(s) -* 3 Si(1) + 2CO (g) (13)
proceeds from a temperature of 1950 K upwards, and together with reaction (5),
listed in Table 8, it takes place simultaneously in the temperature range 1950 to
2800 K. The rate of reaction (13) increases with increasing temperature, while that
of reaction (5) from Table 8 decreases. The respective rates are identical at 2120 K.
Figure 21 shows the results of measuring the vaporization of Si0 2 in contact with
carbon (C) and molybdenum (Mo), according to Pryanishnikov [8].
Noting the breadth of the subject matter concerned with the behaviour of Si0 2
melting at high temperatures, the reader is referred to the relevant literature [35, 36,
37, 39, 40, 41, 43, 50, 52].
Fig. 21 - Vaporization of Si0 2 in contact with C and Mo:

' 1300 1500 1700 1900 1 - in contact with C; 2 - in contact with Mo
m- t (°C)
2.2.2 Conditions for the formation of quartz

Quartz is among the most widely occurring rock-forming minerals. It com
prises 12% of the earth's crust and occurs in almost all petrographic types of rocks,
formed under all kinds of conditions.
The variety and richness of its types reflect the whole subject of the genesis of
minerals, which has never yet been completely explained in a number of respects.
A large amount of quartz is represented directly in rocks. During the magmatic
differentiation, quartz participated in the formation of pegmatite bodies and hydro-
thermal quartz veins. It is a common mineral of various types of ore veins. It may
be decomposed and transferred by alkaline solutions in the earth's crust, mostly
in the course of endogenous processes. In the hypergenetic zone, quartz does not
undergo any distinct changes, is highly resistant to weathering and constitutes the
main component of numerous sedimentary rocks. Under the conditions of regional
metamorphosis, quartz can undergo structural deformation and partial dissolution
by weakly alkaline solutions under favourable geochemical conditions. To a limited
degree, it is substituted by iron and manganese hydroxides.
44
For commercial utilization, particularly in glass manufacture, quartz accumu
lations of particular interest are the deposits of quartz crystals in rock interstices of
quartz veins and pegmatites, as well as quartz veins proper, which can be regarded
as single mineral rocks with a quartz content above 90 to 95%.
Vein quartz exhibits certain deviations in its composition, which correspond to
the conditions of its formation. A special case is the so-called Alpine type of quartz
veins, whose composition exhibits a distinct association with that of the ambient
metamorphic rocks. Soviet authors often distinguish ore-free quartz veins and ore-
bearing quartz veins. Both types show specific properties.
The ore-free quartz veins like Alpine quartz veins, are more distinctly related to the
composition of the ambient rocks. The ore-free veins are mostly smaller bodies in
metamorphic rocks. Alpine-type veins and ore-free quartz veins do not occur in
sediments or magmatic rocks free of any signs of metamorphosis [74]. Ore-free
quartz veins are generally deposited in agreement with the schistosity of the ambient
rocks, in contrast to the Alpine-type veins, which form typical true veins. The differ
ence in spatial orientation of ore-free quartz veins and the Alpine type affected the
rate of filling the vein structure with material, and also its tectonic stability. The
composition of Alpine veins is influenced significantly more by the composition of
the ambient rocks, and fissures frequently occur with a rich mineral occupation:
crystal, adular, rutile, epidote, titanite, chlorite and other materials.
Ore-free quartz veins do not contain such inclusions, and their vein paragenesis is
very poor compared to that of Alpine veins. Insofar as accessory minerals occur, they
are present only in minute amounts. It is interesting to note that even in ore-free
veins the most frequent minerals include for example rutile, chlorite and actinolite,
so that their compositions resemble Alpine-type veins. Some authors distinguish
additional types of quartz veins, such as crystal veins or piezoquartz veins.
In contrast to the types mentioned above, the ore-bearing veins are generally bound
to large tectonic structures and are of larger size, and the ambient rocks have usually
been subject to strong hydrothermal alteration. There is a substantial difference
between the mineral composition of the ore vein filling and the ambient rocks. The
vein quartz, constituting the filling of ore veins, likewise differs considerably from
ore-free vein quartz. The spatial orientations, as well as the relative ages, of ore-free
and ore veins occurring in the same region, usually also show a distinct divergence.
The following important features are used in the classification of quartz:
(a) its structural and textural characteristics;
(b) the properties determining the extent of milky white turbidity, caused by gas
and liquid inclusions;
(c) the paragenesis and formative conditions of the quartz vein.
The classification of quartz into a simple genetic diagram is not always simple,
as there is usually a tendency to classify quartz into groups according to regional
45
units, thus avoiding the genetic interpretation. Paragenetic or structural criteria are
used in some cases. The types distinguished are for example crystal vein quartz,
Alpine vein quartz and ore-free vein quartz, and the so-called granulated (recrystal-
lized) quartz that is described as a separate type.
The principal properties of vein quartz are as follows [74]:
(a) the size of the quartz grains;
(b) the structure of vein quartz — the character of the boundaries, their orientation,
the features of deformation and its type;
(c) the density and apparent density;
(d) the volume of the elementary lattice;
(e) the colour and degree of milky turbidity of the grains;
(f) the structural admixtures (Fe, AI, K, Na and others),
(g) the non-structural admixtures and inclusions, including solid and gas-liquid
inclusions, their amount, composition, shape and orientation.
In terms of specimen size, massive, columnar and drusy quartz is divided into
giant-grained (cross-sections over 100 mm), coarse-grained (20 to 100 mm), and
medium-grained (less than 20 mm). Granular quartz, which constitutes a separate
textural group, is usually divided intofiveclasses according to grain size; it is coarse
grained quartz (6-10 mm), medium-grained (3-6 mm), fine-grained (1-3 mm), very
fine-grained (0.2-1 mm) and micro-grained (up to 0.2 mm). Important formative fea
tures of quartz are the presence of crystal quartz or ore minerals, general paragenesis,
the composition of ambient rocks and the character of their alteration, the structural
features of the quartz vein (its direction, inclination, orientation in the tectonic
regional plan) and some additional characteristics.
Quartz occurrences are frequently divided into the two large groups of (a) pegma
tite and (b) hydrothermal quartzes.
To provide a better idea of the formation of quartz veins, Fig. 22 shows a schematic
diagram (after [75]).
granite magma
+
- silexites (admixtures of Au,As,Fe)
600'C
pegmatites pneumatolites
quartz quartz veins
veins ore veins
pneumatolites
AOO'C ■t
alpine veins postpegmati:ic ore veins
I )lutions (fi
solutions (filling hydrothermalites Fig. 22 — Schematic diagram
jf of cavities)
of the formation of quartz
zeolitic
veins veins (according to [75])
46
The diagram indicates that quartz veins, as a separate element of granitic magma,
may form in two ways. They are either a plain derivative of pegmatites, or split
directly from the magma. The quartz veins which arise as a direct separation from
pegmatites do not contain any ore minerals.
2.2.3 Rock crystal deposits

Rock crystal deposits belong to two basic types: pegmatitic veins, and
hydrothermal veins of the Alpine type. The pegmatite veins are usually more pro
ductive. Brazilian crystal is also of this type. In pegmatites, crystal occurs in para-
genesis with topaz, feldspars, beryl and other minerals.
Alpine quartz veins occur, in addition to their typical alpine region, particularly
in the polar region of the Urals.
Brazilian crystal, which is used in the manufacture of clear silica glass, usually
shows the following composition before refining [77]:
Si0 2 99.750 wt.%

A1203 0.024 wt.%
Fe 2 0 3 0.020 wt.%
Ti0 2 0.002 wt.%
CaO 0.013 wt.%
Na 2 0 0.005 wt.%
κ2ο 0.011 wt.%
Li 2 0 0.002 wt.%
calcinating loss 0.132 wt.%
2.2.4 Vein quartz deposits

As already mentioned, the main quartz deposits are divided into two genetic
types: pegmatite veins, and those of hydrothermal quartz. The pegmatite veins were
formed earlier, are of a high-temperature character and constitute a number of types,
according to various classifications. The hydrothermal veins were produced by
precipitation due to a hydrothermal process, are younger than pegmatites, and thus
represent a further stage of differentiation from the magma and usually exhibit
a significantly simpler composition of their mineral paragenesis, as compared to
pegmatites.
1. Endogenous deposits
(a) Pegmatite deposits are morphologically highly variable but relatively uniform
in terms of quality; they are divided into two subtypes, according to the texturally
paragenetic classification of pegmatites:
— pegmatite veins with a coarse block zone comprising feldspars and quartz;
the content of the latter in this zone is usually 20 to 30%;
47
— pegmatite veins with a quartz core; the quartz deposit is just that part of the
vein which consists of the block zone or the quartz core.
(b) Hydrothermal deposits are divided into two subtypes, according to the vein
shape:
— veins of plate shape, morphologically relatively stable, variable in terms of
quality;
— veins of lenticular shape, morphologically variable, relatively uniform in terms
of quality.
2. Exogenous deposits
These are alluvial deposits with quartz pebbles in the psephitic fraction; they are
morphologically uniform, and variable in terms of quality.
Experimental melting of various types of quartz raw materials has shown that
hydrothermal vein quartzes are of the greatest significance for the manufacture of
clear silica glass. Quartz from pegmatite deposits usually yields unclear silica glass,
or glasses with unsatisfactory physical properties. Quartz from alluvial sediments is
likewise an unsuitable raw material.
2.2.4.1 C o m m e r c i a l q u a r t z d e p o s i t s in C z e c h o s l o v a k i a
Owing to the lack of crystal raw material, the attention of Czechoslovak

geologists has been directed principally to hydrothermal quartz veins. A geological
survey carried out extensively in both republics was more successful in Slovakia.
It resulted in the discovery of deposits such as Grapa, Svedlär and Detkovice. Now
adays there is a satisfactory raw material base for the production of clear silica glass,
particularly for lighting purposes. Figure 23 shows the quartz deposits in Czecho
slovakia (adapted from [79]).
The Svedlär deposit

The Svedlär deposit of vein quartz is the largest deposit of this type in the Spis-
Gemer mountains. Like the Grapa deposits, the vein filling consists of coarse-grained
milky-white vein quartz. The intensity of milky turbidity in the Svedlär deposit is
still more pronounced and homogeneous. It is due primarily to two factors:
(a) high content of very fine gas-liquid inclusions,
(b) a very fine network of microfissures in the quartz substance.
According to [81], the quartz deposit consists of an irregular lenticular body at
the boundary between graphitic-seritic phyllites and porphyroids of the Gelnica
series. The deposit was formed along the tectonic line, of northwest-southeast direc
tion, passing perpendicular to the lines along which ore veins have developed. The
vein quartzes were formed in structures more recent than the hydrothermal miner-
48 .
alization of the Spis-Gemer mountains. Their formation was essentially monogenetic,
and the veins show signs of metamorphously hydrothermal origin with arichtopo-
mineral influence [81]. The occurrence of crystalline chlorite-ripidolite on the quartz
veins is a favourable feature. This chlorite was formed earlier than the basic quartz
mass, and was able to combine with some structural impurities, The Svedlar quartz
has the lowest content of structurally bound aluminium among all Czechoslovak
quartzes. After suitable treatment, the quartz thus provides one of the purest silica
raw materials for the melting of clear silica glass.
Fig. 23 — Quartz deposits in Czechoslovakia (adapted from [79]):

(a) Northern Moravia: 1 — Detkovice, 2 — Dolni Lipovä, 3 — Resov, 4 — Zeleny vrch at Rejviz,
5 — Velka Kras at Zulova, 6 — Vrbno under Praded;
(b) Bohemian-Moravian Highlands and the Sazava Region: 7 — Dolni Bory (pegmatite), 8 — V. Boranov,
9 — Puklice, 10 — Luka on Jihlava, / / — Plandry, 12 — Knez at Zruc on Sazava, 13 — Ostrov at
Ledec on Sazava, 14 — Hradiste at Znojmo;
(c) South and Central Bohemia: 15 — Stf y ·< wice (Kocici Hradek), 16 — Kunejov (Clunek) at Jindfichüv
Hradec, 17 — Mlyny at Tabor, 18 — quartz veins in moldanubik (Prachatiee — Balkan),
Vyrovcice I, II, Nebahovy I, II, Kbelnice, Pfedni Zborovice, Skalka, Jemnice, Friedholz, Svojsice,
Munice, 19 - quartz veins in Central-Bohemian Pluton - Petroviee, Kovafov, Milesov, Kvetov,
^tedronin, Dublovice, Pficovy, 20 — Krasovice-Radesin, 37 — Skalsko at Jilove:
(d) Western Bohemia: 21 — Tatrovice — Cernava, 22 — Sveteckä bora at Tachov, 23 — quartz veins
in the system of the West Bohemian quartz mound - Pavlikov, Cecin, Bela on Radbuza, Ujezd
sv. Krize, Kolovec, Brti- Rybniky, 24 - Javorna at Zelezna Ruda, 25 - Pobezovice region
(pegmatites);
(e) Northern Bohemia: 26 — Rumburk;
(/) Deposits in Veporides: 27 - Befius, 28 - Cierny Balog, 29 — Podkrivan, 30 - Budina I, II,
31 — Mytna, 32 — Grapa;
(g) Spis-Gemer Mountains: 33 — Svedlar, 34 — Smolnik, 35 — Starä Voda, 36 — Mnisek on Hnilec.
49
The deposit has been well surveyed and according to [81], is bound to a very
complex polygenous tectonic structure containing traces of several processes, dif
fering in terms of both time and character. The direction of the deposit structure
is 140°, and it simultaneously separates the porphyroids in the northeast part of the
deposit from the phyllites in its southern part. The deposit structure varies from
NNE
Fig. 24 — Cross-section through the Eastern part

of the Svedlär deposit: 1 — quartz; 2 — debris;
3 — graphitico-sericitic phyllites;
7 2 ^ EH m ^^ 4 — porphyroids; 5 — diggings and cross-cuts;

6 — tectonic effects
3 4 5 6
oblique to perpendicular to the course of the rock streaks and to the b axes in the
neighbourhood of Svedlär, and the course of the structure essentially corresponds
to the ac joint system (Fig. 24). A reverse-slip fault of northeast direction, developed
at the northwest ring of the anticline, along which the older series of strata was
lifted onto the porphyroids, is another significant tectonic element which has taken
an active part in the formation of the deposit. In terms of time, it is an older element,
probably from the Variscian orogenesis, from the period during which the Gelnica
series had formed, and which had additionally been made more distinct during the
period of Alpine orogenesis and preceded the formation of the ac jointing. The
intersecting of these two elementary structures, together with a suitable lithological
medium, provided suitable conditions for the formation of the quartz deposit. The
greatest thickness occurs at the point of fault intersection, which is responsible for
revealing the deposit directionally. The formation of vein quartz deposits can be
ranked, chronologically, behind the formation of ore vein deposits and behind the
formation of the Alpine cleavage, i.e. most probably in the most recent epoch of the
Upper Cretaceous [81]. However, the quartz deposits are older than the neanic
post-Paleogene tectonics which impair the quartz deposits. The quartz veins were
probably formed as a consequence of a separate mineralizing phase.
50
The mineralogical-genetic conditions of the quartz deposits in this region are
described in [85]. The individual quartz deposits in the Spis-Gemer mountains have
common basic features. They differ to some extent only in the presence and represen
tation of accompanying minerals. The main vein mineral is white quartz, representing
about 95% of the deposit capacity. The Svedlär deposit also contains more recent
transparent quartz. The other minerals present include subsidiary amounts of chlorite,
pistomezite, albite-oligoclase, sercite, muscovite and apatite, and the sulphides pyr-
rhotine, pyrite, chalcopyrite, sphalerite, galenite and schapbachite. The Svedlär
deposit further contains the hypergenous minerals limonite, lepidocrocite, chalcosine
and covellite. The individual minerals are described in detail in [85]. The vein quartz
in the Svedlär deposit shows distinct signs of cataclasis and recrystallization, and
the ambient minerals have undergone intensive hydrothermal alteration.
According to [85], all the vein quartz deposits in the Spis-Gemer mountains are
of hydrothermal origin and were formed in a separate (obviously the most recent)
stage of mineralization development. The formation and development of these
deposits took place in two substages: that of preore alteration, and that of the ore
mineralization process proper. The succession in the Svedlär deposit is as follows [85]:
chlorite -sericite -apatite -feldspars -muscovite -chlorite -py rrhotine -pyrite -pistomesite -
sphalerite-chalcopyrite-galenite-the main mass of 1st generation quartz and, finally,
in the second mineralizing stage, separation of clear quartz of the Ilnd generation.
On the basis of an extensive survey, the author [85] ranks the quartz veins in this
region among the group of piezoquartz deposits, stressing particularly the factors
of recrystallization and hydrothermal alteration of the ambient rocks.
These factors are typical also for the other vein quartz deposits in this region.
Figure 24 shows a cross-section through the eastern part of the Svedlär deposit
according to [80].
For the refining of quartz, it is important that the accompanying minerals present
and the concentrates of the ambient minerals be sharply segregated, to allow for ready
classification. Manual sorting of the raw material after extraction can thus be used
to remove most of the mineral impurities. During the refining (dressing) process, the
sulphidic ore and iron carbonates are converted to ferrous oxides, which are very
difficult to leach. Chemical analyses of dressed products show that dressing of the
Svedlär raw materials is capable of ensuring high quality charges for the melting of
clear silica glass. The greatest difficulties concern the attainment of a low content
of ferric impurities. The relatively high contents of alkali oxides are not detrimental,
as they are for the most part eliminated by volatilization during the melting processes
used in Czechoslovakia.
Tables 21 (pp.74 —77) list the data from chemical analyses of the individual com
ponents occurring in the Svedlär raw material.
A survey of the proved reserves of vein quartz, established by geological surveys
carried out in Slovakia in 1960 to 1968, is given in Table 9 (following [81]).
51
Table 9
Reserves of vein quartz in Slovakia [81 ]
Deposit Surveying Reserves of vein Notes

period quartz (Gg)
A B C , C2
Svedlar 1963-65 - - 124 10

Mnisek on Hnilec 1962-68 - - - 63 Stara Voda
Svedlar II
Zävadka
Mnisek on Hnilec
Helcmanovce
Mytna 1960-63 - - - 107
Mytna-Budinä II 1961-63 - - 36 5
Grapa 1963-64 - - 7 5 extracted
Veporides 1964-65 - - - 10
AGR-quartz 1968 - - - 39 Smolnik I, II, III
Stara Voda Π, III
Total - - 167 239
A - reserves explored so precisely that their mode of deposition, the deposit shape and structure, and
quality, distribution and technological properties of the raw materials are completely known;
B - reserves explored in such a way that the main properties of the mode of deposition, shape and
structure of the deposit body are known, and the mean types, natural and technological types
of the raw material and their distribution are known, except for their precise spatial delimitation,
etc.;
d - reserves explored in sufficient detail that the mode of deposition, shape and structure of deposit
bodies, the quality, type and technological properties, and the decisive conditions for processing,
etc., are roughly known;
C 2 - little explored reserves whose mode of deposition, form and structure of the deposit body, and raw
material quality have been determined on the basis of results of geological study and proved by
verification at individual points or in adjacent survey fields;
Gg - gigagrams
The Detkovice deposit

The vein quartz deposit at Detkovice was discovered and evaluated within the
framework of a geological survey of quartz raw materials in northern Moravia.
Quartz from the local quarry had been extracted earlier and utilized in the production
of ferrosilicium.
The deposit consists of several vein bodies [82] situated in a complex of pre-
Devonian epizonally altered rocks of proterozoic age. These rocks represent an
equivalent of the Zabfeh series. They constitute the bed of the Drahan highland
Paleozoic and outcrop in the underlying bed of the Devonian in the southern part
52
of the Konice-Mladec band. They are designated as Kladek phyllites (chloritico-
seritic phyllites with layers of metadiabases).
The quartz deposit proper has developed along a line of north-northeast-south-
southwest direction, more steeply inclined to the west. The vein structure can be
regarded as an easily traced continuous structurally controlled tectonic element
joining the individual lenticular quartz bodies. The proved length of the vein struc
ture is about 1500 m, and along this structure the individual lenticularly elongated
intermittent vein quartz bodies are localized. The length of the longest lenticules
does not exceed 150 m, with a maximum thickness of about 12 m. Alongside the
structure, between the quartz lenticules, there are quite empty zones 100 to 200 m in
length. In some places there are multiple quartz layers, the axes of a multiple layer
being up to 20 m apart. In contrast to most Slovakian deposits, no abrupt dying out
of quartz bodies occurs in depth. The development of the quartz veins is therefore
morphologically more uniform. This is reflected in the favourable exploiting con
ditions and the considerable reserves of the quartz raw materials. Within the frame
work of a geological survey, the deposit was verified by a drift run from the southern
part of the structure northwards. The quartz raw material from the drift as well as
from the surface part of the vein was successfully tested in the manufacture of silica
glass.
The surrounding rocks of the quartz veins are grey, greenish, green-grey, variable
silicate sericite (muscovite, epidote)-chloritic shales, often containing lenticles of
secretory quartz. They are usually partially weathered at the surface and altered
in the neighbourhood of the vein. The entire rock mass is faulted by a number of
dislocations with slicken sides, clay filling or crushed surrounding rocks. Alteration
zones also occur in some places.
From the mineralogical point of view, the veinfillingis compacted to well broken
milky white quartz. It contains larger grains surrounded by small grains, cemented
together with a fine-grained quartz substance. The quartz is badly damaged by
compression, cataclasted, and the quartz grains show undulating extinction and
ruptural deformations. The cracks often contain coatings and infillings of ferric
hydroxides. The vein filling is a single mineral. The main and, apart from the ferric
hydroxides, the only contamination component are shreds and coatings of sur
rounding rock particles, more numerous at the vein edges and in thinner layers. Even
the central parts of the vein rarely contain shreds of rocks. These impurities are
generally quite noticeable and readily eliminated by dressing. However, the higher
content of Ti0 2 in phyllites, connected with the presence of leucoxene, is awkward.
Even if dressing succeeds in eliminating most of the surrounding rock components
(leaching out of sericite and chlorite), the leucoxene remains almost intact in the
product of dressing.
The main problem of the dressing technology is therefore to reduce the leucoxene
content to the required level.
53
Results obtained so far have proved reserves of raw materials suitable for the
production of clear quartz glass in a number of deposit accumulations in the vein
structure, over a length of about 1500 m. The results of geological surveys imply that
the structure, with its occurrence of quartz lenticles, continues over a length of
several kilometres.
The quartz veins in the Detkovice deposit show a regular and uniform trend
development, and a regular morphology of the bodies. They are assumed to reach
to considerable depths. All the proved accumulations have a single mineral quartz
filling, free of sulphidic mineralization. The impurities, in the form of iron hydroxides
and particles and shreds of sericitic-chloritic shales, can readily be sorted. Tables 21
show the chemical analyses of the natural quartz raw material.
The Detkovice deposit is among the largest vein quartz deposits in Czechoslovakia.
Its geological survey has been concluded, even though the quartz reserves are larger
than those in the Svedlär deposit. At present the deposit is closed down, to be re
opened after the Svedlär deposit is exhausted.
2.2.4.2 O t h e r q u a r t z raw m a t e r i a l s
Most countries have so far used crystal quartz raw materials for the manu
facture of clear silica glass. With the gradual exhaustion of the original resources,
attention is now being paid to new crystal resources in Third World countries (e.g.
in the Malagasy Republic and Angola) and to other raw materials.
In spite of its sufficient stocks of crystals in the Urals, the Soviet Union makes
use of a very wide spectrum of raw materials. According to [86], discharge lamp tubes
have been manufactured since 1930 and laboratory silica glass ware since 1932.
Since the late 1950s, the granular vein quartz from the Soviet Kyshtym deposit has
been utilized for these purposes. The name covers a number of deposits in the central
Urals, where the stock amounts to about 1 million tons of quartz. The Kyshtym
quartz is also exported to Czechoslovakia. In addition to this type, use is currently
made of hydrothermal milk white quartz from the deposits at Aktas, Gora Chrustal-
naya and others.
Extra-pure silica glasses are made from either crystals or synthetic crystalline
quartzes (also from synthetic silicon compounds).
Very pure milk white quartzes occur in the Orehovo-Bitola region of Macedonia
and provide high-grade silica glass. The quartz veins also comprise large amounts
of muscovite, which necessitates a special process for dressing the quartz raw material.
New deposits of quartz raw materials have also been found in Bulgaria (Elenovo).
The quartz raw materials Sipur (Taunus) and Sipur (Portugal) are utilized by the
Schott Corporation in Mainz; they contain 25-11 ppm F e 2 0 3 [110] and are used
in the melting of special technical glasses.
54
2.2.5 Quartz sand
Quartz sand is a granular quartz raw material with a high Si0 2 content
which is used in the glass industry in the melting of most silicate glasses, and especially
in the melting of opaque silica glasses. Quartz sand is a natural raw material, which
is extracted and dressed.
Table 10
Minerals disseminated in sand [56]
Disseminated mineral Chemical formula Density (kg m 3)
Brown coal 1200-1500

Halloysite Al 2 [(OH) 4 Si 2 0 5 ]nH 2 0 2000-2200
Montmorrillonite Al 2 [(OH) 2 Si 4 O 10 ]nH 2 O 2500
Potash feldspar KAlSi 3 0 6 2530-2610
Kaolinite Al203.2Si02.2H20 2600
Nepheline Na 2 Al 2 Si 2 0 8 2600-2650
Albite Na(Si 3 A10 8 ) 2610
Anorthite Ca(Si 2 Al 2 0 8 ) 2770
Muscovite H2K(A1, Fe) 3 (Si0 4 ) 3 2780-2880
Biotite K(Mg,Fe) 3 [Si 3 AlO 1 0 ](OH,F) 2 2800-3200
Amphibol mixture of CaMg 2 (Si0 2 ) 3 and Mg 2 Al 4 Si 2 0 1 2 3000-3400
Turmaline complex borosilicate 3000-3250
Apatite (Ca 5 [P0 4 ] 3 )(F,Cl) 3160-3220
Zoisite Ca 2 Al 3 [OH(Si0 4 ) 3 ] 3250-3270
Olivine (Mg, Fe) 2 Si0 4 3270-4200
Epidote Ca 2 (Al,Fe) 3 (OH)Si 3 0 12 3300-3490
Pyroxene (Mg, AI, Fe, Ti)(Ca, Na) [(SiAl 2 )0 6 ] 3300-3600
Diaspor A1203.H20 3400
Staurolite HFeAl 5 Si 2 0 1 3 3400-3800
Topaz Al 2 Si0 4 (F, OH) 2 3500-3600
Pyrop Mg 3 Fe 2 (Si0 4 ) 3 3500
Disthene Al 2 SiO s 3510-3700
Spinel MgO.Al 2 0 3 3600
Corundum A1 2 0 3 3900-4100
Zircon ZrSi0 4 3900-4800
Almandine Fe 3 Al 2 (Si0 4 ) 3 4200
Rutile Ti02 4200-4300
Limonite Fe203.H20 4300-4500
Baryte BaS0 4 4500
Chromite FeO.Cr203 4500-4800
Ilmenite FeTi0 3 , FeO.Ti0 2 4600-4900
Pyrite FeS 2 5000-5200
Magnetite Fe304 5000-5200
55
If the raw material is loose (incoherent) it is called sand, and if the grains are bonded
together, they are called sandstones (the cementing material contains clay, carbonates
or ferric hydroxide) or quartzites (the cement is quartz) [3].
In addition to pure quartz grains, quartz sand usually contains variable amounts
of various disseminated foreign rocks, as listed in Table 10 (following Kotsmid [56]).
According to the content of these foreign substances, quartz sand can be divided
into four groups, namely:
— quartz sand (contains at least 98% Si0 2 after refining),
— clayey sand (contains more than 2% A1203 after refining),
— limy sand (mixed with calcium carbonate),
— ferric sand (usually mixed with glauconite or lava, or other eruptive rocks).
Quartz sand, whose composition (purity) and grain size distribution depends on
the geological formation of the deposit, is of the greatest significance for the glass
Table 11
Grain size fraction of sand for the manufacture of opaque silica glass
according to Czechoslovak Standard CSN 72 1202
Grain size fraction Content of the fraction

(mm) (%)
< o.ioo max. 5.0
0.100 to 0.315
0.315 to 0.500
0.500 to 0.630 min. 85.0
0.630 to 0.800
0.800 to 1.000 max. 10.0
1.000 to 1.250 max. 0.2
> 1.25 0
Table 12
Chemical composition of sand for the manufacture of opaque silica glass
according to Czechoslovak Standard CSN 72 1202
Component Chemical composition (%)
SiO z min. 99.2

Fe203 max. 0.020
Ti02 max. 0.10
AI203 max. 0.2
56
industry. High-grade quartz sands occur in Czechoslovakia in the Provodin, Strelec
and Adrspach regions. Quartz sands have to be refined before use.
The K 20 sand is used in Czechoslovakia for the manufacture of opaque silica glass;
its properties, according to the Czechoslovak Standard CSN 72 1202, are listed in
Tables 11 and 12.
In the USSR, glass quartz sands are extracted in the regions of Lyuberec
(0.02-0.2% Fe 2 0 3 ), Avdeyev (0.06% Fe 2 0 3 ), Novoselkovsk (0.04% Fe 2 0 3 ), Ludsk
(0.03% Fe 2 0 3 ), Papaznyansk (0.07% Fe 2 0 3 ), Charginsk (0.05% Fe 2 0 3 ), Saratov
(0.08% F e 2 0 3 ) and Tashlin (0.02% Fe 2 0 3 ).
In the German Democratic Republic, there are sites at Hohenbock (0.007-0.05%
F e 2 0 3 ) and Weferlinger (0.008^-0.012% Fe 2 0 3 ), in the Federal Republic of Germany
at Dörentrup (0.007% Fe 2 0 3 ), Frechen (0.015% Fe 2 0 3 ), Haltern (0.02-0.04% F e 2 0 3 )
and Ehiingen (0.02% F e 2 0 3 ) and in Poland in the Biela Gora region (0.06% F e 2 0 3 )
and at Kleszcowa (0.006-0.014% Fe 2 0 3 ).
In Belgium, glass quartz sands are taken at Moll (0.022% Fe 2 0 3 ), in Great Britain
in the Loch Aline region (0.012-0.02% F e 2 0 3 ) and at Reigate (0.027-0.034% Fe 2 0 3 ),
in France in the Fontainebleau area (0.005-0.012% F e 2 0 3 ) and at Pont-Saint-Esprit
(0.03-0.08% Fe 2 0 3 ), in Holland in the Heerlen region (0.007-0.03% Fe 2 0 3 ), in Spain
in the Gijon region (0.036% Fe 2 0 3 ), and in the USA in the Rockswood region
(0.019% F e 2 0 3 ) and elsewhere, e.g. Ottawa, Cheshire.
The subject is dealt with in detail in [2, 56, 110].
23 SYNTHETIC RAW MATERIALS
In recent years, high-purity clear silica glass has been manufactured from
synthetic silicon compounds. According to the manufacturing technology, particular
use is made of:
— gels of silicon compounds, whose dehydration and melting yield silica oxide
in an amorphous form,
— liquid SiCl4 and the gaseous compounds SiF 4 , SiH 4 , and others.
The preparation of clear silica glass from synthetic raw materials (cf. Chapter 3)
is particularly advantageous because it allows high purity to be attained and doping
additions to be introduced for special purposes, while at the same time substituting
for natural raw materials which are in short supply (rock crystal).
The preparation of high-purity silica glasses from synthetic raw materials was
surveyed by Gossink [57].
57
2.3.1 Raw materials for the sol-gel method of silica glass production
Esters of some inorganic acids such as ethyl silicate, dissolved in suitable

solvents (e.g. alcohol), can be converted to gel by hydrolysis. The preparation consists,
for example, of hydrolyzing orthosilicic acid tetraethyl ester according to the re
action [62]
(C 2 H 5 0) 4 Si + 4 H 2 0 -> H 4 S i 0 4 + 4 C 2 H 5 O H (14)
To improve the stability of the solution, the hydrolysis is carried out in alcohol.
Dehydration of the H 4 S i 0 4 gel (by firing) and subsequent melting produce silica
in an amorphous form.
An H 2 S i 0 3 gel can be prepared by means of cation-exchanging high-molecular
resin RH (R~COOH—S0 3 H), i.e. by using this cation exchanger to separate N a +
ions from sodium metasilicate solution according to the reaction
2RH + Na2Si03 -> 2 RNa + H 2 S i 0 3

TT n.^ dehydration ^-x-x T T ^ / A J-\
H2Si03 ~ ► Si0 2 + H 2 0 (15)
The latter procedure has the disadvantage of low yields, ageing of the sol, the presence
of small quantities of N a + ions and the required working temperature of 0 °C.
The gel technique can likewise be utilized in the hydrolysis of silicon alkoxide
(SiXnH4_„), which proceeds as follows, according to [64]:
Si(OR)4 + H 2 0 -► (RO) 3 SiOH + ROH

(RO) 3 SiOH + M(OR')„ -► (RO) 3 Si—O—M(OR);_! + R—OH
where M is, for example, Ti 4 + . '
Another method is based on the introduction of gaseous SiCl4 into deionized
water. Si(OH)4 gel is obtained according to the reaction
dehydration
:
SiCl 4 + 4 H 2 0 - * Si(OH)4 + 4 HC1 *"
-»- S i 0 2 + 2 H 2 0 + 4HC1 (17)
Use can likewise be made of heavy water, D 2 0 , so that according to equation

dehydratio
SiCl4 + 4 D 2 0 - 4DC1 + Si(OD)4 %
-* Si02 + 2 D 2 0 + 4DC1, (18)
one obtains silica.

There are further ways to produce silica gel, sometimes as a commercially manu
factured raw material, sometimes as a by-product. Production of high-purity clear
silica glass requires the use of a high-purity initial raw material.
58
According to Gazo [6], physico-chemical methods applied to the study of colloidal
systems have provided certain explanations of the nature of the so-called hydrated
oxides, i.e. gelatinous precipitates obtained from aqueous solutions in the form of
oxides or hydroxides. The gel of Si0 2 is a typical example of these hydrated oxides.
The freshly prepared gel is a suspension of such fineness that X-ray examinations
show it as an amorphous substance. Because its great surface area retains water by
adsorption, and perhaps also partially by capillary forces, it is possible to determine
in individual instances only whether chemically bound water is also present.
Gel of Si0 2 is subject to so-called ageing, which results in the formation of a precipi
tate of a crystalline nature. The atoms can also be observed to rearrange themselves
into an oxidic network. As it is impossible to establish in the amorphous state whether
the gels are present in the form of oxides or hydroxides, they are generally called
hydrated oxides.
2.3.2 Raw materials for the production of silica glass by thermal decomposition
of silicon compounds
Very high purity silica glasses (e.g. those for applications in optics or fibre
optics) are prepared by gaseous phase reactions using plasma oxidation of high-purity
liquid SiCl4 or of the gaseous silanes SiH4 and SiF4. These raw materials are either
prepared synthetically for this purpose or are obtained as by-products from other
processes.
The reactions involved are as follows:
SiCl4 + 0 2 -► Si0 2 + 2C12 (19)
SiH4 + 2 0 2 -> Si0 2 + 2 H 2 0
High purity silica glass can also be prepared by hydrolysis in theflameof an oxygen-
hydrogen burner, according to the reaction
SiCl4 + 2 H 2 0 -► Si0 2 + 4HC1 (20)
According to Remy [73] and Gazo [6], the initial raw material, silicic chloride
SiCl4, is manufactured by heating silica or a silica-coal mixture in a stream of chlorine
according to the reaction equation
Si0 2 + 2C + 2C12 — SiCl4 + 2 CO (21)
SiCl4 is a colourless liquid with a density of 1490 kg m - 3 , fuming in air.
Silicicfluoride,SiF4, can be manufactured by heating a mixture of apatite, silica
and concentrated sulphuric acid according to the reaction equation
CaF2 + H 2 S0 4 — CaS0 4 + 2 HF (22)
Si0 2 + 4HF -» SiF4 + 2 H 2 Q
59
In pure form, it can be obtained by heating barium fluorosilicate, which decomposes
according to the equation
BaSiF 6 -► BaF 2 + SiF 4 (23)
Silicic fluoride is a colourless gas that can be liquefied under pressure.

Monositane, SiH 4 , can be prepared by a reaction of HC1 with Mg 2 Si. The resulting
mixture of silanes can be separated by fractional distillation under reduced pressure.
The reaction
SiCl4 + LiAlH 4 -► SiH 4 + LiCl + A1C13 (24)
produces SiH 4 as a colourless gas which is stable in the absence of air.
Table 13 lists some properties of synthetic silicon compounds.
Table 13
The properties of synthetic silicon compounds
Property SiH 4 SiF 4 SiCl4
State gaseous gaseous liquid

Melting temperature (°C) -184.7 -70
Boiling temperature (°C) -112 sublimes + 57.5
Heat of combination (J mol~ l ) 1507.2- 103 644.8 · 103
2.4 METHODS FOR EVALUATION OF NATURAL QUARTZ

RAW MATERIALS
The decisive factors for the utilization of quartz are its physico-chemical
properties, which together determine the quality of the melted silica glass. The
effects of the individual properties of the quartz on the quality of the resulting silica
glass have so far not been thoroughly established. The suitability of quartz for the
manufacture of silica glass is therefore decided according to refining tests carried
out on promising quartz deposits, and particularly according to the results of exper
imental melting. The minimum quality of the final product of classification required
for the melting of clear silica glass from Czechoslovak raw materials is listed in
Table 14.
The grain size distribution of quartz raw material (for the technology pursued
according to the licence by Quartz and Silice at the Novy Bor Works of Sklotas,
Concern Corporation) is shown in Table 15.
The grain size distribution curve is shown in Fig. 25.
60
Table 14
Allowable concentration of impurities in Czechoslovak refined quartz
Component Maximum concentration (%)
Fe203 0.0007
TiO, 0.0005
A1 2 0 3 0.0056
CaO 0.0020
Na20 0.0053
κ2ο 0.0014
Li20 0.0006
MgO 0.0005
H70 0.6
100 Γ
— — "·
//?
///
w
/'/
£ 50 f-
m
1
1
\
Γ ·'/ / /
1 ^ ,
/ / /
J
Fig. 25 — Grain size distribution of dressed
10 Ü30 025 Q125 0B8 quartzes
Table 15
Grain size composition of Czechoslovak refined quartz raw material
Grain size fraction Lower limit of Upper limit of

K 1111« \ erain size fraction range grain size fraction range
(%) (%)
+0.50 1 3
+0.40 5 12
+0.315 14 31
+0.25 35 55
+0.20 58 73
+0.15 76 86
+0.125 84 93
+0.08 96 99
61
The qualitative requirements that exist in Czechoslovakia are essentially com
parable to the requirements for the quality of quartz in other countries. Table 16
compares the qualitative requirements for refined raw materials in Czechoslovakia,
the German Democratic Republic and the USSR.
Table 16
Comparison of qualitative requirements for refined quartz raw material
Component Maximum allowable content (%)
Czechoslovak Vein quartz Vein quartz Vein quartz

vein quartz GDR GNIIKS USSR
Leningrad
1
Ti02 0.0005 0.0003 0.0010 0.0007
A1 2 0 3 0.0056 0.0100 0.0200 0.0070
Fe203 0.0007 0.0010 0.0100 0.0030
CaO 0.0020 0.0100 0.0010 0.0008
MgO 0.0005 0.0020 0.0005 0.0008
Na20 0.0053 0.0015 not specified not specified
κ2ο 0.0014 0.0010 not specified not specified
The differences in the requirements are partly attributable to variations in the

melting technologies; the stricter demands on the content of alkali oxides in the GDR
are due to the difference in technology compared to that used in Czechoslovakia.
The extensive occurrence of quartz in the lithosphere has directly stimulated
a number of significant geochemical, physico-chemical and mineralogical research
programmes. The structure of quartz was found to depend on tectonic effects, and
precise measuring of some properties (orientation of grains, plastic and ruptural
deformations, the presence of inclusions and their composition) even allow the
general geological conditions of development to be assessed for entire regions.
Quartz raw materials are evaluated by quantitative methods in the dressed state,
and laboratory melting has still retained its significance. In suitably adjusting the
parameters (technology) of melting, it is possible to influence, to a certain degree,
the required properties of quartz and to obtain clear silica glass even from quartz
raw materials which would provide opaque silica glass with the use of other tech
nologies.
In assessing the properties of quartz, physical methods (such as the determination
of density, transmittance, dispersion of light, decrepitation) are combined with
chemical (analytical) methods such as the determination of structural and non-
structural admixtures and the composition of gaseous-liquid inclusions, and with
mineralogical methods (microscopy, separation of heavy minerals).
62
2.4.1 Density characteristics
Determination of the density characteristics is a very appropriate physical

method used in the testing of quartz. The density of a mineral, measured with adequate
accuracy, provides a good picture of both the micro- and macro-defects in its struc
ture. Study of the Ural quartzes [74] showed that their density could be regarded
as constant, to the level o f ± l - 1 0 _ 1 k g m " 3 . The density of quartz under normal
pressure (0.1013 MPa) was established to show the following changes with tem
perature:
temperature (°C) 15 20 25 30
-3
density (kg m ) 2651.4 2650.9 2650.4 2649.9
Precise determination of density is very difficult, due especially to the demanding
preparation and selection of defect-free grains. On the other hand, to determine
differences between quartz raw materials it is necessary to find these defects in the
540
300
Fig. 26 - Flotation tube Fig. 27 — Gradient tube
63
quartz grains and express them quantitatively. This purpose is best served by deter
mination of the apparent density of individual quartz grains, followed by statistical
processing of the measurement results. The structural macro-defects (fracturing,
presence of admixtures) can be studied microscopically, after separation of quartz
grains into several classes according to their apparent density. This process is facili
tated by the grain separation method using a gradient tube described by Kostyleva
[97]. The distribution curves expressing the apparent densities of various types of
quartz can be obtained from visual observation of quartz grain separation in the
gradient tube immersion liquid (bromoform and ethyl alcohol). The required density
gradient can be obtained by changing the temperature of the bottom end of the
gradient tube, so that the quartz grains in the liquid will take up positions corre
sponding to their apparent densities. The individual density levels are determined by
means of calibrated glass standards whose apparent density can be measured by the
so-called flotation method [87]. Changes in the concentration of micro-cracks,
admixtures and inclusions are revealed by changes in apparent density of the order
of 0 to 10 kg m" 3 , most frequently up to 10-20 kg m" 3 .
To determine changes, it is necessary to use a method having a sensitivity higher
by at least one order of magnitude. This requirement is met by the gradient tube
method. The standards employed are small glass beads with fused-in platinum wires,
the size of the wire determining the apparent density of the standard. The standards
are calibrated by the flotation method, which is based on determining the speed of
ascent and descent of the grain (standard) in a liquid of similar density, in terms of
changes in the density of this liquid. Figure 26 shows a diagram of the flotation tube
and Figure 27 one of the gradient tube. The method utilizes the fact that the coef
ficient of thermal expansion of liquids is substantially higher than that of solids.
To change the density of a bromoform-ethyl alcohol mixture by 25 kg m~3, its tem
perature has to be raised from 15 to 25 °C; over the temperature range, the density
of quartz will change by only 1 kg m~3. If one knows the so-called grain flotation
temperature, i.e. that at which the grain density is identical with that of the liquid
and the speed of the grain in the liquid is zero, the apparent density of the grain can
be determined with an accuracy of ± 1 kg m - 3 .
The flotation tube (cf. Fig. 26) is an adapted glass cuvettefilledwith a heavy liquid
which is heated by water recycled from a thermostat (passing through the cuvette
jacket). The cuvette wall is provided with two index lines 100 mm apart, between
which the speed of the grain ascent and descent is measured. Let us describe the
apparent density determination for one grain of quartz as an example. The grain is
introduced into a liquid having a density of 2642 kg m" 3 at 20 °C. On increasing the
water temperature in the thermostat, the density of the bromoform-ethyl alcohol
mixture will decrease, and the grain begins to descend. As soon as the grain passes
the upper index line, the temperature t1 of the water is recorded and the time t{1)
of passage of the grain between the index lines is measured. When the grain passes
64
the lower index line, the temperature t2 is recorded and the thermostat is switched
over to cooling. Similarly, the temperatures t\ and t'2 are obtained during the grain
ascent, and the time i(2) of grain passage between the index lines is again measured.
From the values obtained, temperature t = (tl + t2)j2 and the speed of grain descent
— v (mm s"1), and temperature t' = (t[ + r'2)/2 and the speed of grain ascent +v
(mm s"1) are calculated. The measurements are repeated three times and the results
plotted to show the temperature dependence of the speed of the grain in the immersion
liquid, as in Fig. 28.
Fig. 28 — Determining the flotation

temperature tF by the flotation
method
The intersection of the line connecting the two speeds (during grain ascent and
descent) with the temperature ordinate will determine the flotation temperature
(v = 0). For the given case, the mean flotation temperature iF = 21.07 ± 0.65 °C,
which corresponds to a mean apparent grain density ρ = 2639.0 ± 1.5 kg m~3. This
value is read off the diagram shown in Fig. 29.
- ^ 2.74%
M'C)
Fig. 29 — The temperature dependence of the density of the bromoform-ethyl alcohol mixture
(the percentages indicate the ethyl alcohol content of the mixture)
65
Table 17
Apparent densities of quartz from various localities in Czechoslovakia
Locality Calculated Grain size distribution (%) in he Appearance

apparent apparent density class of melted ingot
density
(kgrO 2636 2639 2642 2645 2648
to to to to to
2639 2642 2645 2648 2651
Mnisek 2639.7 36 59 5 clear

Starä Voda 2640.3 12 86 2 clear
Zävadka 2640.1 22 76 2 clear
Svedlar 2640.7 5 80 15 clear
Smolnik 2639.7 37 55 8 clear
Stofova dol. 2640.4 12 80 8 clear
Budina I 2640.9 3 72 25 clear
Budina I 2640.9 13 57 30 clear
Grapa 2643.8 17 56 27 clear
Mytna 2643.8 3 20 41 36 opaque
Podkrivan 2645.1 10 46 24 20 clear
tierny Balog 2646.8 10 18 33 39 clear
Detv. Huta 2645.7 2 3 27 59 9 opaque
Budinä II 2643.6 18 62 20 opaque
Budina II 2645.5 6 39 39 16 opaque
Cerveny Vrch 2644.5 3 57 40 clear
Fucna 2645.7 38 52 10 opaque
Dolni Bory 2646.1 1 28 56 15 opaque
Skalsko 2646.8 10 16 40 34 opaque
Velka Kras 2646.4 3 31 34 32 opaque
Velkä Kras 2648.5 5 28 67 opaque
61 26 opaque
Benus
Javorna
2643.8
2644.0
13
14
1 57 29 opaque 1
Krasovice 2642.9 3 32 48 16 1 opaque
Krasovice 2644.2 2 28 27 33 10 opaque
Tatrovice 2643.8 16 57 27 opaque
Novy Pafezov 2643.6 10 70 20 opaque
Revuca 2645.0 2 5 42 39 12 opaque
Brazilian crystal 2649.5 100 clear
Magadaskar quartz 2649.4 6 94 clear
Chocovice 2648.8 1 15 84 clear
Detkovice 2642.9 35 50 15 clear
Englovy domky 2641.2 11 49 26 10 1 clear
Zeleny vrch 2648.5 3 31 66 opaque
Dolni Lipovä 2643.1 1 32 47 20 opaque
Helsmanovce 2641.0 3 71 20 6 opaque
Ovcinec 2640.7 15 51 17 10 1 opaque
Hradiste 2645.7 7 34 40 19 opaque
Modry Kamen 2642.0 15 30 33 17 opaque
Tachov 2645.0 3 6 42 29 20 opaque
Slovinky 2646.1 1 20 79 opaque
Moravskä Tfebovä 2646.6 2 90 8 opaque
Resov 2646.8 11 84 5 opaque
Bily Kamen 2649.5 1 99 opaque
In the Ovcinec quartz, 6% of grains are present in the class below 2636 (kg m 3) and the same for 3%
grains in the Englovy domky quartz and 5% of grains in the Mokry Kamen quartz.
The results of apparent density measurements on quartz from various Czecho
slovak deposits are summarized in Table 17.
As has already been mentioned, the apparent density value depends on the degree
of compressive damage of the quartz (the number and location of microcracks),
and on the quantity of gas and liquid inclusions. Both factors cause the apparent
density values to decrease. Values above 2651 kg m" 3 could be due to inclusions of
heavy minerals in the quartz grains, but in fact such inclusions are very rare in single
mineral quartz veins. The value of the mean apparent density is macroscopically
reflected quite well by the intensity of the milk-white turbidity:
(a) quartzes with apparent density close to 2640 kg m" 3 have homogeneous milk-
white turbidity;
Table 18
Porosity of quartz from various localities in Czechoslovakia
Locality Porosity (%)
before refining after refining
Mnisek 0.43 0.68

Smolnik 0.43 0.77
Stara Voda 0.41 0.52
Zavadka 0.41 0.56
Hummel 0.40 0.54
Detkovice 0.40 0.75
Rejviz 0.39 0.61
Svedlär 0.39 0.61
Helcmanovce 0.38 more than 2
Detkovice 0.31 0.37
Dolni Lipovä 0.30 0.31
Budinä I 0.30 0.31
Grapa 0.27 0.28
Budinä II 0.25 0.35
terveny Vrch 0.25 0.29
Krasovice 0.23 0.25
Javornä 0.20 0.26
Hradiste 0.20 0.23
Dolni Bory 0.19 0.20
Cierny Balog 0.17 0.23
Moravska Tfebova 0.17 0.17
Skalsko 0.16 0.24
Resov 0.16 0.27
Velka Kras 0.11 0.13
Zeleny Vrch 0.09 0.17
Brazilian crystal 0.00 0.00
67
(b) quartzes with apparent density close to 2644 kg m " 3 are grey-white, with
a mildly variable intensity of milky turbidity; a lower homogeneity will also affect
the distribution of grains according to their apparent density;
(c) quartzes with apparent density close to 2648 kg m~ 3 and higher, e.g. crystal
raw materials, pegmatite quartzes and some secretion and ore quartzes, are usually
grey or of "water" colour, translucent to clear (e.g. Brazilian crystal).
In the manufacture of clear silica glass, the quartz raw materials are heat treated
(calcined) before the actual dressing (refining). For a calcination temperature of
800 °C and calcination time of 4 h, the density characteristics were determined and
the porosity values calculated from the values of mean apparent densities, using the
equation
4, = ( l - £ ) - 1 0 0 (25)
where Av is the porosity of quartz in %,

ρ is the density of quartz, 2651 kg m" 3 ,
σ is the apparent density of quartz (kg m" 3 ).
The results are listed in Table 18.
2.4.2 Quartz-cristobalite phase conversion
The conversion of quartz to cristobalite by heating is accelerated by the

presence of further components acting as mineralizers, and by structural defects in
the quartz. The effects of mineralizers are described in greater detail in Section 3.2.1.
Mention will therefore only be made here of the effect of structural defects, such as
plastic compressive deformations (revealed under the microscope by undulating
extinction) or fine ruptural deformations of individual quartz crystals, and the
presence of gaseous-liquid inclusions.
Microjointing is particularly common. The effect of compressive deformations
already appears in the course of heat treatment of quartz. Whereas crystal quartz
free of structural defects is virtually unaffected by heating at 600 to 800 °C and sub
sequent slow cooling, compressively deformed quartz tends to decrepitate in the
course of heating, and turns strongly white due to the formation of a dense lattice
of microfissures resulting from equalization of internal stress. The completeness and
rate of conversion then depend on the degree of compressive deformation. The con
versions of quartz to cristobalite and the amorphous phase can be studied by radio
graphy. The mineralogical character of just-fused quartz was found to differ with
quartzes from individual deposits, the differences being associated with the clarity
of the final silica glass, as shown in Table 19.
68
Table 19
Concentration of quartz, cristobalite and glassy phase during the melting of quartz
Concentration (%)
Locality
quartz cristobalite glassy phase
clear melt
Grapa 3.5 96.0 0.5
Budinä I 1.3 98.5 0.2
Svedlär 2.0 98.0
Zävadka 3.0 96.5 0.5
Mnisek 3.5 96.5
Mnisek 0.5 99.5
Starä Voda 0.5 99.5
Cierny Balog 3.0 96.0 1.0
Smolnik 4.0 78.0 18.0
Hummel 3.5 95.5 1.0
Hradiste 3.5 94.5 2.0
opaque melt
Budinä II 13.0 73.0 14.0
Mytna 3.0 90.5 6.5
Helcmanovce 0.5 99.5
Helcmanovce 1.0 97.0 2.0
Revuca 5.0 95.0
Resov 3.5 96.0 0.5
Detkovice 2.7 92.0 5.3
Benus 3.3 73.0 23.7
Zabica 18.5 60.5 21.0
Skalsko 76.5 4.5 19.0
Javornä 46.5 26.0 27.5
Dolni Lipovä 4.5 19.5 76.0
Rejviz 33.0 38.5 28.5
Vrbno 23.0 62.5 14.5
Velky Luh 18.0 76.5 5.5
Moravskä Trebovä 20.0 73.5 6.5
Dolni Bory 30.0 65.0 5.0
Velkä Kras 33.0 64.0 3.0
Vrbno 40.0 58.0 2.0
Krasovice 64.0 34.0 2.0
2.4.3 Chemical analysis

The continously increasing demands on the amount and quality of silica
glass brought more exacting requirements for the speed of analytical checking of
natural quartz as the starting raw material and of silica glass as the final product.
69
The systematic development of analytical procedures carried out at the State Glass
Research Institute in Hradec Krälove since 1960 has recently led to the introduction
of instrumental methods, particularly atomic absorption and emission spectrometry
(AAS, AES), optical emission spectrometry with a plasma excitation course (CMP),
and photometry.
Preparation of samples for analysis and their decomposition
A ground sample of quartz or silica glass is decomposed with hydrofluoric and

perchloric acid, in a special device made of Teflon. The device (Fig. 30) consists of
a decomposition vessel with a convex bottom and a double lid. The bottom part
of the double lid, provided with four openings connecting the inner space with the
outer environment, is inserted in the conically expanding part of the decomposition
vessel. On the upper surface of the lid is seated its second part, whose edges overlap
the level in the bottom lid; it is provided with four segments on its circumference.
By turning a part of the lid these segments seal the openings in the bottom lid, thus
closing the decomposition device.
Fig. 30 — Decomposition vessel
The sample to be analysed is placed in the decomposition vessel, the decomposing

agent is added and the decomposition vessel is fitted with the double lid. The device
is placed on an electrically heated plate with a controlled input, whose temperature
is gradually raised until the vapours of the decomposition agent or decomposition
products begin to develop. As soon as the gases have ceased to be generated, the
decomposition device is closed, removed from the heating plate and allowed to cool
down. The content of the decomposition device is then quantitatively transferred
into a measuring flask. The design of the decomposition device allows samples with
weights of the order of tens of gram to be decomposed without risk of contamination
during the process. The volatile products of decomposition, such as silicic fluoride
70
or the vapours of the decomposition agents, escape from the decomposition device,
simultaneously performing the following two functions:
— they prevent dust particles from the environment entering the device,
— in the course of the decomposition, the reaction products are removed from
the decomposition device, thus disturbing the reaction equilibrium and speeding up
the decomposition.
The weight of the sample used in the analysis is significant for the subsequent course
of analyses of both natural and synthetic compounds of silicon and of silica glass.
The sample weight is selected for the analytical procedure as follows:
— samples of higher weight require larger amounts of the decomposition agent,
in line with the probability of obtaining higher values of the blank test and longer
times of decomposition;
— the sample weight should be chosen with respect to the limits of determination
of the given element and the instrumentation employed.
On the basis of experimental experience in the analyses of natural quartzes and
silica glasses, the sample weight is usually chosen in the range 10 to 30 g. Two samples
are usually decomposed under identical conditions, the decomposition period being
20 to 35 hours and the consumption of hydrofluoric acid 40 to 120 ml.
Determination of the individual components
Determination of Na20, K20 and Li20. These components are determined by
means of atomic emission spectrometry in an acetylene-air flame, or by optical
emission plasma spectrometry. To suppress the chemical and physical effects in both
cases, use is made of Schink-Schuhknecht's buffer based on alumina and caesium
chloride.
Determination of CaO, MgO, SrO and BaO. Use is again made of atomic absorption
and emission spectrometry, this time in an N20-acetylene flame, screened by nitrogen,
in the presence of a buffer based on K 2 0 or oxides of La, Li, Cs or La, Li, Cs and
di-Na-ethylenediaminetetraacetic acid (EDTA) at pH 5.1 to 5.3.
With emission plasma spectrometry, spectral buffers based on the oxides of La,
Li, Cs or La, Li, Cs and EDTA are also used. To determine a concentration level of
strontium oxide and barium oxide lower than 0.5 μg ml" *, it is best to use the AES
method in an acetylene-N20 flame in the presence of a buffer based on potassium
oxide.
Determination of Al203. Alumina is determined by atomic emission spectrometry
in the N20-acetylene flame in the presence of a buffer based on La, Li, Cs or La, Li,
Cs and EDTA. In this case, A1203 concentrations of about 1 μg ml" 1 can be de
termined.
Considerably lower concentration levels (by one order of magnitude) can be
measured by the use of emission plasma spectrometry in the presence of a spectral
buffer based on La, Li, Cs or La, Li, Cs and EDTA.
71
The spectrophotometric determination of A1 2 0 3 is based on the formation of
a coloured colloid of alumina with chromazurol S in an acetate-buffered medium
at pH 5.5-6.0. The addition of polyvinyl alcohol stabilizes the colloid. The interfering
ferric ions are reduced, by an addition of ascorbic acid, to ferrous ions which do not
interfere with the determination. Further interference is caused particularly by
fluorides, which have to be eliminated by repeated heating to dryness with perchloric
acid after the sample has been decomposed with hydrofluoric acid.
Determination of Fe203. This is carried out by atomic absorption spectrometry
in the air-acetylene flame. However, difficulties arise in practice due to background
instability at concentration levels lower than 0.5 μg m l - 1 . It is therefore advisable
to use emission plasma spectrometry, which allows concentration levels of 0.1 μg ml" *
and lower to be measured in the solutions being analysed.
The AAS and CMP methods are suitably supplemented with the sensitive and
selective determination of F e 2 0 3 using beta-phenanthroline in an acetate-buffered
medium of pH 4.0 to 6.0. The measurement sensitivity can be substantially increased
by extracting the coloured complex compound into chloroform or n-hexanol.
Determination of Ti02. Application of the AAS method using the N 2 0-acetylene
flame is restricted by its low sensitivity.
The use of emission plasma spectrometry, capable of determining T i 0 2 in amounts
of the order of 0.1 μg m l - 1 in the sample, has proved very successful.
The spectrophotometric determination of T i 0 2 is based on its coloured reaction
with chromotropic acid in a formate buffer medium at pH 3.5, producing a coloured
chelate whose absorption is measured at 470 nm. The interfering effect of ferric ions
is eliminated by reducing them to ferrous ions with ascorbic acid.
The spectrophotometric methods used in the determination of F e 2 0 3 , A1 2 0 3 and
T i 0 2 are a convenient component of the spectral methods. Due to their high sensi
tivity, they are usually employed whenever the content of the oxides is lower than
5 · 10" 4%. They have the disadvantage of being rather tedious and time-consuming.
Table 20 lists the measuring conditions for atomic absorption and emission flame
spectrometry (AAS, AES) and emission plasma spectrometry with microwave-
excited plasma (CMP).
It may be concluded that the present analyses of natural quartzes and silica glasses,
based on rapid and precise spectral and photometric methods, have proved successful
in practice. However, owing to the use of very high purity synthetic silicon raw ma
terials in the preparation of some types of high-purity silica glasses, adequate atten
tion should be paid to the further development of analytical methods and proper
laboratory instrumentation. It has been necessary to increase the number of elements
in the determinations (e.g. the colouring oxides NiO, CuO, MnO, Cr 2 0 3 ) as well as to
work out new methods, for example atomic absorption spectrometry with electro-
thermic excitation (graphite cell), and optical emission spectrometry with induction
bound plasma.
72
Table 20
Survey of methods and measuring conditions in chemical analyses of quartz and silica glasses
\v Method AAS AES CMP
λ (nm) excitation spectral λ (nm) excitation spectral λ (nm) excitation spectral

Component \. source buffer source buffer source buffer
Ti02 - - - - - - 363.5 plasma La, Li,

Cs (EDTA)
A1 2 0 3 — — — 396.1 AC—N20 La, Li 396.1 plasma La, Li,
Cs (EDTA)
Fe203 248.3 AC—air La, Li, — — — 371.9 plasma La, Li,
Cs (EDTA) Cs (EDTA)
MgO 285.2 AC—N 2 0 La, Li, — — — 279.5 plasma La, Li,
Cs (EDTA) Cs (EDTA)
CaO 422.7 AC—N 2 0 La, Li, — — — 422.6 plasma La, Li,
Cs (EDTA) Cs (EDTA)
BaO — — — 553.6 AC—N20 κ2ο 455.4 plasma La, Li,
Cs (EDTA)
SrO — — — 460.7 AC—N20 κ2ο 407.7 plasma La, Li,
Cs (EDTA)
Na20 — — — 589.0 AC—air ss 588.9 plasma La, Li,
Cs (EDTA)
κ2ο — — — 766.5 AC—air ss 404.4 plasma La, Li,
Cs (EDTA)
Li20 670.8 AC—air ss 690.3 plasma La, Li,
Cs (EDTA)
Table 21a
Comparison of analyses of the Czechoslovak standard Svedlär sample
Laboratory Content of impurities (10 4%)
Ti02 A1 2 0 3 F e 2 0 3 CaO MgO Na20 κ2ο Li20
Quartz et Silice 2.2 20.8 2.9 3.9 0.7 79.5 48.2 1.1
UNS, Kutna Hora 1.0 20.0 7.0 tr tr 60.0 10.0 nd
RD. N.C., Jesenik 2.9 26.0 2.1 tr tr 64.0 nd
Dept. of the Technology of
Silicates, Institute of
Chemical Technology, Prague 1.7 26.7 4.3 17.0 nd 75.9 20.5 8.0
State Glass Research Institute,
Hradec Kralove 1.9 22.0 2.0 8.0 1.0 116.0 21.3 1.4
Sklotas, C.C, Novy Bor(1) 3.8 24.6 2.8 nd nd 107.3 22.0 nd
Sklotas, C.C, Novy Bor(2) 3.4 22.0 5.3 nd nd 107.3 22.0 nd
VUUS Novy Bor 1.2 17.9 1.9 0.4 nd 121.2 14.3 2.1
arithmetic mean x 2.26 22.5 3.54 7.32 0.85 95.3 22.6 3.15
standard deviation σ 1.02 2.83 1.84 7.16 (0.21) 21.6 11.3 3.26
variation V 45.2 12.6 52.0 98.0 (24.7) 22.6 50.0 103.3
Explanatory notes: (1) analysis by the method of Sklotas, Novy Bor,

(2) analysis by the Quartz et Silice method;
tr = traces;
nd = not determined
Tables 21 list chemical analyses of dressed quartz raw materials, carried out at the
Institute of Mineral Raw Materials in Kutna Hora, at the State Glass Research
Institute in Hradec Kralove, at the Concern Corporation Sklotas at Novy Bor and
at the Quartz and Silice Corporation in France.
In most instances, the contents of alkali earth oxides either indicate the presence
of alkalis in the form of separate crystals (muscovite, feldspars) or imply a content
of gaseous-liquid inclusions. Evidence for the presence of inclusions is provided
particularly by an elevated content of Na 2 0, whereas the presence of muscovite
and sericite is indicated by a higher K 2 0 content. Similarly, a higher concentration
of Ti0 2 may be indicative of an isomorphic bond or the presence of rutile or anatase
(common minerals of Alpine paragenesis, to which some quartz veins are closely
related). Rutile grains occur quite commonly in Soviet raw materials such as Kyshtym
or Aktas, and to a lesser extent also in Czechoslovak quartz raw materials. The Ti0 2
content may likewise indicate the presence of another titanium-containing material.
The Detkovice quartz may also contain leucoxene from the environment. In this
deposit, it is possible to distinguish zones with a lower and a higher content of
leucoxene, depending on the texture of the quartz vein.
74
Table 21b
Comparison of analyses of the Czechoslovak standard Grapa sample
Laboratory Content of impurities (10" 4 %)
Ti02 A1 2 0 3 F e 2 0 3 CaO MgO Na20 κ2ο Li20
Quartz et Silice 2.7 49.1 4.7 5.7 0.7 45.8 38.6 3.0
Quartz et Silice 2.5 43.5 1.8 5.3 0.3 67.4 15.7 4.3
Institute of Non-Metallic Raw
Materials, Kutnä Hora 1.0 40.0 5.0 tr tr 20.0 10.0 nd
Ore Mines, N.C., Jesenik 2.9 30.0 2.5 tr tr 32 .0 nd
Dept. of the Technology of
Silicates, Institute of
Chemical Technology, Prague 3.1 38.5 5.2 9.0 nd 38.2 13.9 7.9
Hradec Krälove 2.5 41.0 2.7 11.0 2.4 58.7 14.2 3.6
Sklotas, C.C., Novy Bor(1) 3.1 44.3 2.5 nd nd 54.3 15.0 nd
Sklotas, C.C., Novy Bor(2) 4.0 46.0 2.6 nd nd 54.3 15.0 nd
VUUS, Novy Bor 2.7 44.1 3.1 tr tr 57.7 25.4 tr
arithmetic mean x 2.72 41.8 3.34 7.75 1.13 49.6 18.5 4.70
standard deviation σ 0.75 5.15 1.20 2.34 (1.11) 14.8 9.2 2.18
variation V 27.6 12.3 36.0 30.2 (98.2) 29.9 49.7 46.4
Explanatory notes: (1) Method of Sklotas Novy Bor;

(2) Method of Quartz et Silice;
tr = traces;
nd = not determined
Interesting data are also provided by the ignition loss, which indicates the presence
of gaseous-liquid inclusions. In the USSR, this method is included among the limiting
specifications and for silica glass manufacture, the ignition loss should be at most
0.005% [88].
The highest value of ignition loss exhibited by Czechoslovak quartzes is that of
milk-white quartz from the Spis-Gemer Mountains, the lowest that of pegmatite
quartzes and some secretory quartzes from Northern Moravia.
Low ignition loss values are likewise exhibited by clear quartzes, e.g. Brazilian
crystal, Kyshtym, Yugoslav quartzes from the Orehovo region, and others.
Like the T i 0 2 content, that of F e 2 0 3 also indicates above all the presence of
heterogeneous components in the form of grains or residual coatings on the grains.
The components are usually goethite, limonite and lepidocrocite, in the form of
grain coatings and infiltrations in joints. This ferric pigmentation appears macro-
scopically as a pink to brownish colour, which is rendered more distinct by heat
treatment. The A1 2 0 3 content is a very interesting value. On the basis of this content,
it is possible to assess the geochemical and genetic processes that have taken place
75
Table 21c
Chemical composition of refined quartz
Locality Content of the component (%) Calcination Appearance

loss of glass
1
Si0 2 T i 0 2 A l 2 0 3 ! F e 2 0 3 CaO MgO N a 2 0 lΓ
K20
;
1
i
I |
Grapa 99.80 0.002 0.0081 0.003 0.01 tr 0.006 0.006 0.18 clear
Svedlar 99.82 0.001 0.003 ; 0.002 0.01 tr 0.002 : 0.004 0.16 clear
Hummel 99.90 tr 0.0021 tr tr tr tr | 0.002 0.08 clear
Zävadka 99.75 0.001 0.006 0.010 j 0.01 tr 0.006 j 0.004 0.20 clear
Starä Voda I 99.78 tr 0.006 0.001 | 0.01 tr tr ; 0.003 0.19 clear
Starä Voda II 99.74 0.001 0.004! 0.002 ! tr tr 0.001 0.002 0.20 clear
Starä Voda III 99.71 0.001 0.005 0.002 | tr tr 0.002 tr 0.24 clear
Smolnik I 99.78 0.002 0.006 0.001 tr tr 0.005 0.004 0.18 clear
Smolnik II 99.65 0.001 0.004 0.002 tr tr 0.004 tr 0.31 clear
Smolnik IV 99.78 tr 0.003 0.001 tr tr 0.002 tr 0.22 clear
Helcmanovce 99.90 tr 0.004 0.010 tr tr tr 0.002 0.08 opaque
Mnisek 99.83 tr 0.006 0.001 tr tr 0.002 0.001 0.16 clear
Budinä II 99.90 tr 0.006 0.001 tr tr tr 0.002 0.10 clear
Cierny Balog 99.88 tr 0.007 0.001 tr tr tr 0.001 0.10 clear
Hradiste 99.84 tr 0.006 tr 0.01 tr tr 0.002 0.14 clear
Velkä Kras 99.88 tr 0.016 0.002 tr tr tr 0.002 0.08 opaque
Dolni Lipovä 99.66 0.001 0.033 0.002 0.02 tr tr 0.004 0.26 opaque
Dolni Lipovä 99.80 tr 0.0411 0.002 0.02 tr 0.003 0.005 0.10 opaque
Detkovice 99.86 tr 0.005 0.001 1 0.01 tr tr 0.002 0.12 clear
Detkovice 99.84 tr 0.008 0.001 | tr tr 0.001 0.002 0.12 clear
Detkovice 99.93 tr 0.0061 0.002| tr tr tr 0.001 0.05 clear
Detkovice 99.80 0.001 0.008J 0.006 tr tr tr 0.001 0.16 clear
Moravskä Tfebovä 99.79 0.001 0.024 0.006 0.01 tr tr 0.005 0.17 opaque
Resov 99.84 tr 0.004 0.001 tr tr tr tr 0.15 clear
Zeleny vrch 99.87 tr 0.003 0.001 0.01 tr tr tr 0.08 clear
Rejviz 99.68 0.001 0.072 0.009 0.01 tr 0.002 0.003 0.12 opaque
Javornä 99.90 0.001 0.010 0.001 tr tr tr tr 0.08 opaque
Cerveny Vrch 99.88 0.001 0.009 0.001 tr tr tr 0.001 0.10 clear
Krasovice 99.82 0.002 0.018 0.002 tr tr tr tr 0.14 opaque
Skalsko 99.77 0.009 0.028 0.001 tr tr tr 0.001 0.18 opaque
Provodin 99.87 0.011 0.024 0.012 j 0.01 tr tr 0.002 0.06 opaque
Velky Luh 99.82 0.007 0.038 0.002 ! 0.01 0.01 tr 0.002 0.11 opaque
1 J i 1 I
For explanatory notes refer to Table 2Id
in the quartz vein. The low values for the Orehovo and Svedlar quartzes indicate
that most of the quartz filling was formed only after aluminium had precipitated
in the form of muscovite (Orehovo) or chlorite (Svedlar).
The alkalis to alumina ratio shows how the current admixtures are bound. Insofar
as the content of alkali oxides significantly exceeds that of A1 2 0 3 , it may be assumed
76
Table 21d
Quartz leached in HC1
Locality Content of the component (°0 Calcination Appearance

loss of glass
Si0 2 T i 0 2 A1 2 0 3 F e 2 0 3 CaO MgO N a 2 0 κ2ο
Helcmanovce 99.66 0.002 0.077 0.005 tr tr tr 0.026 0.20 opaque
Hradiste 99.50 0.002 0.175 0.018 tr tr tr 0.062 0.20 opaque
Cierny Balog 99.83 tr 0.005 0.002 tr tr tr 0.002 0.14 clear
Smolnik III 99.76 tr 0.004 0.001 tr tr 0.002 tr 0.20 clear
Modry Kamen 99.60 0.002 0.160 0.006 0.02 tr 0.014 0.019 0.18 opaque
Ovcinec 99.44 0.002 0.180 0.005 0.01 tr 0.009 0.049 0.24 opaque
Stofovä dolina 99.76 tr 0.002 0.001 tr tr tr tr ♦ 0.20 clear
Starä Voda HI 99.85 0.001 0.002 0.001 tr tr tr tr 0.14 clear
Slovinky 99.52 0.001 0.075 0.008 0.01 tr 0.006 0.014 0.26 opaque
Hnilec 99.80 0.004 0.030 0.013 0.01 tr 0.005 0.021 0.15 opaque
Zavadka 99.74 tr 0.007 0.003 0.01 tr tr 0.006 0.22 clear
Starä Voda 99.80 tr 0.006 0.004 ^ tr tr 0.004 0.18 clear
Stofovä dolina 99.91 tr 0.002 0.001 0.01 tr 0.002 tr 0.07 clear
Starovodskä dolina 99.90 tr 0.002 tr tr tr tr tr 0.08 clear
Smolnik VI 99.89 0.023 0.003 0.001 tr tr 0.004 tr 0.08 opaque
Roznava I 99.90 0.002 0.003 0.001 tr tr tr 0.001 0.08 clear
Roznava II 99.90 0.002 0.002 tr tr tr tr tr 0.07 clear
Biela Skala 99.92 0.002 0.002 tr tr 0.02 tr 0.001 0.06 clear
Nemrlov 99.93 tr 0.004 0.002 tr tr 0.006 tr 0.06 clear
Spälene 99.96 tr 0.004 tr tr tr tr tr 0.04 clear
Resov 99.94 tr 0.003 tr tr tr tr tr 0.05 clear
Note: tr (traces) of T i 0 2 , F e 2 0 3 , N a 2 0 , K 2 0 mean a content lower than 0.001%,

tr (traces) of CaO and MgO mean a content lower than 0.01%.
Table 21e
Composition of industrially utilized refined quartzes
Locality Content of the component (%) Calcination

loss
TiO A1 2 0 3 Fe203 CaO MgO Na20 κ2ο
Grapa 0.0003 0.0042 0.0003 0.0008 0.0001 0.0050 0.0018 0.08
Svedlär 0.0002 0.0019 0.0014 0.0002 0.0001 0.0066 0.0018 0.08
Detkovice 0.0007 0.0082 0.0009 0.0003 0.0002 0.0037 0.0016 0.11
Kyshtym - USSR 0.0004 0.0014 0.0009 0.0001 0.0001 0.0006 0.0003 0.01 1
IOTA - USA 0.0002 0.0034 0.0007 0.0002 0.0001 0.0004 0.0003 0.01
Brazilian crystal 0.0004 0.0011 0.0018 0.0001 0.0001 0.0004 0.0001 0.01
77
that the alkalis are bound in the gaseous-liquid inclusions. Sometimes the contents
of these oxides are in a certain simple relationship (in molecular values); the ratio
1: 3 is characteristic of micas, and the ratio 1:1 is typical of feldspars.
Alumina may also be bound in the quartz lattice, on the principle of heterovalent
isomorphic substitution.
Expressed as the ratio A given by the equation
Na 2 0 + Κ 2 0 , ,
A
- AW · < 26 >
the following values of A were found for quartzes from various deposits:
Svedlär 3.7 to 6.2
Grapa 1.0 to 2.0
Detkovice 0.4 to 1.2
Kyshtym 0.2 to 0.7
Brazilian crystal 0.3 to 0.7
Figure 31 shows the relationship between the content of A1203 and Ti0 2 for ten
samples of quartz raw material from the Detkovice deposit.
The Svedlär quartz differs significantly from the other quartzes in the high value
of its A ratio. This is due to a very low content of A1203 and a high content of gaseous-
liquid inclusions.
2500
2000
^ 1500
o
eg
<
1000
1
500
25 50 75 100 125 150

A
- TiO 9 .10 (%)
"Ί'
Fig. 31 — A1 2 0 3 content vs. T i 0 2 content in quartz raw materials from the Detkovice deposit
(quartz samples treated by chemical refining)
78
2.4.4 Mineralogical analysis
A mineralogical analysis of quartz should be carried at each stage of the

deposit survey, in order to determine the ease of refining of the raw material and to
assess the quality of the raw material supplied for silica glass melting. It is possible
to distinguish diverse varieties of quartz macroscopically, and the main impurities
and their distribution in the raw material can be determined; at the same time, it is
advantageous to study the structural and textural properties of the quartz and the
quartz vein.
Microscopy is used in studying the composition and bonding of impurities, and
the structural peculiarities of the quartz in question. The individual macroscopically
determined minerals can then be determined precisely. Their distribution, grain
sizes, inversions, and the possibility of their elimination by suitable dressing pro
cedures are all of interest.
Table 22
The main accompanying minerals in quartz from the Svedlär deposit
Mineral Composition Solubility, ease of melting
Ripidolite Fe-Mg aluminosilicate Soluble in acids

Pistomezite (Fe. Mg, Mn)C0 3 Soluble in acids — similar to siderite, which
dissociates at 450 °C
Albite NaAlSi 2 O g Insoluble in acids, melting temperature
1118°C
M usco vite-sericite KAl 2 (AlSi 3 O 10 )(OH) 2 Liberates water above 850 °C, insoluble
in acids, melting temperature 1260-1290 °C
Sulphides F " e i - Ä pyrrhotine Pyrrhotine is barely soluble in HC1;
FeS 2 pyrite, marcasite on ignition, sulphides produce pyrite,
CuFeS 2 chalcopyrite marcasite and chalcopyrite; at 535 °C,
PbS galenite marcasite is converted to pyrite, which
ZnS sphalerite in turn dissociates to FeS + S at 600 °C;
the other sulphides are rare (in the Svedlär
deposit)
Hydropergenous y-HFe0 2 lepidocrocite At 180-300 °C, goethite gives up H 2 0
minerals a-HFe0 2 goethite and is converted to hematite, lepidocrocite
a - H F e 0 2 . n H 2 0 limonite losing H 2 0 at 160-180 °C converts to
Cu 2 S chalcosine maghemite, limonite loses H 2 0 up to
CuS covellite 300 °C, maghemite (y-hematite) at
460-600 °C, converting to hematite;
hematite dissolves very slowly in HC1,
converting to magnetite in air at 1388 °C,
and melting at 1597 °C
79
Clear silica glass has been melted mainly from quartzes faulted by compression.
These quartzes show distinct marks of plastic deformation, which the environment
has metamorphosed into green slate faces. Such conditions occur for example in
the case of Grapa, Budinä, Svedlär and Detkovice quartzes. They exhibit undulating
extinction, a dense network of microfissures and numerous micro-size inclusions
with two-phasefilling.Their formation is generally linked to hydrothermal conditions
and affected by the character of the environment in the course of its metamorphosis.
Sequential formations of ore-free quartz veins at the end of the mineralization process,
and the succession of quartz separation on the vein only after the main accompanying
minerals have precipitated (micas, chlorite, sulphides), are regarded as favourable
features.
Some separation methods of mineralogical surveys deserve special attention, as
they represent a practical link to the dressing processes. They include separation of
heavy minerals, magnetic separation, selective dissolving of minerals and elimination
of inclusions by heating. Determination of the grain size distribution of minerals
in the individual classes is also significant.
The main minerals accompanying quartz in the Svedlär deposit are listed in
Table 22.
2.4.5 Sieve analysis
The granularity of the dressed product is a critical parameter, which is

specified in technological directions for the melting of silica glass. In most countries,
silica glass is melted from fine-grained silica raw material. The maximum grain sizes
are usually given by the sieve in the range 0.5 to 1.2 mm, the lower limit being in the
range 0.08 to 0.15 mm. Finer fractions are not desirable, as they cause difficulties
during the melting and tend to contain impurities. The grain size distribution of the
charge influences the value of apparent density, and thus also the melting yield.
A suitable granularity can also directly affect the degassing of quartz, and subsequently
also the quality of the silica glass. Even coarse-grained quartz raw materials have
been shown to be suitable for the melting of clear silica glass.
The grain size composition of dressed quartz is evaluated, according to the re
spective standards, by the use of the appropriate set of sieves. The results of the sieve
analysis are then compared with the standard grain size curve.
2.4.6 Evaluation of the distribution of impurities
Chemical analysis provides basic information on the amount of admixtures

in the quartz raw material (or in the glass). The admixtures can be divided into those
structurally bound and non-structural admixtures.
80
Quartz has a stable crystalline lattice with a limited possibility of isomorphous
substitution of silicon by other elements. The total content of structural admixtures
does not exceed hundredths of a percent [74], and the additions are in particular
Ge, Ti and W (isovalent isomorphism) and Al, Fe, Ca, Mg, Ga and possibly B
(heterovalent isomorphism). Electron paramagnetic resonance has revealed the
possible presence of H, Li, Na and K in structural channels. In the vein quartzes
under consideration, the structurally bound additions are mainly Al, Ca and some
alkaline metals.
Dressing has so far been unable to influence the structurally bound impurities.
This makes the methods for the determination of non-structural additions in quartz
increasingly important. Investigation of their bonding leads to more efficient dressing
of quartz and to the production of high-grade silica glass. The non-structural additions
in quartz are the following:
(a) coatings and infiltrations of hypergenous minerals, particularly those from
the limonite group;
(b) finely dispersed ferric pigmentation of quartz, comprising limonite or hematite;
(c) separate minerals (albite, rutile, leucoxene, actinolite, micas, etc.);
(d) gaseous-liquid inclusions containing dissolved salts of sodium and potassium.
The individual forms can be distinguished under the microscope or concentrated
by physical methods. The limonite coatings can generally be easily leached in acids.
Ferric pigmentation cannot be eliminated by leaching; quartz contaminated in this
way is eliminated by hand sorting, usually after heat treatment which makes the
colours more distinct. The separate minerals belong to concentrated impurities and
are therefore least desirable in dressed quartz. They can be eliminated in several
ways: by electromagnetic separation, electrostatic separation, in heavy liquids of
different density, or just by hand sorting and microscopic examination. The gas-
liquid inclusions are evaluated either semiquantitatively by microscopy, or by means
of indirect physical methods, as described below. Assessment of quartz on the basis
of detailed analysis of the individual gases released from it during its heating has not
so far provided explicit results. Important information is provided by chemical
analysis of the finished glass, where the difference in the content of alkali elements
allows their content in gas-liquid inclusions to be assessed.
In addition to the admixtures mentioned above, there are frequently secondary
impurities introduced into the quartz raw material in the course of extraction,
shipment and dressing. These are usually pieces of coal, fireclay from the furnaces,
metallic particles or residues of greases, fats and wood. Their occurrence should be
reduced to a minimum.
In the USSR, the admixtures in production plants are assessed by hand sorting
of the so-called point impurities and restricted to the amount of 4 grains in 1 kg of
dressed quartz [88], or 10 grains in 1 kg (the Leningrad dressing plant). The point
81
impurities are determined in samples of 50 g of quartz (two determinations). The
sorted point impurities are evaluated under the microscope. The amount of point
impurities of organic origin is determined from the difference before and after ignition
in a laboratory crucible furnace.
In terms of their significance, the point mineral impurities are divided into two
groups: impurities producing glassy inclusions in glass after melting, and those
responsible for coloured inclusions. The glassy inclusions are formed from feldspars,
muscovite, biotite, chlorite, turmaline, epidote, zoisite and garnets. According to
Soviet Standards, the sum of mineral admixtures producing glassy inclusions should
not exceed 1· 10" 3 wt.%.
Coloured points in glass are formed from the following minerals: rutile, ilmenite,
titanite, hematite, sulphides, apatite and actinolite, and also from secondarily intro
duced abraded iron from the plant, rust and further impurities. The sum of mineral
admixtures yielding coloured inclusions in glass should not exceed 10 grains in 1 kg
of quartz.
Qualitative evaluation of minerals is most conveniently carried out by separation
in heavy liquids. All the minerals producing coloured inclusions in glass belong
among the so-called heavy minerals. These include substances with density higher
than 2900 kg m" 3 . This limit is given by experimental conditions, i.e. the density
of liquids most frequently used in the separation (bromoform, CHBr 3 , and tetra-
bromoethane, C 2 H 2 Br 4 ).
Each of the two liquids has its advantages and disadvantages. Bromoform is con
siderably more expensive, its density at room temperature is a maximum 2880 kg m~ 3 ,
it is more volatile, and it decomposes in sunlight; tetrabromoethane, which is less
volatile, does not decompose in light and has a higher density (2920 to 2950 kg m " 3
at room temperature). The latter liquid has the disadvantage of a somewhat higher
viscosity, which is responsible for longer times of separation. Acetone or ethyl
alcohol can be used to adjust the density and to wash the fractions obtained.
The heavy minerals are separated in suitable dividing funnels, beakers, dishes,
etc. The method is described in [89]. An adjusted variant is used to separate the heavy
minerals from ground quartz raw materials. In view of the low content of heavy
minerals in quartzes (of the order 10" 4 %) it is necessary to use larger samples, i.e.
about 100 g. It is, moreover, necessary to carry out separation from several samples
and to consider the arithmetic mean of all the determinations.
The dressed Svedlär raw material was found to contain heavy minerals (separation
in bromoform) in amounts of 4.8 to 15.5 · 10" 4 %, or 950 to 3500 grains of heavy
minerals per 1 kg of dressed raw material. The mean value of 24 determinations
amounts to 9.4 · 10" 4 %, or 2300 grains per 1 kg of the raw material.
With the Detkovice raw material, the average content of heavy minerals (14 deter
minations) was 19.1 · 10" 4 %, or 3800 grains per 1 kg of the raw material. The content
of iron oxides and leucoxene in the heavy fraction was determined microscopically.
82
The mineralogical quality of the fractions obtained is assessed microscopically.
The Svedlär raw material contains mainly grains of hematite, pyrite, and lower
concentrations of rutile, anatase, leucoxene, chalcosine and hercynite. The Detkovice
raw material contains mostly hematite with leucoxene, and the accessory minerals
pyrite, garnet, rutile, anatase and ilmenite. The applicability of quartz raw materials
for the melting of clear silica glass depends largely on the extent to which the heavy
minerals are removed by the dressing process.
2.4.7 Light transmittance measurement
The method is based on measuring the transmittance of light radiation

through the quartz raw material in an immersion liquid. It is measured in cells, the
most important problem being uniform distribution of quartz throughout the cell
volume. The dust fractions of the sample have to be removed before the measurement.
Benzyl alcohol is a suitable immersion liquid with respect to the refractive index
of quartz. Any arbitrary type of spectrophotometer can be used in the measurements,
and the values obtained have to be related to a blank measurement, of the cell filled
with the immersion liquid.
The practical results indicate that the method is suitable for the evaluation of
quartz containing at least 50% of clear grains.
2.4.8 Light scattering measurement
Optical methods based on scattering of light radiation caused by scattering

centres are important in the study of the microheterogeneous structure of both
crystalline and amorphous substances. The subject was surveyed by Fanderlik [101],
Prod'homme [102], Eskin [103] and others.
Dubsky [104] studied vein quartz raw materials by measuring the intensity of the
scattered light flux at an angle of 90°, but the method was incapable of explaining the
differences between the inner structures of quartz raw materials of various geological
origins. It was only the method based on measuring the angular distribution of
scattered light flux, published by Fanderlik and Dubsky [109], which was capable
of assessing the character of the scattering centres in quartz raw materials.
It is known that if the size of the scattering centres does not exceed Α/4π, Rayleigh's
theory [105], based on Tyndall's findings [106], is capable of explaining the circular
shape of the indicatrix for a vertically polarized incident light flux Φ (Fig. 32(a)).
Rayleigh's scattering is first of all a phenomenon of light diffraction. In the case of
quartz raw materials, the factors involved are the smallest inclusions, structural
defects, etc.
A vertically polarized light flux is one polarized perpendicular to the plane over
which the scattered light flux is measured, while a horizontally polarized light flux
83
is polarized parallel to the plane of scattered light flux measurement. The plane
formed by the ends of vectors passing from an infinitely small surface element or
volume of the scattering body is called the scattering indicatrix. The indicatrix curves
are plotted in rectangular coordinates, i.e. plots of scattered light flux Φτύ vs. the
measurement angle Θ. To simplify interpolation of the measurements a vertically
polarized incident light flux Φ is mostly used so that the intensities of the scattered
light flux for Rayleigh scattering do not depend on the measurement angle Θ (cf.
Fig. 32(a), curve 3).
a 180*—l·
90·
135° ,
45° Fig. 32 — Intensity distribution of
180 t
v·.
2
\.
Y'o·
scattered light flux:
(a) - Rayleigh's scatter; (b) - Mie's
scatter; (c) — scattering in Rayleigh-
\ s ^ / *>'' 315* Gans's approximation; incident light
flux non-polarized (1), horizontally
225° 270" polarized (2), vertically polarized (3)
If the scattering centres attain a size approximately comparable with the wave
length of the incident light, the light passage through the scattering centre requires
a certain time which is already not negligible relative to the period of the electro
magnetic field (the phases displacement must be considered in terms of the scattering
angle Θ). The scattering centres then exhibit an explicit change in local polarizability
84
(the phase boundary between the scattering centres and the ambient phase is sharply
bounded) and Mie's theory [107] can be used in the theoretical interpretation of
the results.
For a vertically polarized incident light beam, the indicatrixes are no longer
circular, as they show a greater intensity of scattered light for small angles and lower
values for larger angles, as demonstrated in Fig. 32(b). This type of scattering is
characteristic, for example, of suspensions, colloidal particles, sharply bounded in
clusions, etc.
If the refractive index of scattering centres is close to that of the ambient medium
and the variation of the refractive index in a scattering centre is a function of radial
distance, the phase concentrated in the scattering centres has no sharply bounded
phase boundary but has instead a concentric diffusion zone. In this case, the theory
of scattering in Rayleigh-Gans's approximation [108] can be used to interpret the
measurements. The theory assumes that each volume element of the scattering centre
acts as a Rayleigh scatter, independently of the other elements. According to the
positions of the scattering centres in space, the scattered light waves show a mutual
phase difference and are responsible for the interference effect. In contrast to the
types of scattering mentioned above (Rayleigh's, Mie's), higher values of scattered
light flux are obtained at larger angles, and vice-versa (cf. Fig. 32(c)).
Typical examples of this type of scattering in quartz raw materials are the various
inclusions in quartz grains, coatings and larger structural defects.
All the inhomogeneities occurring in quartz raw materials, as described in detail
in Sections 3.2.2 and 3.2.3, affect the angular scattering of light in various ways,
depending on their character. It is thus possible to distinguish the quartz raw ma-
I I
MX Bo
)
^3-€ 8
Fig. 33 — Schematic diagram of the optical part of the photogoniodiffusiometer by ARL-FICA 42000:
I — Water-cooled high-pressure mercury discharge lamp; 2 — prism; 3 — condenser; 4 — turntable
with filters; 5 — polarizer; 6 — iris diaphragm; 7 — reference diffusion element; 8 — photocell;
9 — iris diaphragm; 10 — vessel with toluene or benzene in which the sample being measured is placed;
II — type RCS IP 28 photomultiplier including optical system, revolving by 0° to 180° around the
sample; 12 — sample being measured
85
terials according to the results of measuring. Figures 52, 53 and 54 (pp. 104-134)
show micrographs of inhomogeneities in grains of quartz raw materials.
The intensity of scattered light flux, Φτα, in terms of the measuring angle Θ, can be
measured by means of a photogoniodiffusometer (e.g. ARL-Fica 42 000), whose
optical schematic diagram is shown in Fig. 33.
/
12 /
/
/
/
/
/
/
/
10
/
ll
I
I
i si
I ii
I !
io
/
// ii
6
/ /·'
ii
/ //
/ //
/ / /
'' / ·' Fig. 34 — Intensity of

/ / /
/ y / scattered lightfluxΦτά vs. the
/ / / measuring angle Θ for:
/" y 1 — Czechoslovak Grapa
s*·'S quartz raw material;
,-' 2 — Czechoslovak Detkovice
L_L quartz raw material;
30 Λ5 60 75 90 105 120
. 135
, 150
. q3u —
a r tCzechoslovak
z r a w materialSvedlär
The measurement is always carried out at the same incident intensity of mono
chromatic vertically polarized radiation Φ, at wavelength λ = 436 nm. The quartz
raw material being measured (rc436nm = 1.547 to 1.549), with a grain size of 0.1 to
0.5 mm, is introduced into a cylindrical cell, jointly with benzyl alcohol of A.R.
purity (rc436nm = 1.549 at 20 °C), which serves as immersion liquid. As the dispersion
is always recorded for a different dispersion volume at various angles of the photo-
multiplier adjustment, the values obtained have to be recalculated to the unit volume
86
according to Eskin [103] by multiplying the intensity of scattered light flux Φτά for
various measuring angles Θ by sine Θ. The measurements are plotted as indicatrix
curves, using rectangular coordinates. The errors involved in the measurement of the
relative intensity values of scattered light flux Φτά in terms of the measuring angle Θ
do not exceed ±0.02.
9r
w3
\\
\\
1 \
5
I \
\
\
\
\
\
\
\
\\
\\
\
30 45 60 75 90 105 120 135 150

Θ C)
Fig. 35 — Intensity of scattered light flux Φτά vs. the angle of measurement Θ for: 1 — Brazilian
crystal; 2 — raw material used by Thermal Syndicate Co.; 3 — Soviet Kyshtym raw material
Figures 34 to 36 show measurements on natural quartz raw materials supplied

for the melting of clear silica glasses, dressed by the standard refining procedures.
The effect on the angular distribution of scattered light flux of the temperature
used in the heat treatment of the Soviet MBK raw material is shown in Figs 37
and 38, and the effect of Fe 2 0 3 concentration in the Czechoslovak Svedlär raw
material is plotted in Fig. 39.
Of the inhomogeneities that act as scattering centres, the most important are
gaseous-liquid or gaseous inclusions. The refractive index of these inclusions is lower
than that of the medium (the quartz raw material), for both the gaseous and liquid
phases.
The scattering of light is also noticeably influenced by minerals and pigments
dispersed in the individual grains of the quartz raw material (inclusions of ac-
87
9
\
\
8 \
\
7 -
γ
\
6
\,
I
5
1
1\ \
»θι
\\ /
A \ /
4
\ / \
\ ,' \
Υ \
3 /' \ Fig. 36 - Intensity of
/ \\ scattered light flux Φνά vs.
s \ the angle of measurement Θ
2 / \
\ for: 1 - Soviet MBK raw
\
\ material (Svetlorechensk);
1 2 — African raw material
from Angola (quality B);
1 Ι__ 1 1 1 1 1 1 L
3 — American raw material
30 45 60 75 90 105 120 135 150 Arkansas I
11 11
r*
,ό
10 10 - ill
6Jil·5,
y
8 /
/TV / / .S2
9-
8-
!l7/ 'l·
r /" //9\
!
7 7_
'//
';
I!
' i
■ο
- / ' / / / \ :*ι β
A / / i
| 5 5
l· // / / /
4 4 \- // / / /
V / / /
3 3L
- ss
2 2
^
1 1Γ
•s ''' S
"" ^-
"^ ^'
*·**
1 ι I 1 1 Li 1 1 1 1
30 60 90 120 150 30 60 90 120 150
- Θ(·) — Θ C)
Fig. 37 - Intensity of scattered light flux Φτύ vs. Fig. 38 — Intensity of scattered light flux Φτά vs.
angle of measurement Θ for the Soviet MBK raw angle of measurement Θ for the Soviet MBK raw
material after various heat treatments: 0 — no heat material after various heat treatment:
treatment, 1 - 800 °C; 2 - 900 °C; 3 - 1000 °C; 5 - 1200 °C; 6 - 1300 °C; 7 - 1300 °C, 1 h;
4 -1100°C 8 - 1400 °C; 9 - 1500 °C
companying minerals). Compared to the ambient medium (quartz raw material),
the refractive indices of these minerals are higher.
As a result of their low concentration, the loose accompanying minerals in quartz
raw materials do not in practice affect the scattering of light to an extent which would
influence the angular distribution of the light flux significantly.
H
I
t
I
I
I
I
I
I
I
I
I 2A
3
! It
i IHH
1
a
/ ///
/ / ·· I Fig. 39 - Intensity of
/ // / scattered light flux Φτύ vs.
/ /' / / angle of measurement Θ for
xx •///' the Czechoslovak Svedlär
./>£> raw material with various
*z££*»''' contents of F e 2 0 3 :
:
^^ , | | | 1 - 6.5 ppm; 2 - 24.4 ppm;
90 105 120 135 150 3 - 38.9 ppm; 4 - 43A ppm
- 0 C)
Scattering centres conforming to Rayleigh's condition of maximum dimension

can be observed in the quartz raw material used by the Thermal Syndicate Company
to produce clear silica glass.
Centres scattering the light flux in accordance with the Rayleigh-Gans approxi
mation are present in Czechoslovak vein quartz raw materials from the Svedlär and
Detkovice deposits.
A transient type of scattering centre is present in the Soviet MBK quartz raw
material, and scattering centres of Mie's type occur in the Soviet Kyshtym raw
materials, the African raw material from Angola, the American Arkansas I raw
material and Brazilian crystal.
2.4.9 Other supplementary methods
We conclude with a brief mention of other supplementary methods used to

evaluate quartz raw materials.
89
The DTA method [differential thermal analysis) allows the phase transformation
jS-quartz -» α-quartz to be compared to the theoretically determined temperature.
The temperature shift of the phase conversion from the theoretical value is mainly
due to impurities and structural defects. According to data from the literature, the
conversion temperatures are in the range of 540 to 590 °C, while the theoretical
value is 573 °C (575 °C).
The GTA method (gravimetric thermal analysis) is a much more precise variant of
evaluating quartz according to the so-called ignition loss; some vein quartzes exhibit
up to 0.5% of weight loss at 1400 °C.
The ignition loss is that due to exposure to 900 °C for a period of 1 hour. A standard
ignition loss of 0.005% is stipulated by Soviet Standards. The Czechoslovak dressed
quartz raw materials exhibit the following values:
Svedlär 0.03 to 0.04%,

Detkovice 0.08%,
Kyshtym 0.02 to 0.03%,
Brazilian crystal 0.02 to 0.03%.
With non-dressed quartzes, the ignition losses are in the range of 0.19 to 0.22%.
Centrifuging methods can be used to evaluate the homogeneity of quartz raw
materials. The device used consists of a Gentrifuge provided with a speed control,
a light source, glass cells, a cathetometer and an ultrathermostat. The principle
of the method is based on weighing washed and dried quartz of 0.125 to 0.200 mm
grain size in cells in amounts which produce a layer about 3 mm in thickness on
centrifuging in an immersion liquid. The liquid, a mixture of tetrabromoethane and
α-monobromonaphtalene, is mixed in a ratio corresponding to the density of the
quartz sample at 28 °C. The centrifuging is started at 12 °C, when the immersion
liquid density is higher than that of the quartz. At this temperature and a speed of
2000 r.p.m., all the quartz moves towards the centre of the centrifuge within 20 to
30 minutes, and forms a layer there. The layer height is read with the cathetometer.
The temperature is then raised by the thermostat at a rate of 1 °C per 5 minutes, and
the change in the height of the sample, which starts to move to the outer circum
ference and thence to the bottom of the cell, is noted. After the transfer is completed,
the measurement is repeated while cooling at the same rate. The sample homogeneity
is indicated by the temperature range over which the sample has passed from the
cell bottom to the centrifuge centre. For example, in comparison with Brazilian
crystal, the following values were obtained for Czechoslovak vein quartzes:
Total transition interval
(°c)
Brazilian crystal 5
Grapa 14
90
Svedlär 16.5
Detkovice 5
Laboratory melts provide useful methods insofar as the conditions are similar to
operational conditions. But where the operational conditions cannot be simulated
on the laboratory scale, the suitability of a quartz raw material for melting can be
assessed according to the quality of laboratory-melted quartz glass.
Pilot plant melting is usually carried out in a production furnace. Pilot plant
melting is used to establish the technological melting procedure which has been
suggested on the basis of laboratory melts.
The methods mentioned above allow the results of melting a silica raw material
to clear silica glass to be determined, approximately, in advance. However, further
methods are likely to be developed in future as this subject is receiving considerable
attention.
REFERENCES (Chapters 1 and 2)

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1978
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[4] FLÖRKE, O. W.: Fortschr. Mineral., 44 (1967), 2, p. 181
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[7] PAULING, L.: The Nature of the Chemical Bond and the Structure of Molecules and Crystals,
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stroyitelstvu, Leningrad, 1971
[9] PAULING, L. - SHERMAN, J. A.: J. Am. Chem. Soc, 59 (1937), 8, p. 1450-1456
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Academici-Abacus Press, Bucuresti-Tunbridge Wells, 1976
[11] MILLIKEN, R.S.: J. Am. Chem. Soc., 72 (1950), 10, p. 4493^t503
[12] SLATER, J.C.: Phys. Rev., 36 (1930), 1, p. 57-64
[13] LAZAREV, A.N.: In: Strukturnye prevrashchenya v steklach pri povyshennych temperaturach
(Structural Conversions in Glasses at Elevated Temperatures) (Collected papers). Izdatelstvo AN,
Moscow, 1965
[14] SOSMAN, R. B.: The Phases of Silica, Rutgers University Press, New Brunswick-New Jersey, 1965
[15] FENNER, C. N.'.J. Wash. Acad. Sei., 2 (1912), p. 471-480
[16] FENNER, C. N.: Am. J. Sei., 36 (1913), 214, p. 331-384
[17] MACKENZIE, J. D. - WHITE, J. L.: J. Am. Ceram. Soc., 43 (1960), 3, p. 170-171
[18] SLATER, J.C.: Quantum Theory of Molecules and Solids. 2 — Symmetry and Energy Bands in
Crystals. New York, 1965
[19] WABER, J. T. - CROMER, T.: J. Chem. Phys., 42 (1965), 12, p. 4116-4123
[20] BRATCEV, V. F.: Tablici atomnych volnovych funkciy (Tables of Atomic Wave Functions), Nauka,
Moscow, 1966
91
[21] BRAGG, W. L.: Philos. Mag., 40 (1920), 236, p. 169-189
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SSSR, Moscow, 1962
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Moscow, 1970
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94
3 THE TECHNOLOGY OF SILICA GLASS MANUFACTURE
3.1 INTRODUCTION
The first part of the present treatise, i.e. Chapter 2, presented a brief account
of the phase transformations of quartz and synthetic raw materials to silica glass.
However, from the standpoint of technology, these phase conversions are signifi
cantly affected by the geological origin (purity) of natural quartzes and by the chemi
cal composition of synthetic silica raw materials.
The phase transformations are further influenced by the processing technology
and the melting technology employed. These so-called technological factors have
a marked effect on the physico-chemical properties of melted silica glasses, as
demonstrated in Chapter 4.
This matter will therefore receive attention in the present Chapter.
3.2 SILICA GLASS
On heating, crystalline jS-quartz (stable at temperatures lower than 573 °C

and containing less than 0.01% of foreign admixtures) undergoes a phase trans
formation to high-temperature α-quartz, which is stable up to 1400-1450 °C [1]
(Fig. 40).
Further heating converts α-quartz to high-temperature α-cristobalite, while
simultaneously producing a transient amorphous phase. The proportions of the
J>
amorphous / ^
0) ^ phase ' /
Ϊ
Q.
& ^.---^^to-cristo-
balite
^^-~<Γ~ϋ>Φ^ !
Ύ
1 ! ' |
1 ' 1
1 i i i i Fig. 40 - Diagram of phase
250-270 573 •1400 1723 transformations of crystalline
fCC) Si0 2 at normal pressure
95
crystalline and transient amorphous phases depend on the concentration of foreign
admixtures (particularly alkalis), which cause nucleation and thus a decrease of the
temperature of phase conversion to 1360-1380 °C (the so-called cristobalitization).
The high-temperature α-cristobalite melts at 1723 °C, and its subsequent super
cooling produces silica glass of amorphous structure. The transient amorphous
phase formed at about 1400 °C from α-quartz is likewise converted to melt jointly
with α-cristobalite, so that the formation of the melt is a result of these two processes.
The phase diagram in Fig. 40 therefore differs in part from Fenner's diagram
(Fig. 9), reflecting newer findings on the phase conversions.
Glass (the supercooled melt) is generally defined as a substance in an amorphous
state, i.e. a substance not exhibiting the properties of a crystalline lattice. Within
the limits of accuracy of measuring methods (e.g. the X-ray diffraction method),
glass therefore does not show the symmetrical periodicity of structure over consider
able distances typical of a crystalline substance.
.Cooling of the S i 0 2 melt, stable above 1723 °C, below the melting temperature
of α-cristobalite thus does not bring about crystallization, but produces a supercooled
liquid (glass).
During the cooling of the S i 0 2 melt at a given temperature, pressure and com
position (with admixtures in minor amounts) a certain state of equilibrium is estab
lished, the so-called metastable equilibrium, which corresponds to a certain configur
ation of molecules, i.e. to a certain structure.
The establishment of the equilibrium always lags behind the change in tempera
ture or pressure, because the creation of an equilibrium configuration of molecules
always requires a certain so-called relaxation time. This relaxation time increases
very rapidly with decreasing temperature. At a given cooling rate the equilibrium
configuration, corresponding to a certain higher temperature, is thus retained in
the glass and does not change on further cooling down; it is the so-called frozen-in
structural state.
The supercooled liquid thus turns into a solid amorphous phase called silica glass.
The temperature at which the freezing-in has taken place depends on the cooling
rate, and is thus not a characteristic material constant.
This brief introduction outlines the fundamentals of phase conversions involved
in the formation of silica glass. The subject will be dealt with in more detail in
following chapters.
3.2.1 The quartz to silica glass phase transformation
Section 3.2 presented a brief account, and Section 2.2 a more detailed one,
of the phase transformations taking place in the course of heating low-temperature
β-quartz up to the formation of a melt. The given phase conversions are affected in
96
particular by the purity of the quartz raw materials, i.e. the concentration of ac
companying minerals and impurities present in the structure or in the fissures, by
the presence of inclusions (gaseous, gas-liquid, liquid), the surface texture of the
individual grains, and the like. It obviously also depends on the melting technology
employed.
As the impurity content varies considerably, depending on the geological origin
of the quartz raw materials, and the impurity distribution is usually non-uniform,
the phase transformation
/ transient amorphous phase -► melt
p-quartz -> a-quartz
\ a-cristobalite -► melt
usually takes place over a certain temperature range.

In accord with this, there are also differences in the results of studies by various
authors who have used quartz raw materials of different purity.
Pryanishnikov [1] presents the results of a study of the formation of the transient
amorphous phase during the heating of quartz raw materials of various geological
origins (Table 23).
The Table shows that the transient amorphous phase already begins to form at
about 1400 °C. The concentration of the transient amorphous phase at various
temperatures of heat treatment, for different types of quartz raw materials, is given
in Table 24 [1].
In this case, the raw materials of 0.20-0.25 mm grain size were heated in an open
gradient furnace under atmospheric pressure for 30 minutes (I) and in a suite furnace
for 40 minutes (II).
The transient amorphous phase has a refractive index ηΌ ~ 1.460 to 1.540 (close
to that of jß-quartz: ηΌ = 1.544) and a density similar to that of jß-quartz. Depending
on the time of heat treatment and with increasing temperature, the density decreases
down to the value of 2200 kg m~3, which corresponds approximately to the density
of the melt at temperatures higher than 1700 °C.
Table 23
Formation of the amorphous phase in quartzes of various purity on heating
Raw material Content of admixtures (%) Temperature of initial formation

of amorphous phase (°C)
in an atmosphere of
r
Σ ' Fe 2 0 3 " R20 air vacuum nitrogen
i | i i
Brazilian crystal
5.3· 10" 3 : 3.2· 10" 5 - 1-10" 3 1 1420 1430 1450
Soviet Kyshtym raw material
2.7· 10" 3 1.2· 1 0 " 4 : 1 1 0 " 3 ! 1380 1430 .1400
Synthetic Si0 2 crystal
110"2 5.5· 10" 5 6 1 0 " 3 1360 1430 , 1380
97
Table 24
Concentration of the amorphous phase for various temperatures of heat treatment of quartzes
t(°c) Content of amorphous phase (°

$ \
Brazilian crystal Soviet Kyshtym Synthetic Si0 2
raw material crystal
I II I II i | ii
1
1500 up to 10 _ 17 — up to 20
1
1470 7-8 - 12-15 -
1450 5 up to 5 up to 10 up to7 12-14 8
1420 up to 3 2.5 8-10 5.5 10 7.5
1400 2 up to 10 4 up to 3 up to 5 up to 4
1380 1-1.5 - 3 1 3-4 2 i
1360 1 — 1.5-2 - 2.5 - j
1350 - - 1.5 - 1.5-2 - 1
1340 - - - - 1
1320 - - - - 1
Table 25 lists the phases forming by the melting of α-cristobalite, according to

Pryanishnikov [1].
Table 25
Phases forming during the heating of a-cristobalite
' (°C) min Phase being formed
1700 10 cristobalite
30 cristobalite
1720 10 cristobalite
30 cristobalite + glass(1)
1750 10 cristobalite + glass 0)
30 cristobalite + glass 0 '
1770 10 cristobalite + glass 0 ]
30 cristobalite 0) + glass
1800 10 cristobalite 0 ] + glass
30 glass + traces of cristobalite
1830 10 glass + traces of cristobalite
30 glass
1870 10 glass + traces of cristobalite
30 glass
1900 10 glass
30 glass
1
in a low concentration
98
A number of studies, e.g. those by Chaklander and Roberts [2, 3, 4, 5, 6] and
Grimshaw, Hargreaves and Roberts [7] indicate that this phase conversion of
α-quartz to α-cristobalite occurs over the temperature range of 1400 to 1650 °C via
a transient phase with a density of 2300 kg m" 3 , whose concentration first increases
and then decreases.
100
\ quartz
50 h
cristobalite
transient phase ..··
\
/
y
Fig. 41 — Phase transformations due to heating
6 8 10 of Brazilian quartz at 1560 °C in terms of time
f(h)
The time change in the phase conversions of quartz at 1560 °C is shown in Fig. 41
(according to Roberts and Chaklander [5]).
Mackenzie [8, 12] also assumes the phase conversion
quartz -» transient phase -► cristobalite and quartz -► cristobalite.
Fanderlik and Dubsky [9] studied the phase transformations of quartz raw
materials of various geological origins in the course of heat treatment. The raw
materials were heated in a vacuum electric furnace (Balzers VSG-02) in graphite
crucibles (French FHAI graphite), using the procedure illustrated in Fig. 42.
1800
1400
- 1000
»
Fig. 42 - The rate of heating of

quartz raw material (t) and the
course of pressure (p1 — Brazilian
crystal, Kyshtym; p2 — Detkovice,
Svedlär)
99
On attaining the required temperature, the furnace was in each case switched off,
the sample quenched and its content of quartz and cristobalite determined by
quantitative X-ray diffraction phase analysis. The results of the determinations on
Brazilian quartz, the Soviet Kyshtym raw material and the Czechoslovak Svedlär
and Detkovice raw materials are given in Figs 43 to 46.
quartz
IOOHV-.^ L
80
£ 60
40
20r cristobalite \ îg- 43 — Quartz and cristobalite content in

! , i L.4 i -i terms of heat treatment temperature
800 1000 1200 1400 1600 1800 (Brazilian crystal)
■— f C O
quartz
100
80
n^ c
- 60
o
"* 40
cristobalite \ Fig. 44 — Quartz and cristobalite content
20
__, N—-r^. \ i in terms of heat treatment temperature
HV-
800 1000 1200 1400 1600 1800 (Soviet Kyshtym quartz raw material)
f CO
quartz
™ HK /.__
80
^60 cristobalite
/V
V \\\ Fig. 45 — Quartz and cristobalite content
\\ in terms of the temperature of heat treatment
N^v | (Czechoslovak quartz raw material from the
800 1000 1200 1400 1600 1800 Detkovice deposit)
f CO
quartz
100
80
60 .cristobalite
40 h
Fig. 46 — Quartz and cristobalite content
20 in terms of the temperature of heat treatment
(Czechoslovak quartz raw material from the
^ 800 1000 1200 1400 1600 1800 Svedlär deposit)
- t CO
100
Micrographs of quartz raw materials heat treated at 1600, 1700 and 1800 °C
respectively are shown in Figs 47, 48 and 49.
The results of X-ray structural analysis indicate that the Czechoslovak vein quartz
raw materials (Svedlar, Detkovice) form clear silica glass via the transient amorphous
Fig. 47 - Pictures of quartz raw materials heat treated at 1600 °C: from the left - Soviet Kyshtym
quartz raw material, Brazilian crystal, Czechoslovak quartz raw material from the Detkovice deposit,
Czechoslovak quartz raw material from the Svedlar deposit
Fig. 48 — Pictures of quartz raw materials heat treated at 1700 °C (for designation refer to Fig. 47)
Fig. 49 - Pictures of quartz raw materials heat treated at 1800 °C (for designation refer to Fig. 47)
101
phase (the balance up to 100%) and cristobalite, whereas the formation of cristobalite
is substantially limited in the Kyshtym raw material, and only very small amounts
of cristobalite arise in Brazilian crystal. On the basis of a study by Sinelnikov [10],
these experimental results can be explained by the presence of the so-called miner-
alizers. Tables 21 list the chemical compositions of the quartz raw materials in
question.
The mineralizers form readily melting eutectics well wetting the quartz surface
and decreasing the intersurface energy, which facilitates the creation of nuclei of
cristobalite as a new phase. The significance of the liquid phase is therefore based
on the formation of crystallization nuclei, which is followed by the conversion of
quartz to cristobalite in the solid phase.
Moriya [11] examined the temperature pattern of the phase transformations of
quartz for various times of heat treatment. The results are plotted in Fig. 50.
As mentioned before, the process in which the melt is formed is also affected by
the presence of inclusions, microfissures, accompanying minerals, etc. The subject
is given more attention in the following sections.
100
£. 60
silica glass
20 cristobalite \
1450 1500 1550 1600 1650 1700
- fCC)
100
quartz . Λ ...
I - ^ S silica glass
Γ
v /
\ cristobalite ,
i · 1
I 20 1550 1600 1650 1700
~- f ( X )
Fig. 50 - The content of quartz, cristobalite and amorphous phase in terms of temperature; grain size
of the quartz 0.25 mm, heating for 60 h (a), heating for 12 h (b)
The synthetic raw material to silica glass phase transformation

A diagram of the phase conversion taking place during the heating of a synthetic
silica raw material (Si0 2 gel) in an oxidation atmosphere is shown in Fig. 51 (fol
lowing Pryanishnikov [1]).
102
In the case of Si0 2 gel, cristobalite is already formed at 1100 to 1150 °C. As follows
from Fig. 51, the formation of glass is a complex process depending on the technology
employed, the structure of the initial raw material, the dispersion of the amorphous
gel, its water content, etc. It is interesting to note that rapid quenching of the melt
Si 0 2
_>melt
2?
melt of variable
//J
ST
to density s,
1_
Q.
1 //j>T amorphous t ι
a-cristobalite
I
I
I
Fig. 51 - Diagram of phase transformations of
amorphous Si0 2 at normal pressure in an
' / i| phase | | | I
1/ !i i l l I
1
oxidizing atmosphere
220-270 1150-1250 -1400
fCC)
from 1400 to 1450 °C yields an amorphous semitransparent substance containing

closed pores about 5 to 10 μιη in size. The refractive index of this substance
(ηΌ = 1.462) is higher than that of silica glass. The infrared absorption spectra do
not differ from those of silica glass, so that the substance is probably a so-called
low-temperature modification of glassy Si0 2 .
3.2.2 Liberation of gaseous components during the heating of quartz
As mentioned in Section 2.2.2, natural quartz raw materials serving for the
production of silica glass have formed under various geological conditions of press
ure, temperature, composition of solutions from which they have crystallized and
composition of the ambient rocks, and under various tectonic influences. They
therefore differ in the types and numbers of heterogeneous centres associated with
compressive faults, and with the various types of liquid, gas-liquid or gaseous in
clusions, which may have various shapes and sizes as well as content. In addition
to this, they may differ in their content of inclusions of accompanying minerals,
various coatings of foreign substances, colouring with pigments, type and number
of structural defects, and other factors, as described by Kostyleva [13], Cherenisin,
Boganov [14], Shchekoldin [15] and others.
The present Chapter deals with the subject of liberation of gaseous, gas-liquid
and liquid inclusions in the course of heating various quartz raw materials of diverse
geological origins. Figure 52 shows micrographs of inclusions occurring in the
grains of quartz raw materials of various geological origins, and Fig. 53 illustrates
the detailed character of the inclusions.
103
Fig. 52 — Micrographs of inclusions in the grains of quartz raw materials, magn. 80 x and 500 x ;
(a) — Brazilian crystal
104
(b) - American raw material Arkansas I
105
^βτ ***%*|||# φ
(c) — African raw material from Angola I
106
(d) — Soviet raw material Kyshtym
107
(e) — raw material of Thermal Syndicate Corp.
108
ff,
(f) - Soviet raw material MBK (Svetlorechensk)
109
(g) — Czechoslovak raw material Grapa
110
(h) — Czechoslovak raw material Svedlär
111
(i) — Czechoslovak raw material Detkovice
112
(j) - Bulgarian raw material
113
l*Wl;· "^βΡ:
Jp^^M
(k) — Libyan raw material
114
Fig. 53 - Detailed characteristics
of two-phase inclusions in grains of
the Czechoslovak raw material from
the Svedlär deposit
115
Figure 52 indicates that the concentration, character and size of inclusions in raw
materials of various geological origins show distinct differences which affect not only
the quality of the quartz, from the standpoint of its utilization for the melting of
silica glasses, but also necessitate selection of the melting processes and technologies
suitable for reducing substantially the content of inclusions. The problem is as
sociated with the liberation of gases.
A number of studies, e.g. that by Kostyleva [13], Pryanishnikov [1] and others
[16, 17] show that liquid inclusions contain solutions of alkali chlorides, and tend
to open up (crack) already at the lower temperature stages of heat treatment, as
a result of pressures acting on the walls of the inclusions.
In contrast to this, inclusions containing a gaseous phase only, e.g. N 2 , H 2 , 0 2 ,
CH 4 , H 2 0 , C 0 2 , open up much less readily and at much higher temperatures during
heat treatment.
From the standpoint of opening up (decrepitation), the gas-liquid inclusions are
somewhere in between.
Inclusions of larger sizes are already partially liberated during calcination of the
quartz raw materials in the course of refining (dressing); however, their character,
size and concentration will change during heat treatment only at the higher tem
peratures (melting) and under reduced pressure, as shown in Fig. 54 for the Czecho
slovak Svedlär and the Soviet Kyshtym raw materials. The heat treatment was
carried out by the procedure illustrated in Fig. 42.
The micrographs taken during microscopic evaluation reveal changes in the
concentration and size of inclusions, formation of microfissures, cristobalitization,
decrepitation of grains and formation of the amorphous phase. These changes,
taking place in the course of heat treatment, are specific for the individual quartz
raw materials.
One of the methods used to study the so-called decrepitation of inclusions in the
grains of quartz raw materials is the so-called acoustic thermal analysis, which was
described in detail by Kostyleva [13], Hlaväc [46] and Jefäbek [47]. The method
is based on measuring and recording the acoustic effects that result from the cracking
of quartz grains due to the pressure created in the inclusions during heat treatment.
The results of measurements on Czechoslovak quartzes of 1 to 4 mm grain size from
the Detkovice and Svedlär deposits are shown in Fig. 55.
The decrepitograms show the temperature region of intensive decrepitation effects
and their frequency, while the intensity of the explosions is proportional to the
intensity of the acoustic effects. The mechanism involved in the releasing of liquids
and gases from the inclusions is therefore based on mechanical destruction of the
inclusions, resulting from rising pressure. Inclusions of foreign minerals or changes
in volume accompanying the conversion of modifications show much weaker effects
compared to the destruction of primary and secondary two-phase inclusions.
Heating will therefore liberate gases and moisture adsorbed in the surface of quartz
116
Fig. 54 - Micrographs of inclusions in heat-treated grains of quartz raw materials, magn. )x and
500 x respectively: Czechoslovak raw material Svedlär:
(a) - 800 °C
(b) - 900 °C
118
3ra*
!#ä^
fc/W#J
*.■&*
*'^*HL»!·
mW
(c) - 1000 °C
119
* i *
Ψ -Z5 s»' *
I % -
(d) - HOO°C
120
(e) - 1200°C
121
122
(g) - 1400°C
123
m
% > &
;
M
V"««-*.
(h) - 1500°C
124
(i - 1600 °C
125
I +*
Soviet raw material Kyshtym - (aj - 800 °C
126
, . *·***"
(b.) - 900 °C
127
mm
λ *^
(c t ) - 1000 °C
128
(d,) - 1100°C
129
·■">-....,. · V «
■ *\%&&&&*; 4*** t - *#
# 4 *» ^ :%>
:*#
(et) - 1200 °C
130
(f,) - 1300 °C
131
( g l ) - 1400 °C
132
st;
"mm m %
133
134
330 320 290 280 270
fCC) —
"~Ί
500 400 300 200 100
fCC) —
Fig. 55 - Acoustic effects due to cracking of quartz grains during heat treatment: (a) - Czechoslovak
quartz raw material Detkovice; (b) — Czechoslovak quartz raw material Svedlar
N-5
~ 5.10 Λ
It
<v
"6
E
il .5
Ü 10.10*
o -Detkovice
§
O 8.10" /
o V / Svedlar
3.10" h5 Brazilian
7
"o , crystal cn *»...'
6.1Ö5 /
o "Svedlar
o o
\
X 4.1Ö5 \
\ Brazilian
1.10
\\ Detkovice ...I crystal
2.10"
y j
Kysthym
Kyshtym
_!_
11001300 1500 1100 1300 1500
-fCC) -fCC)
Fig. 56 — The amount of liberated C0 2 in Fig. 57 - The amount of liberated H 2 0 in
terms of temperature (for various quartz raw terms of temperature (for various quartz raw
materials) materials)
135
grains, as well as the gases contained in inclusions. High-temperature vacuum
extraction, which allows the degassing to be studied, and tensiometric determination
of the components of the gaseous mixture following extraction at temperatures
higher than that used in acoustic thermal analysis, were used to evaluate quartz raw
materials having a grain size of 0.1 to 0.5 mm on samples 0.3 to 0.4 g in weight. The
degassing was effected by evacuation (6.7 to 8.0 Pa, time of extraction 30 minutes).
o
E 5.1Ö 3 o 1 Detkovice
i /
/ Detkovice o%
o E
o A. 10 °* A.1Ö3
E "o
o 3.1Ö3 § 3.1Ö 3
cn
en
c
Co Έ I
c O -3
* 2.1Ö3 U | 2.10 I
c
/^/Svedlar a //v-Svedlar
8
■'Ί \
C
o
c
I
1.1Ö3
y i\ ( 1.1Ö h ' ί'\ Brazilian
/'·'' \ / Kysthym /.··' \ · · . / crystal
/ > - — N ,; -' Brazilian
Γ , ' ^ - r crystal
7 ^•-r^^ Kysthym
1100 1300 1500 1100 1300 1500
-M'C] -M"C)
Fig. 58 — The amount of liberated Fig. 59 — Total amount of liberated gases in
non-condensing gases in terms of temperature terms of temperature (for various quartz raw
(for various quartz raw materials) materials)
The liberation of H 2 0 , C 0 2 and of the non-condensing gases (H 2 , N 2 , 0 2 , CH 4 and

others with a boiling temperature lower than —78 °C) at temperatures from 1100
to 1500 °C is plotted in Figs 56, 57, 58 and 59.
Significant differences in the degassing of quartz raw materials of various geo
logical origins and from different deposits in the course of heat treatment have to
be considered, particularly in devising the technological melting processes.
In connection with the results of high-temperature vacuum extraction of gases and
with the character of inclusions, a brief mention should be made of the liberation
of alkalis in the course of heat treatment. The results of chemical determination of
Z N a 2 0 + K 2 0 in quartz raw materials [18], heat treated by the process illustrated
in Fig. 42, are plotted in Fig. 60.
136
Heat treatment, particularly that of quartz raw materials containing higher
amounts of alkalis, has been found to result in a distinct decrease of L N a 2 0 + K 2 0
concentrations at temperatures higher than 1400 °C.
140
* Svedlar
~i 120
\
ji100| \
o \
\
£ 80 \
4 60 ι
o
μ ^ , ^ . ν ^ : ΐ 4 _ _ . _ \^ - Detkovice
MBK
* 20 Kyshtym \
Uu. z \ Brazilian
1i-S- " "' ΐ ^ ν ^ crystal pig. 60 - The content of N a 2 0 + K 2 0 in
800 1200 1600 terms of temperature (for various quartz raw
*- M*C) materials)
The concentration of alkalis in silica glass affects substantially its physico-chemical

properties, so the problem of attaining a minimum concentration is highly topical,
in particular in the melting of Czechoslovak vein quartz raw materials.
3.2.3 The effect of admixtures and accompanying minerals on the formation

of silica glass
Colourless and coloured accompanying minerals occur in natural quartz

raw materials which have formed under various geological conditions, temperatures,
pressures, composition of their maternal solutions, composition of the ambient
rocks and tectonic influences. In silica glass, these minerals form characteristic
heterogeneous (anisotropic) colourless, coloured and crystalline centres of various
shapes, which impair the quality of the ware.
The following minerals usually occur in natural quartz raw materials:
Actinolite (Ca2(Mg, Fe) 5 [Si 4 0 1 i] 2 (OH) 2 );its physical properties change with the
Fe content. Its colour is green in various shades, the mineral is transparent, its density
is 3000 to 3300 kg m" 3 , nm = 1.614 to 1.658, ηΌβ = 1.625 to 1.660, ηΌγ = 1.641
to 1.667,
Ankerite (FeC0 3 , CaC0 3 ); the Fe is usually partially substituted by Mg and Mn.
The density is 2900 to 3100 kg m" 3 , ηΌ ~ 1.518 to 1.526.
Apatite (Ca 5 [P0 4 ] 3 (F,Cl)) contains admixtures of OH, Mn, Nd, Pr, Ce, La. Its
colour is green to blue, density 3160 to 3220 kg m" 3 , ηΌω = 1.632 to 1.655, ηΌε =
= 1.630 to 1.651.
137
Biotite (K(Mg,Fe)3[Si 3 AlO 10 ](OH,F) 2 ), brown to black-brown in colour, density
2800 to 3200 kg m" 3 , ηΌα = 1.584, ηΌβ = 1.648, ηΌγ = 1.648.
Epidote (Ca2(Al,Fe) 3 [Si30 12 ](OH)); the composition varies and the Fe content
changes; the species rich in Mn is called piemontite. Its colour is bottle green to brown-
green, density 3300 to 3490 kg m" 3 , ηΌα = 1.729 to 1.734, ηΌβ = 1.750, nDy = 1.771
to 1.780.
Garnet (RSR^SiOja), where R" is Ca, Hg, F e 2 + , M n 2 + and R"' is Al, F e 3 + , Cr,
M n 3 + , Ti. The individual basic components are isomorphously miscible, and garnets
are divided into two subgroups: I — almandinic, II — andraditic. The colour is
brown, black, yellow, green, red, the density 3300 to 4300 kg m~ 3 , nD = 1.70 to 1.89.
Hematite (Fe 2 0 3 ), usually with an admixture of Ti and Mg. Its colour is brown-red
to dark red, density 5200 kg m" 3 , ηΌ ~ 3.101 to 3.220.
Chlorite (hydrated aqueous silicates of Mg, Fe, Al, sometimes also of Cr and Ni),
does not contain alkalis, in contrast to micas. The colour is green, white-grey to
black, the density is 2600 to 3000 kg m~ 3 , ηΌ ~ 1.562 to 1.660.
Ilmenite (FeTi0 3 , FeO.Ti0 2 ); usually contains Mg and Mn as isomorphous ad
mixtures. The colour is black, metallic glossy, density 4600 to 4900 kg m" 3 ,
ηΌ ~ 2.720.
Calcite (CaC0 3 ), contains admixtures of Mg, Mn, Fe. The colour is pink to reddish,
translucent, density 2710 kg m" 3 , ηΌε = 1.486, ηΌω = 1.658.
Leucoxene (Ti0 2 .nH 2 0) is formed by conversion of ilmenite. Translucent to
brownish in colour, density 3500 to 4500 kg m~ 3 , the ηΌ is approximately the same
as that of ilmenite.
Limonite (a mixture of F e 3 + hydroxides); a varying H 2 0 content and purity are
its characteristic features. Yellow-brown colour, opaque, density 4300 to 4500 kg m~ 3 ,
ηΌ ~ 2.060.
Muscovite H 2 K(Al,Fe) 3 [Si0 4 ] 3 ; the K 2 0 is usually substituted by up to 2.5%
N a 2 0 , H 2 0 is likewise substituted by up to 1% F. The colour depends on com
position, the density being 2780 to 2880 kg m~ 3 , ηΌ ~ 1.590.
Pyrite (FeS2), usually contaminated with Ni, Co, As, Sb, Se, Cu. Its density is
5000 to 5200 kg m" 3 .
Rutile (Ti0 2 ), usually contaminated with Fe. Red-brown to black-brown colour,
metallic glossy, density 4200 to 4300 kg m" 3 , ηΌ ~ 2.616.
Siderite (FeC0 3 ), usually contaminated with Mn. Yellow-brown to grey-brown
in colour, translucent, density 3780 to 3890 kg m" 3 , ηΌ ~ 1.855.
Turmaline (a complex borosilicate) may contain Li, Mg. Its colour is black or pink
(rubellite), brown (dravite), colourless (achroite), blue (indigolite), green (verdelite),
density 3000 to 3250 kg m" 3 , ηΌε = 1.62 to 1.66, ηΌω = 1.65 to 1.70.
The concentrations of some of these minerals in quartz raw materials (depending
on the dressing method and the geological origin of the raw material) are listed
in Table 26.
138
Table 26
The number of grains of heavy minerals in refined quartz raw materials
Quartz raw material ι Number of grains of heavy Character

minerals in
1 kg of raw material
1
Kyshtym (refined) 70-2000 black, yellow
Svedlär (refined) 10-1000 black, red, brown, brown-red
Detkovice (refined) 250-2800 black, red, brown, brown-red
MBK-Svetlorechensk 50-200 black with metallic lustre
Shchekoldin, Gladov, Bazurin, Pryanishnikov and Krivko [15] separated the

foreign minerals from the Soviet Kyshtym raw material and introduced them into
a pure quartz raw material. After melting it into silica glass, they determined the
characteristics of the heterogeneous colourless and coloured centres, as shown in
Table 27.
Figure 61 presents a micrograph of typical heterogeneous centres occurring in
silica glass melted from the Czechoslovak Svedlär quartz raw material.
The separation of admixtures and accompanying minerals is dealt with in Sec
tion 3.3.
Fig. 61 — Impurities in melted silica glass

Table 27
Assessment of the character of minerals dissolved in silica glass [15]
Mineral Property Glass block Polished section
incident light transmitted light crossed nicols
Rutile shape consists of spherical core and mesentery black core
colour
optical properties green-blue dark green isotropic
Titanite shape ellipsoidal, drop-shaped, kidney-shaped core also

consists of core and mesentery crystallized
colour
optical properties grey-blue grey-blue strong birefraction
at inclusion
boundary
Hematite shape irregular, sometimes with spherical cracks and veil around core partially or
cosists of core and mesentery completely
crystallized,
core dark brown,
colour mesentery light
optical properties white brown isotropic, slight brown
birefraction at
boundaries
Pyrite, shape spherical

goethite, consists of gaseous bubble with mesentery around
iron
colour colourless bubble black bubble
optical properties grey mesentery brown mesentery isotropic, slight
birefraction at the
boundaries
Actinolite, shape spherical crystallized core

apatite, consists of core and mesentery, sometimes veil around
calcite, a spherical crack
ankerite
colour core light grey,
white, veil bluish
optical properties isotropic, intensive
birefraction in the
neighbourhood
Feldspars, shape irregular differs from glass

muscovite, consists of fibriform bundles in refraction only
biotite,
turmaline, colour colourless almost
chlorite, optical properties indistinguishable well discernible birefraction along
garnet shade boundaey fibres and inclusion
boundary boundaries
3.2.4 The effects of furnace atmosphere and furnace material on the formation
of silica glass
Under ideal conditions, conversion of quartz to the amorphous phase on

heating should only involve the rearrangement of bonds. The melting would of course
have to be carried out in a neutral or oxidation atmosphere, in the strict absence of
other substances.
In practice, these conditions can only be met on the assumption of using high-
purity granulated Si0 2 monocrystal and melting in an oxygen, argon or nitrogen
atmosphere.
It is further necessary to take into account the materials in which the melting takes
place; for example, a graphite crucible is responsible for a reduction atmosphere, and
even the presence of a neutral gas cannot prevent reduction, as shown in Chapter 2.
Most technologies used in the melting of clear silica glass (apart from the special
ones) proceed under more or less reducing conditions, which result from the presence
of admixtures in the material of the melting furnace, the atmosphere produced by the
reaction of Si0 2 with the furnace material, etc.
The effect of the furnace atmosphere and that of the material of the furnace parts
(crucible, heating element, thermal insulation, etc.) are usually interrelated. More
over, gases with a reducing effect are intentionally introduced into the melting space
(e.g. H2 in the oxygen-hydrogen flame, H2 + N 2 to protect molybdenum crucibles
from oxidation).
Decomposition of quartz under reducing conditions yields mostly SiO, whose
vapour pressure at 1700 to 1750 °C is higher by two orders of magnitude, and at
2000 °C higher by one order, than the vapour pressure of Si0 2 . The reaction of Si0 2
141
with graphite produces CO, SiC, Si and other silicon compounds (cf. Chapter 2). The
SiO and CO arising in gaseous form, whose amount and pressure increase with
increasing temperature, penetrate the charge between the Si0 2 grains where SiO
may condense under suitable conditions, or where Si0 2 may be further decomposed
and reduced. A survey of the main possible reactions is given in Chapter 2. Their
product is the so-called reduced glass, of the non-stoichiometric composition 8ί0 2 _*.
The presence of the so-called unsaturated bonds in the structure of glass is revealed
by absorption of radiation at 242 nm, where the depth of the absorption band is
proportional to the degree of reduction.
1.4
1.2
1.0
0.8
* 0.6
Q4
0.2
300 280 260 240 220

λ (nm)
Fig. 63 - Characteristic absorption bands in glass samples taken

from the ingot shown in Fig. 62
In agreement with the idea of the reducing effect of SiO, CO or other reaction
products in the gaseous state, the distribution inhomogeneity of the reduction degree
was determined in a commercially-melted ingot of clear silica glass (technology of
Quartz and Silice Corporation) with an outer diameter of 140 mm and inner diameter
of 50 mm, and 500 mm in height. The points of sampling are shown in Fig. 62.
142
1Ah
1.2 h
1.0Γ
0.8 l·
tH
ΟΛ[
0.2r
Fig. 64 — Characteristic absorption

bands in glass samples taken from
300 280 260 2A0 220 the ingot in Fig. 62
■ λ nm)
0.8 r
0.7 \
Q6l·
0.A
A
03
0.2
0.1 Fig. 65 - Characteristic absorption

bands in samples of glass melted in
the laboratory under various
300 280 260 240 220 conditions
λ (nm)
143
Figures 63 and 64 are plots of the exponential absorption coefficient vs. wavelength,
and indicate that the maximum absorption was exhibited by samples taken from the
point farthest from the exhaust ports, i.e. at the bottom part of the ingot, where the
gases pass through a perforated "chimney" to the crucible centre, upwards and out
of the furnace.
The effect of various conditions of melting in the VSG 02 laboratory vacuum
furnace is shown in Fig. 65.
The glass was melted from the Svedlär Czechoslovak vein quartz raw material,
in a graphite crucible. In the first case (Fig. 65, curve 1) the glass was melted in vacuo
by the standard process, with a maximum melting temperature of 1800 °C for
15 minutes. In this case, the absorption band has the highest intensity. In the case of
curve 2, the glass was melted in the same way, but then reheated in vacuo and argon
was introduced at 1900 °C. The absorption band is less distinct, and the absorption
of radiation is markedly lower over the range of 220 to 300 nm.
Curve 3 characterizes glass melted in the same way as for curve 1, but direct
contact between the quartz and graphite was prevented by placing a silica glass
crucible within the graphite one. The absorption can be seen to be minimal.
The so-called darkening of silica glass is an extreme case of the influence of a re
ducing medium and reducing substances. The darkening proper is therefore due to
the non-stoichiometric composition of Si0 2 , the presence of submicron particles
of Si and C, or possibly other products of reduction in a colloidal state.
The effect of Mo and W materials (used in some technologies as melting vessels)
is described in Section 2.2.1.4, from the standpoint of their interaction with the silica
glass melt.
3.2.5 Reactions of synthetic raw materials
This subject is adequately considered in connection with the account of the

properties of synthetic raw materials suitable for the melting of clear silica glasses
(Section 2.2.6) and the description of production technologies (Section 3.4). For
more detailed information, the reader is referred to the literature [73 to 76, 78, 82,
84, 86, 87, 92, 93, 94].
3.2.6 Thermodynamic aspects of the formation of silica glass
The terms amorphous and glassy state were briefly dealt with in Section 3.2.
Silica glass can thus generally be defined as a substance in the amorphous state, i.e.
a substance not exhibiting the properties of a crystaline substance. Figure 66 shows
X-ray diffraction patterns of crystalline ß-quartz and amorphous silica glass, demon
strating the validity of the given definition.
144
Fig. 66 — Diffraction X-ray patterns of crystalline quartz (a) and amorphous silica glass (b)
Silica is therefore capable of forming a supercooled liquid (glass) on over-cooling

(supercooling) from a temperature above the melting temperature of high-tempera
ture a-cristobalite (1723 °C) and "freezing" into an amorphous (glassy) state.
The melt to silica glass phase conversion differs somewhat from the conversion
of multicomponent silicate glasses, in spite of their containing Si0 2 as the main
component. In explaining the formation of glass by supercooling its melt, let us first
consider, with Bruckner [19], the typical behaviour of silica glass and express the
dependence of its volume on temperature (Fig. 67).
The so-called transformation temperature, tg (Fig. 67(a)) differs from the so-called
second-order transformation point t2 (Fig. 67(b)) in its kinetic behaviour. On quenching
from a high temperature a substance exhibiting a second-order transformation point,
the point will shift towards temperatures lower than if a lower rate of cooling were
used. In contrast, the transformation temperature tg will shift towards higher tem
peratures, which distinguishes the group of glasses from other crystalline and amorph
ous substances.
In the case of silica glass, the curve of the temperature dependence of volume
exhibits a minimum at about 1500 °C (in the region of structural metastable equi
librium of the supercooled liquid), and another minimum at about - 80 °C (in the
glassy state), as demosntrated in Fig. 68.
At temperatures above 1500 °C, the change in volume due to rapid quenching
is similar to that of current types of silicate glasses (Fig. 68). However, the behaviour
of silica glass differs from that of current silicate glass over the anomalous tempera
ture region of 1000 to 1500 °C, particularly with respect to changes in volume due
to reheating of rapidly quenched glass (indicated by arrows in Fig. 68). These changes
145
slow heating
metastable
melt
rapid heating Q
glassy state / I ^J^C stable melt
f
Fig. 67 — Specific volume V vs. temperature for glass (a) and other amorphous substances (b):
tm — melting temperature, tgs and tgf — transformation temperature at various cooling rates,
t2f and t2s — second-order transformation for various cooling rates
crystallization
Fig. 68 - Specific volume

of silica glass
—\ stable melt vs. temperature
in volume have a character opposite to that of current silicate and other types of
glass, but are qualitatively identical in respect of the shift of transformation tempera
ture with the rate of cooling.
3.2.7 Structure of silica glass
The lack of periodicity and symmetry of the structure of silica glass, which
produces a significantly less clear pattern in X-ray diffraction analysis, is one of the
main factors which have so far restricted general knowledge of the structure of the
glassy state. The structure of glass is thus similar to that of liquids.
The elementary structural formations, i.e. the groupings of atoms, ions or molecules
constituting silica glass at the shortest distances, are nowadays known in principle;
however, no explicit concept of the mutual arrangement of these formations has so
far been found. A brief account of some theoretical ideas on the structure of silica
glasses is therefore given below.
The basic theory of the structure of glasses was introduced by Tammann [20];
Lebedev [21] developed the crystallite theory, and Zachariasen's theory [22] was
expanded by Warren [23]. On the basis of these structural concepts, which differ
in their principles, some aspects of the formation and structure of the glassy state
were investigated in detail e.g. by Smekal [24], Stanworth [25], Winter [26], Sun
[27], Porai-Koshits [28], Botvinkin [29], Weyl and Marboe [30], Rawson [31],
Mackenzie [32] and others.
Zachariasen's theory was extended by Warren [23], who carried out X-ray exam
inations of glassy Si0 2 (silica glass). The X-ray diffraction curves of glassy Si0 2 ,
cristobalite and Si0 2 gel are shown in Fig. 69.
cristobalite
\
\ / x Si0 2 gel
/' χ silica glass
0.04 a08 0.12 0.16 0.20 0.24 0.28 Fig. 69 - X-ray diffraction curves of cristobajite, Si0 2 gel
-*- sin Θ/Χ. and silica glass
147
The agreement of the X-ray diffraction band of glassy Si0 2 with the main line of
crystalline cristobahte had earlier led to the assumption that silica glass consisted
of cristobahte microcrystals. However, from a comparison with the results of measure
ments on S i 0 2 gel (maximum X-ray scattering at small angles), Warren concluded
that the agreement of the position of the diffraction band with that of the main
cristobahte line corresponded preferentially to an approximately identical inter
atomic distance.
To evaluate the results of X-ray diffraction analysis, he generalized Zernicke-
Prince's equation for liquids into the form
2r f00
£/cm · 4nr2Qm = X>m · 4nr2Qo + — sH(s) sin rs ds (27)
π Jo
where km is the effective number of diffracting electrons in atom m,
ρ0 is the mean number of electrons in unit volume,
4πΓ2ρΙΏ dr is the number of atoms multiplied by the effective number of their
electrons at a distance of r to r + dr from atom m,
s = 4
sin Θ
and i(s) = /-Σ/»2
where / is the experimentally determined intensity of coherent scattering,
fm is the atomic scattering factor of atom m,
L=
Σζ„
and Z m is the atomic number of atom m.
Using the experimental curve (Fig. 69) for glassy Si0 2 and calculations from
equation (27), Warren plotted a radial distribution curve whose apex positions
specify the distances of atoms. The radial distribution curve for glassy Si0 2 is shown
in Fig. 70.
Fig. 70 - Radial distribution of electron

density in silica glass
148
The first apex on the radial distribution curve lies at a distance of 0.162 nm and is
in satisfactory agreement with the mean Si—O distance in the quartz crystal. Measure
ments in the area of the peak indicate that each silicon atom in glassy Si0 2 is sur
rounded, on the average, by four oxygen atoms located at an approximate distance
of 0.162 nm.
If the silicon atom is therefore surrounded tetrahedrally by four oxygen atoms,
the interatomic distance O—O should be
'3
Si—O 2 1.62
x = 0.264 nm (28)
O—O h x
This distance is in good agreement with the O—O distance in crystalline quartz.
The maximum at 0.32 nm corresponds to the Si—Si distance, and that at 0.45 nm
to the O—O n distance. The angle of the Si—O—Si bond is close to 180°. However,
at distances greater than 0.6 nm, the interatomic distances already depend consider
ably on the mutual orientation of the tetrahedral groups and the individual peaks
on the radial distribution curves slowly vanish (Fig. 70).
Stevel's structural parameters [33] further indicate that for the grouping of oxygen
atoms around a silicon atom in silica glass (Z = 4) the oxygen to silicon ratio
# = 2/1 = 2, so that
X = 2R-Z = 4-4 = 0 (29)
Y =2Z - 2R = 8 - 4 = 4 (30)
where Z is the mean number of all oxygen atoms in the polyhedron (mean coordi
nation number),
R is the ratio of the total number of oxygen atoms to the total number of
silicon atoms,
X is the mean number of non-bridging oxygen atoms in the polyhedron,
Y is the mean number of bridging oxygen atoms in the polyhedron.
The given calculations show that all the oxygen atoms are of the bridging type and
that all the apices of the basic tetrahedra are common. A maximum strengthening
of the structure is therefore achieved in the case of silica glass (glassy Si0 2 ).
According to Smekal [24], substances capable of forming glass must have the
so-called mixed bonds, because on cooling the melt the otherwise "disarranged"
structure of silica glass could not form. The bonds and bond angles in crystals are
strictly defined. This is why Smekal assumes a partially covalent and partially ionic
character of the bonds in the case of silica glass.
The problem of mixed bonds in glasses was also dealt with by Stanworth [25].
On the basis of the electronegativities determined by Pauling, he calculated the
proportion of ionic bonds in glassy Si0 2 .
149
If the electronegativity of Si = 1.8 and that of U = '5.5, the difference
3.5 — 1.8 = 1.7 indicates that the share of the ionic bond amounts to 50%.
During conversion of the Si0 2 melt, which constitutes structural units of large
dimensions (Bernal's type of liquid), to a supercooled liquid, the original bonds are
destroyed and new ones formed. In this instance, the strength of the bonds is unusually
high. The phenomenon was utilized by Sun [27] to determine the so-called single-bond
strength, by dividing the association energy by the number of oxygen atoms sur
rounding the cation (silicon). For the Si—O bond and the coordination number 4,
he determined a dissociation energy of 1775.2 · 10" 3 J, and the single bond strength
to be 443 · 103 J.
Rawson [31] made Sun's criterion of the single bond strength more precise by
dividing this value by the liquidus temperature, 1993 K.
The structure of defect-free glassy Si0 2 was demonstrated by Stevels [33] in
Fig. 71(a).
O O a) —
—
4000
|Si-0
ΟΟΌ.ΟΌ.Ο ^ 3000 I 0-Oj Si-Ojr.
O O Q ' B\
Si-Oj S]
A^>^^^
A
2000
i\f^>^
oA ό / b) IN - Si-Si
o /o ^ 1000
Yc\ \IE F
O.OWO.O t ^<^rWnJ
0.1
Ti/v
0.2
i
0.3 0.4
i |
0.5
|
0.6
i_
0.7
.-O^W O2 »- r (nm)
Fig. 72 — Radial distribution of electron density in
ΟΌ.ΟΌ.ΟΌ Amersil silica glass
o o
^ o o Fig. 71 — The structure of glassy S i 0 2 :
ondfojo'o (a) - free of defects; (b) - one silicon
o3+o
ion replaced by an aluminium ion short of
one electron, one electron hole in the
O Ό ·<*) network; (c) — one empty place at the point
οοοΐσοο of the missing oxygen atom; in the
o o o< neighbourhood, one silicon ion was

substituted by an aluminium ion and one
ΟΌ.Ο?Ο.ΟΌ
o lo electron retained; (d) — empty place of
a missing oxygen atom with two aluminium
ions substituting silicon atoms
The disarranged and aperiodic structure of glassy Si0 2 may be responsible for the
formation of structural defects of a local point nature, i.e. vacancies, or for the
positioning of interstitial ions in the structure. These defects may even have different
charges. The defects in the structure of glassy Si0 2 are illustrated in Fig. 71(b), (c)
and (d), following Stevels.
150
Mozzi and Warren [35] measured the radial distribution of electron density in
Amersil silica glass; the results are plotted in Fig. 72.
On the radial distribution curve, the maxima £, C and D correspond to the distances
Si—O (0.162 nm), O—O (0.265 nm) and Si—Si (0.312 nm) respectively. The equation
fsi-si = 2r
si-o sin - (31)
was used to calculate the Si—O—Si bond angle. The function V(a) of the change in
angle a is plotted in Fig. 73 and shows that in silica glass, the angle a changes from
120° to 180° with a probable peak at 144°. Another peak A, on the curve (Fig. 72)
appears at r = 0.415 nm and corresponds to the distance between the silicon atom
and the second oxygen atom (rSi_0lI). The fifth peak at r = 0.510 nm corresponds to
the superposition of the O—O,, and Si—Si„ distances apart. The last weak peak
at r = 0.640 nm probably corresponds to the rSi_0lII distance.
The given study indicated that the basic structure of silica glass probably consists
of [Si0 4 ] 4 " tetrahedra arranged non-uniformly throughout the space. The inter
atomic Si—O distance is 0.162 nm, the Si—O—Si bond angle varying over the range
of 120° to 180° with a probable maximum of the angular distribution at 144°. This
corresponds to the covalent model of the basic tetrahedron, with sp2 limit states
and sp-hybridization. However, this X-ray structural analysis was not capable of
examining the structure of the small regions, where a more arranged structure is
assumed to exist.
Neutron diffraction was used by Milligan [36] to study the structure of glassy
Si0 2 . Although the results of his study differ somewhat from the results by Mozzi
and Warren [35], the calculated Si—O—Si bond angle (146°) is in agreement.
10 000
og
J5 5 000l·
1000
120 130 140 150 160 170 180

ocC)
Fig. 74 — Radial distribution of electron density
Fig. 73 - Function V(x) in silica glass: 1 - at 20 °C, 2 - at 1600 °C
151
Further weak peaks were found at 0.59 nm, 0.66 nm, 0.74 nm, 0.9 and 0.97 nm, and
are explained by the presence of regions with a higher degree of arrangement.
Zarzycky [37] carried out an X-ray structural study of glassy Si0 2 at 20 and
1600 °C; the results are shown in Fig. 74.
He determined the interatomic distances Si—O (0.160 ± 0.005 nm), Si—Si
(0.30 ± 0.005 nm) and the Si—O—Si bond angle over the range of 126° to 160°
(the mean value was 143° ± 17°). There was a characteristic linking of some peaks
of curve 2 from measurements at 1600 °C with those of curve / measured at 20 °C,
particularly at the viscosities of 107 to 108 dPa s, when the glass is in a viscoplastic
state.
On the basis of their research, Dean and Bell [38,40] assume the structure of glassy
Si0 2 to be composed of uniform [ S i 0 4 ] 4 ~ tetrahedra (Fig. 75(a)) joined by a common
oxygen atom (Fig. 75(b)).
\
NJ^
Q2
■QA 0.6 0.8
r (nm )
Fig. 75 - Basic [ S i 0 4 ] 4 ~ tetrahedron (a) and Fig. 76 — Radial distribution of electron density
two tetrahedra bound through an oxygen atom in silica glass: a — measured by the neutron
(b) in silica glass diffraction method; b — histogram of a model
of disarranged spatial structure;
c — histogram of a model, after Tilton
In agreement with the data by Warren, Milligan, Zarzycky and others, these
authors explain the disarrangement of the structure by the variable values of the
Si—O—Si bond angle and by the thermal oscillation of bonds in the tetrahedron
(particularly of the silicon-common oxygen bonds). Based on the assumption of
a disarranged spatial network with an Si—O—Si bond angle of about 150°, they
constructed various models of glassy S i 0 2 consisting of 600 atoms. The computed
histograms of these models were compared with experimental values obtained from
scattering of X-rays and neutrons, as shown in Fig. 76.
The EPR method [1] revealed that the signal of the E' centres depends on the type
of silica glass, the initial raw material and the melting method, as demonstrated in
Fig. 77.
152
The measuring results imply that the EPR spectra of silica glass melted from
natural quartz raw materials (1) and from SiCl4 (2) are identical with, or similar to,
the spectrum of ß-quartz. A much more complex signal analogous to that of synthetic
cristobalite (3,4) is found in the spectra of glasses melted from synthetic cristobalite.
The results showed the structure of silica glass to be close to that of the initial raw
material.
Balashov, Chernyshev, Sanin, Varshal and Pavlova [39] present the results of
measuring the speed of absorption of ultrasound in pure silica glass containing
A1 2 0 3 and T i 0 2 , over the temperature range of 0 to 300 K. The results are plotted
in Fig. 78.
* M
200 300
— r (K)
Fig. 77 - EPR signal in Fig. 78 — The speed of ultrasound (a) and absorption of ultrasound (b)
various modifications of silica in silica glass: 1 — clear silica glass; 2 — silica glass containing
glass: 1 — silica glass melted 5 mol% A1 2 0 3 ; 3 — silica glass containing 6 mol% T i 0 2 ;
from /?-quartz; 2 — silica 4 — silica glass containing 11 mor% T i 0 2
glass melted from SiCl 4 ;
3 — silica glass melted from
synthetic cristobalite;
4 — silica glass method
from cristobalite;
5 — cristobalite
It may therefore be concluded that Pryanishnikov's assumption of the existence

of a number of possible structures of silica glass, differing only very slightly (depending
on the structure of the starting raw material), appears to be justified. Also, it appears
that it should be possible to synthesize silica glass with a prevalence of a certain
type of hybrid bonds.
For details on the structure of multicomponent glasses the reader is referred to
the literature [22, 24, 25, 27, 28, 30, 31, 32, 33, 34].
153
3.3 R E F I N I N G O F NATURAL QUARTZ RAW MATERIALS
FOR THE PRODUCTION OF SILICA GLASS
The manufacture of refined quartz is a demanding technological process

consisting of a number of operations. The sequence of the operations has to be
maintained, while also maintaining the working procedure of the individual oper
ations. The grinding and milling of quartz and the final handling of dry fine quartz
require suitable pneumatic equipment.
The chemical refining of quartz with the use of relatively corrosive acids likewise
demands strict adherence to safety regulations. The concluding operations, the
drying and packing of refined quartz, have to be performed in a special clean environ
ment in order to rule out secondary contamination of the refined product.
3.3.1 Basic refining processes for the quartz raw materials
The refining of the raw materials is indispensable for all types of natural
quartzes because of the strict quality requirements on the raw material for the
manufacture of clear silica glass, as described in Chapter 2. The refining must ensure
the required grain size and reduce the heterogeneous impurities to the level laid
down by the technical specifications.
The refining process should generally include the following operations:
(a) crushing and grinding the quartz, to limit the grain size and to open up the
grains and gain access for the refining bath to crystals interspersed with foreign
minerals;
(b) classification according to grain size, to obtain the required grain size distri
bution of the material.
(c) elimination of harmful admixtures by suitable methods, e.g. electromagnetic
separation, flotation or chemical refining;
(d) dewatering, drying, packing and sampling of the product obtained.
Each raw material exhibits certain specific peculiarities which have to be respected
in the refining procedure. The general refining procedure is therefore usually modified
on the basis of chemical and mineralogical analyses of the respective raw materials.
For example, the raw material from the surface parts of the Svedlär deposit are
characterized by numerous ferric coatings and crusts or infiltrations of ferric oxides
in fissures deep inside the grains. Heat treatment converts the accessory minerals
of the limonite and sulphidic groups into oxides and sulphides which are difficult
to dissolve. Some of the annealed sulphides can be eliminated by electromagnetic
separation, and the rest have to be removed by chemical refining under suitable
conditions.
Similarly, problems arise in connection with the removal of leucoxene in the
refining of quartz raw material from the Detkovice deposit. Mineralogical analysis
154
shows that the grains of leucoxene originate from the ambient phyllites. The refining
of such quartz must include separation, as completely as possible, of rock fragments
and phyllite-quartz twins during the initial collection of the raw material from the
deposit, and then during the hand sorting of raw material at the dressing plant.
The conditions of heat treatment have to be strictly adhered to in the case of
Macedonian quartzes with a higher content of well crystallized muscovite. Imper
fectly calcinated muscovite is less readily soluble in the refining bath.
The refining process must be sufficiently flexible to provide for small variations in
quality of the raw material. When the raw material has changed, it is necessary to
reassess the complete refining procedure according to the properties of the new
quartz raw material, to determine precisely the conditions of refining and to produce
a so-called standard sample. The technological conditions of the melting process
for the quartz raw material have to be adjusted at the same time.
3.3.2 Methods of refining the quartz raw materials
The quartz raw material is mostly extracted from quartz veins by quarrying.
The optimum weight of the explosive charges is chosen according to the tectonic
faults and the characteristics of the quartz. Careful handling of the quartz raw
material is necessary, because lump quartz is best suited for the refining processes.
Fine-grained or powdered quartz formed during mining increases the weight of
waste in refining and decreases the yield values of the deposit. Under Czechoslovak
conditions, the quartz raw material is supplied in lumps of 30 to 250 mm. In the
Soviet Union, the raw material is sorted and ground to a suitable grain size on the
deposit, and supplied to the dressing plant in this pre-treated state.
Work on the deposit should be arranged with a view to subsequent processing
of the raw material. It is thus advantageous to prepare a pure quartz pre-concentrate
of the required lump size already on the deposit, thus making the entire extraction
and refining process more effective.
The raw material from the deposit is stockpiled at the dressing plant, in a way
precluding any secondary contamination. Then the raw material is introduced into
a washing drum, provided with holes 10 mm in diameter. The drum is revolved and
a stream of water removes clay particles, while also partly eliminating thick coatings
of the softer rock components. From the washing drum, the quartz lumps pass onto
a wide conveyer belt, where they are hand sorted. The lumps of quartz which do not
guarantee obtaining a satisfactory refined product after all the subsequent oper
ations are removed. Hand sorting is thus a largely subjective operation, requiring
certain experience. All the rock material has to be sorted on the belt; the operation
is particularly important with raw materials whose accompanying rocks are the
sources of some heavy minerals that are difficult to leach, e.g. leucoxene (the Detko-
vice deposit). Hand sorting also removes all foreign materials such as wood, coal,
155
wrappings, etc., quartz lumps containing large accumulations of minerals (admix
tures), and those with nests of mica minerals or with thick crusts of hypergenous
iron oxides. Also rejected are quartz lumps in which the impurities are not restricted
to sharply bounded fissures but penetrate long fine fissures deep into the quartz
material proper. These impurities are sometimes indicated by a more or less distinct
colouring of the quartz in its original state, but sometimes their presence is only
revealed after heat treatment. This is why the so-called second manual sorting is
carried out after heat treatment. This sorting allows the impurities to be removed
from the lump quartz, because it disintegrates readily after heat treatment.
The heat treatment (calcination) consists of heating the quartz throughout its
volume to a temperature exceeding that of the /?-quartz -> α-quartz conversion, i.e.
above 573 °C. If the heat treatment is carried out in a chamber furnace, the calcination
temperature has to be stabilized for 5 to 7 hours over the range of 600 to 800 °C. The
temperature gradient is equalized during this time, and the quartz raw material is
thoroughly heated even in the central part of the furnace.
Following calcination, the heated quartz raw material is quenched by pouring it
into a tank of cold water; the raw material cracks up extensively, and the quartz
becomes easy to grind. Some of the gas-liquid inclusions are simultaneously elimin
ated by the decrepitation process, and the dehydrated mica-type minerals are more
readily soluble in acids. The heat treatment has the main disadvantage of converting
ferric hydroxides of the limonite group to ferric oxides such as hematite, which is
more difficult to dissolve in acids. The sulphidic minerals (pyrite, chalcopyrite) give
up some of the sulphur on heating, and the resulting monosulphides can be more
easily removed by magnetic separation. The improved visibility of impurities and
the breaking up of the large quartz lumps in the cooling water tank allow the re
maining impurities, which escaped notice during the first sorting, to be removed
during the second.
The sorted and calcinated material passes into a jaw crusher with an output gap
25 mm in width. The crushed material is further conveyed into the grinding circuit.
Satisfactory results in the grinding of quartz are obtained with bar mills (or other
types of mills lined with non-metallic material) linked into a circuit with a spiral
classifier and a vibration screen. The material passing out of the mill is divided by
the spiral classifier into the coarser recycled fraction and the fine fraction flowing
onto a vibration screen. The size of the openings corresponds to the maximum grain
size required by the technical specifications. The oversize grains, together with the
coarse fraction from the spiral classifier, are recycled to the bar mill. The grinding
schedule depends on the characteristics of the raw material, and can be suitably
adjusted.
The undersize grains are pumped into a countercurrent water classifier, where the
ground quartz raw material is further classified in two stages. The fine fractions are
removed in the part falling over from the metering head of the classifier, as well as
156
in the so-called first overflow, where the required ascending current can be adjusted
by using a suitable nozzle, thus affecting the classification limit. In principle, most
of the fine fractions are removed in the overflow from the metering head; the classi
fication limit is set precisely in the first overflow, and the remaining fine fractions are
eliminated. The coarser undersize grains are the required product, whose grain size
in the technology used at the Sklotas Concern Corporation amounts to 0.08 to
0.5 mm. This product, with a standard grain size distribution, is pumped to the next
refining stage, the so-called electromagnetic separation.
As the grinding of quartz may be carried out in a steel plant, extensive abrasion
occurs and the quartz grains carry abraded particles of iron on their surfaces. Even
separate grains of iron and rust frequently occur among the quartz grains. The
former are dissolved during chemical refining (except in the case of alloyed materials),
but this operation prolongs the required time of refining. So the metallic particles
are separated from the material by wet high-intensity electromagnetic separation.
Use is made, for example, of the MSB-600 separator in line behind a ferrite magnetic
separator working with afieldintensity of 800 to 1000 k Am"1. The magnetic fraction
separated contains grains of abraded metal and relatively small concentrations of
hematite grains and quartz grains twinned with hematite grains. Although this
separation is in practice capable of removing only concentrated iron-based impurities,
it is very important for the overall effect of quartz refining.
The non-magnetic product is concentrated by settling and then dewatered in an
industrial centrifuge. The dewatered product is metered in 200 kg batches into a dis
continuous refining line.
Leaching of quartz is the most demanding of the technological operations. This
chemical refining is carried out in a medium of strong mineral acids, usually at
elevated temperature. The bath is highly corrosive, which puts considerable demands
on working safety. In Czechoslovakia, the vein quartz is refined in 20% hydrofluoric
acid (HF) for 2 hours at 50 to 60 °C. Hydrochloric acid has proved unsatisfactory,
because Czechoslovak quartzes contain accessory silicates (micas, chlorites) whose
elimination requires a highly corrosive bath.
The chemical refining of quartz in dilute HF was found to be most effective during
the first fifteen minutes of refining. During the further refining, the leaching removes
accessory point impurities, so that the two-hour refining obviously has a considerable
time reserve.
The leaching plant consists of several units. The refining of quartz is effected in
a revolving PVC or polypropylene drum. The drum material must show great
resistance to the hot bath of dilute HF, and high thermal endurance. The refining
temperature is raised from the initial 55 °C as a result of the strongly exothermic
reaction of HF with the fine quartz fractions, attaining 65 to 70 °C during the first
fifteen minutes of refining. During this time the bath temperature is monitored by
the operator.
157
The leaching bath is prepared in a storage tank. This is also used to hold used bath
liquid from previous leaching, with a residual concentration of 10 to 12% of HF.
The concentration of the bath is adjusted to 20% by adding fresh concentrated HF.
The bath is heated in a special heater before the refining proper, then passed into
the refining drum already containing the relevant charge of quartz material. Fol
lowing the refining, the pulp is discharged into nutsch filters, where the leaching bath
is separated. The leaching quartz is then thoroughly washed with pure potable, or
distilled, or deionized water.
The requirements for chemical purity are very strict, and have to be suitably
checked in commercial production. The quality inspection usually consists of taking
samples from each leached charge and chemical analysis of them, based on deter
mining some chosen important impurities. The analysis is mostly concerned with
determining the content of F e 2 0 3 . According to technical acceptance specifications,
samples of quartz raw materials to be shipped are subjected to complete chemical
analysis and sieving analysis. Mineralogical analyses are also carried out in some
cases.
Diverse procedures of quartz refining are used in various dressing plants. Quartz
is refined either in its original state, or after heat treatment (calcination). For example,
the Soviet Kyshtym quartz raw material is refined in a non-calcined state. However,
most quartz raw materials, including rock crystal, are refined by calcination.
The heat treatment of quartz may either be discontinuous, as in Czechoslovakia,
or continuous as in Poland, the German Democratic Republic and the USSR, where
the ground quartz is introduced into heated (600 to 800 °C) suitably inclined silica
glass tubes.
The crushing and grinding of quartz raw materials is also carried out in various
ways. Cylindrical mills are used for dry grinding in the USSR and the German
Democratic Republic, ball mills for wet grinding in the German Democratic Republic
and Poland, bar mills in Czechoslovakia and Poland and cone mills in the Federal
Republic of Germany.
In the USSR, the quartz raw material is ground in a device working on the prin
ciple of the electrohydraulic effect. This grinding method has the advantage of
producing isometric grains; the disintegration proceeds along the boundaries of
the individual grains, which facilitates refining in acids. However, the plant is com
paratively expensive, large in size and consumes considerable energy at a low output.
Whereas the crushing and grinding of quartz are standard dressing processes, the
second part of dressing, i.e. refining, must be based on the specific properties of the
particular raw material. Gravity, electromagnetic and chemical refining methods are
combined to achieve the required quality. As already mentioned, a suitable calci
nation schedule has to be chosen to improve the solubility, e.g. that of muscovite
in HF. In the case of Macedonian quartzes, the calcination temperatures have to be
raised to 800-900 °C to dehydrate the muscovite completely and render it leachable.
158
In the USSR, a number of dressing plants remove rutile and other non-magnetic
heavy minerals by a very expensive and slow method of separation in heavy liquids.
In spite of the rutile contents in quartz raw materials being only 10" 4%, their pres
ence in the manufacture of silica glass is detrimental, so that even such demanding
separation is justified. Rutile currently occurs in ore-free quartz veins.
The occurrence of leucoxene in quartz veins in the Detkovice deposit is of a similar
character. Some of it occurs in association with magnetic ferric oxides, and can
therefore be removed by electromagnetic separation. However, the remaining oxides
are considerably resistant, so that the leucoxene grains tend to remain in the refined
product. Titanium minerals are known to occur in silica glass in the form of dark
point heterogeneities, which form dark long capillaries on drawing into tubes. For
this reason, they are regarded as undesirable impurities.
To select a suitable refining process it is necessary to know the form in which the
impurities occur, which determines the choice of the refining method and its effective
utilization. It is therefore convenient to divide the mineral admixtures into several
groups:
(a) clay minerals and the hypergenetic zone minerals (ochres, limonite);
(b) granular mineral admixtures released in the process of grinding, i.e. rock-
forming minerals (feldspars, micas) and heavy minerals (turmaline, pyrite, rutile,
actinolite and others);
(c) coating-forming minerals (limonite, manganese oxides) and infiltrations in
cracks, finely dispersed pigmentations;
(d) solid inclusions in the quartz substance;
(e) gas-liquid inclusions, determining the degree of milk-white turbidity of quartz;
(f) admixtures bound in the structure.
Special methodical procedures have been developed, based on gradual separation
of the individual groups of admixtures using phase analysis methods and on the
determination of Fe 2 0 3 and other accompanying impurities, to evaluate the dis
tribution of iron in the forms mentioned above. This analysis assesses the distri
bution and significance of the individual admixtures, and determines the appropriate
refining methods.
In most instances, the refining is aimed at eliminating the first three groups of ad
mixtures. The residual content of iron bound in the forms (d) to (f) can be regarded
as a limit of standard refining methods. The processes used in the refining of quartz
do not affect solid inclusions and structural admixtures. The content of gas-liquid
inclusions is influenced only partially. However, the inclusions are eliminated in the
course of melting.
Washing of the raw material is used to remove the fine clay and hypergenous
minerals. The other minerals are eliminated by flotation, electromagnetic and electro
static separation, gravity separation, leaching, etc.
159
Special non-traditional refining procedures have been worked out to eliminate
certain minerals; for example, in Czechoslovakia muscovite is separated by chemical
refining in dilute HF, following ignition of the raw material.
Three-stage flotation (gradual separation of micas, heavy minerals and feldspars)
is used in the refining of vein quartzes in Japan. A pneumatic separation of micas,
working on the principle of different behaviour of mineral grains with diverse shape
characteristics in a stream of air, has been developed in the USSR.
Some muscovites have a higher content of iron, and are therefore at least slightly
magnetic, thus being separable with the use of suitable types of high-intensity dry
electromagnetic separators. Satisfactory results are also provided by electrostatic
separation of micas from quartz.
To improve the results of chemical refining, a combination of several acids can be
used, with additions of reducing agents or mechanical agitation of the bath, and
possibly also leaching supplemented with ultrasound.
Crystal raw materials require comparatively simple refining. Vein quartzes demand
more aggressive baths, or longer times of leaching and elevated bath temperatures.
Dilute HF is used for this purpose.
An account of some complete procedures for the refining of quartz raw materials
is given below.
Refining of rock crystal

Rock crystal is the basic material for the production of clear silica glass.
The methods used in the refining of rock crystal are appropriate to the low content
of removable impurities (foreign minerals, coatings), and are thus usually not appli
cable for vein quartzes.
The Heraeus Corporation (FRG) uses a refining procedure including hand sorting
of visible impurities, rinsing of quartz in dilute HF and subsequent washing, drying
and calcination at 800 °C. The calcined crystal is ground to a grain size of 0.2-0.1 mm
in an agate cone mill. The refining process was introduced in 1966.
The French Corporation Quartz et Silice refines its raw materials continuously
in the vapours of hydrochloric acid. The quartz is preheated in a horizontal rotary
kiln at 900 °C and then introduced into a reactor containing HCl vapours. The
consumption of the acid amounts to 2-3 kg Mg" 1 , the throughput being 80 to
90 kg h _ 1 . The procedure is capable of reducing the content of Fe 2 O a from 0.0100
to 0.0001%.
According to Revnicev [49], crystal is refined as follows in European, Japanese
and American dressing plants.
Batches of sorted quartz raw material, in lumps 50 to 100 mm in size, are first
leached in hydrofluoric acid to remove surface impurities from the crystal grains.
This leaching makes use of 72 to 75% HF in lead vessels.
Following the leaching, the crystal is carefully washed and hand sorted. In this
160
way, raw material lumps with non-leached coatings and with enclosed solid impurities
are removed. The rejects from this operation amount to up to 40%.
The sorted crystal is heat treated in an electric furnace at 600 °C for 30 minutes.
The heated raw material is then rapidly quenched in a tank filled with distilled water.
The crystal cracks up extensively and can then be readily ground to the required
grain size in a cylindrical mill. The 0.3 to 0.5 mm fraction is removed in vibration
sieves, and the oversize grains are continuously recycled for regrinding. The useful
grain size fraction is further treated in aqua regia in glass apparatus. The long-term
refining takes two or three days, and the suspension is agitated occasionally.
The leached material is washed with water six to eight times until the reaction
is neutral, and subsequently twice or three times with distilled water. It is dried in
glass dishes in an electric oven at up to 110 °C.
After this drying, the charge is inspected carefully and the defective grains are
removed. To ensure uniform melting, grains of identical shape characteristics are
selected. The selected charge is kept in glass vessels sealed with ground glass stoppers.
The Polish Polam Corporation refines lump crystals 20 to 40 mm in size by leaching
in cold 6% HF. The washing is followed by calcination in a continuous furnace,
manual removal of impurities and grinding of quartz in a ball mill. Charges of 0.2
to 0.5 mm grain sizes are prepared from the ground material by sieving.
In the Staaken Works in the German Democratic Republic, crystal raw materials
in lumps of 10 to 30 mm in size are calcined in chambers or continuous kilns at
600 °C; the ignited quartz is washed in deionized water and ground in a ball mill
to a grain size of 0.4 to 1.6 mm. Chemical refining is carried out discountinuously,
on 10-kg charges in two leaching baths: at first for 3 hours in 20% HC1, then for
a further 3 hours in 20% HF.
The leached product is washed, dried and sieved. Then follows dry electromagnetic
separation, packing, taking of samples and shipment.
There are a number of dressing plants in the Soviet Union for the treatment of
quartz. For instance, in one of them quartz with a grain size of 50 to 100 mm is refined
by washing with water, heating to 250-300 °C (decolorization of morion) and sorted
visually. The raw material treated in this way is then leached in HC1, in silica glass
dishes. The following heat treatment at 800 to 850 °C is continuous. After drying,
the crystal is hand sorted and ground.
In another crystal refining process, lumps 10 to 70 mm in size are washed with
water and calcined in a muffle kiln at 850 °C. Following hand sorting, the raw ma
terial is ground in a cylindrical mill with silica glass discs. The useful grain size
fraction of 0.1 to 0.5 mm is separated by sieving. Chemical refining takes place in
boiling dilute (20%) HC1 for 5 hours. After leaching, the quartz is washed with
distilled water, dried in ovens at 150 °C, packed and shipped.
The heat treatment of quartz and grinding of the calcined material in non-ferrous
plant are important parts of all the above technologies. Chemical refining often uses
161
only dilute HC1, and the methods mostly avoid processes aimed at removing separate
grains of minerals. These minerals are obviously removed just by visual sorting
of the non-calcined (transparent or translucent) raw materials.
Some impurities can also be eliminated by the final high-intensity electromagnetic
separation which is used in the German Democratic Republic. Some new technologies
have recently been introduced even into the refining of crystal raw materials, parti
cularly in the field of mechanization and general modernization of the plants.
Refining of vein quartz
In the Soviet Union, vein quartz is used as the main raw material in the production
of clear silica glass. The raw materials are divided according to the severity of the
demands for the final glass:
- milky white vein quartzes are satisfactory for the less demanding glasses (e.g.
chemical laboratory ware);
- higher-grade types of milk-white quartzes are used to make clear lighting
silica glass (e.g. the Gora Chrustalnaya, Aktas and Kyshtym deposits);
- the highest grade optical silica glass is made of crystal, synthetic quartz, etc.
Quartz from the Kyshtym deposit has found a very wide field of application. Its
refining is carried out as follows. The raw material, 0.2 to 1.2 mm in grain size, is
ground to a size of 0.15 to 0.4 mm in a special device based on the electrohydraulic
effect. The ground material is dried, sieved and subjected to magnetic separation
on the MS-2 separator, working with a field intensity of 1000 to 1300 kA m" 1 .
Leaching of 5 kg charges in boiling dilute HC1 for 2 hours is followed by washing
with distilled water and drying, and finally by visual inspection for purity, on a special
inspection table. Quartz from the Aktas deposit, supplied in lumps 50 to 150 mm in
size, is crushed to grains less than 30 mm in size in a jaw crusher and then ground
in an electrohydraulic device. The fraction of 0.1 to 0.4 mm, obtained by sieving, is
then subjected to electromagnetic separation. This is followed by gravity separation
of heavy minerals. Batches of ground quartz 10 kg in weight are treated in a heavy
liquid with a density of 2670 kg m - 3 .
After drying, the vein quartz is refined in a mixture of HC1 + H 2 S 0 4 , at boiling
point or at a lower temperature under the combined effect of ultrasound.
Washing and drying is again followed by visual sorting on an inspection table.
Some new elements in the treatment of quartz have been introduced by Toshiba
Ceramics (Japan). The quartz raw materials from the Kyshtym deposit are treated
as follows: the crushing and grinding using conventional methods is followed by
low-intensity, electromagnetic separation at a field intensity of 100 kA m _ 1 . How
ever, the main refining method is based on a three-stage flotation of feldspars, Fe-Ti
minerals and micas.
The purified raw material is subsequently heat treated at 800 °C, washed in H F
162
and submitted, after drying, to additional high-intensity electromagnetic separation
at a field intensity of 1600 kAm" 1 .
The process allows the content of the main impurities to be cut down from tenths
of a percent to 0.002% Fe 2 0 3 , 0.004% A1203 and 0.001% Na 2 0. The Ti0 2 content
in the flotation product, amounting to 0.0008%, indicates that the flotation of rutile
is not successful.
A schematic diagram of the refining of vein quartz raw materials in Czechoslovakia
lump quartz
fine fractions .. * .
and sludge ^ — washing drum
minerals,accumulation sorting belt
of impurities >^ ψ
calcination furnace 700'C, holding 6 h

iron pigmentation -*— sorting belt
j
crushing and grinding (jaw crusher,ball mill
~T in circuit with spiral
* classifier)
screening and countercurrent sludge removal
fine sludge - 0.08mm — -preparation of class-0.5; 0.08mm
I
wet electromagnetic separation
magnetic particles ■<— in MSB 600 separator
dewatering, weighing, metering
soluble impurities - « - chemical refining (20%HF,50-65°C,2h
Fig. 79 — Schematic diagram
fine f r a c t i o n s - 0 . 0 8 m m ^ washing,dewatering,drying
J of
of the
the refining
refining of
of vein
vein
sampling,packing quartzes in Czechoslovakia
The refining technology has been continuously improved and adjusted to the
quality of the vein quartz materials, so that nowadays the technological line conforms
fully to the requirements of clear silica glass manufacturers in Czechoslovakia.
3.3.3 Evaluation of refining methods
At present, the refining of quartz raw materials is carried out extensively

even in countries where these procedures had not originally been used. As a result
of a shortage of crystal raw materials, most silica glass manufacturers have been
obliged to adjust their technologies to vein quartz raw materials. These represent
a much more plentiful homogeneous raw material which, however, has the disadvan
tage of showing a higher degree of heterogeneous contamination requiring a more
complex refining technology. The dressing plants have been gradually introducing
mass production methods showing a high degree of mechanization and automation.
163
Increasing use is made of gravity, electromagnetic and flotation separation methods.
The aspect of complex utilization of the raw material is increasingly being taken
into account. The former waste materials from the refining of quartz can be utilized
in the manufacture of finely ground quartz for ceramics, foundries, and other purposes.
The diverse fields of application of silica glass require initial raw materials of
different qualities. The special types of silica glasses demand highly complex and
extensive refining procedures, even when processing quartz raw materials of high
quality.
In Czechoslovakia, silica glass is mostly employed to manufacture semifinished
products for mercury or halogen-type discharge lamps. Vein quartzes of Soviet and
local origin are mostly used for this purpose. Table 28 lists the chemical composition
of quartz raw materials from the Svedlär deposit in the individual refining stages.
Table 28
Chemical analyses of quartz raw material from the Svedlär deposit at various stages of refining
Product Concentration of the components (\)
Fe203 Ti02 A1 2 0 3 Na20 κ2ο

Ground fraction 0.67 0.0002 0.028 0.011 0.0009
Classified fraction
- 0 . 5 + 0.1 mm 0.34 0.0002 0.022 0.010 0.009
Non-magnetic fraction 0.032 0.0003 0.021 0.0077 0.0074
Leached product 0.0007 0.0001 0.0013 0.0070 0.0019
Waste sludge after grinding 0.36 0.0010 0.120 0.011 0.022

Waste sludge after leaching 0.012 0.0007 0.014 0.0056 0.0034
1000
800 Ά f
(%HF
1\^·^
yl v 4v^ -J° - ^ , . . _
£ 600 •60 -15
i
A00 .'rΊ μο MO
l i
\l
200 -\i •20
Fig. 80 - The pattern of refining of quartz
'■y:.'*>«^..>« mynv JJ <o«n«u(p«<jÔ· ■■» »ι^
from the Svedlär deposit: 1 - heavy
30 60 90 120 minerals; 2 - F e 2 0 3 ; 3 - leaching bath
-■*- f (min) temperature; 4 - leaching bath concentration
164
The results of chemical analyses indicate that chemical refining has the greatest
purifying effect; however, electromagnetic separation and sieving are also definitely
effective.
Similar conditions hold for the refining of other quartz raw materials, e.g. those
from the Detkovice or Kyshtym deposits.
The course of chemical refining in dilute HF of the quartz raw material from the
Svedlär deposit is shown in Fig. 80.
The greatest refining effect is achieved during the first fifteen minutes of refining
when the bath temperature culminates and the concentration of H F is the highest.
3.4 TECHNOLOGICAL METHODS O F MANUFACTURE

O F SILICA GLASS
From the application standpoint, silica glass is mainly divided into

(a) opaque glass, (b) clear glass, (c) optical glass, (d) silica glass for special appli
cations.
The first three types of silica glasses differ in the content of bubbles.
Opaque silica glass contains such a concentration of microbubbles as to be white,
turbid and non-transparent, the bubbles being closed and the glass impermeable
to gases.
Clear silica glass may also contain bubbles of various sizes, but in substantially
lower concentration, so that its clarity is not affected.
Optical silica glass meets the requirements for optical quality in its content of
bubbles; with respect to the concentration of bubbles, silica glasses for special
applications are on the level of the latter two types mentioned above, but of course
must also meet the requirements with respect to specific properties.
A more detailed classification of the various types of silica glasses is shown in
Section 1.1 and Chapter 4. The classification is based on technological manufacturing
processes, the types of raw materials employed (natural, synthetic), the subsequent
treatment, properties, and the like.
The technological procedure for the manufacture of silica glasses differs basically
from the technology used in the melting of conventional types of glasses. As follows
from the phase diagram (Fig. 40, p. 95), high temperature has to be used to achieve
the phase transformation into glass (above 1730 °C); these temperatures can be
attained by the use of gaseous fuels, electrical energy (arc heating, resistance heating,
induction heating) or by the use of plasma.
The melting from natural raw materials is not carried out in the way employed
in the melting of conventional types of glasses, but is based on gradual sintering of
grains or particles of the quartz raw material. If the sintering proceeds with the
access of air, the silica glass melted contains such a large number of bubbles as to be
165
opaque. If the melting is conducted under reduced pressure (i.e. by evacuating the
furnace interior), the melting yields clear silica glass.
The subsequent working of silica glass into its final shape usually starts from
a cylindrical semiproduct of silica glass, which can be formed with heat treatment
in suitable equipment.
3.4.1 Opaque silica glass
Opaque silica glass is made from quartz sand whose qualitative parameters
are specified in Standards (cf. Section 2.2.5). The melting is carried out in electric
resistance furnaces and proceeds under atmospheric pressure.
The melting process devised by Bottomley takes place in a drum-shaped horizontal
furnace about 1500 mm in length. The heat is provided by a centrally placed graphite
rod about 50 mm in diameter, situated between two graphite electrodes about
150 mm in diameter. An electric current of 1000 to 1500 A at 10 to 15 V heats the
graphite rod to a temperature of about 1800 to 1900 °C and the quartz sand begins
to melt at first at the rod. Several hours of melting produce a cylinder of opaque silica
glass whose thickness depends on the time of melting and temperature. After the
melting, the unfused sand is removed and the graphite rod is withdrawn from the
cylinder, which is then lifted from the furnace and subjected to subsequent techno
logical operations. With the use of compressed air, the hot cylinder is drawn into
a tube or a hollow semiproduct of another shape, or moulded into blocks under
pressure. The forming must be very fast, as the silica glass cylinder remains able to
be formed only down to about 1400 °C.
The cooling is retarded by additional heating with an oxygen-hydrogen flame.
Figure 81 shows a schematic diagram of the melting furnace.
Fig. 81 - Schematic diagram of a melting

furnace for the manufacture of opaque silica
glass in tubular form: (a) - before melting,
(b) - after melting; 1 - graphite heating
resistance rod; 2 — protective tube of silica
glass; 3 — silica sand; 4 — thermally
insulating layer; 5 — furnace body;
6 — opaque silica glass
The melting furnace according to Fortey utilizes centrifugal force to form silica
glass in a drum furnace. A steel cylinder, on the surface of which a layer of unfused
sand is first deposited, is allowed to revolve inside the drum. The fusion induced by
an electric arc takes place at the drum axis. This technology is suitable for the manu
facture of cylinders of various wall thicknesses, crucibles, vessels, etc.
166
Silica glass blocks of large sizes are manufactured in Bottomley's furnaces, shown
schematically in Fig. 82.
The furnace consists of several graphite resistance rods and a base which can be
moved slowly downwards. The furnace is first charged with silica sand, the resistance
heating produces a melt and the furnace base is gradually moved down. Further
quartz sand is introduced continuously, and the fusion proceeds until a block of
silica glass of the required dimensions is obtained. After cooling, the glass block is
cut into the sizes desired.
Fig. 82 - Schematic diagram of a melting furnace for the production of opaque silica glass blocks
according to Bottomley: (a) - side view, (b) - plan; 1 - silica sand; 2 - graphite heating resistance
rods; 3 — melt; 4 — moving furnace base
3.4.2 Clear silica glass
3.4.2.1 Survey of technologies
The manufacture of clear silica glass is technologically more demanding

than that of opaque silica glass. It is necessary to use high-grade silica raw materials
such as rock crystal, vein quartz, purified quartz sand or synthetic silicon compounds.
Natural raw materials have so far been more commonly used, mainly for reasons
of economy.
The manufacture of silica glass is technologically limited by the following factors:
(a) a high fusion and working temperature, which varies over the range of 1800
to 2000 °C,
(b) a very high viscosity at the temperatures of melting and working,
(c) a high vapour pressure (Fig. 83).
167
At the given temperatures, the melt has a viscosity in the range of 107 to 10 5 · 5 (dPa s),
which rules out the refining process (characteristic of the melting of conventional
types of glass) and makes working of the melt very difficult (Fig. 83).
760
100
o
10 ^
CO
10"1
Fig. 83 — Temperature
dependence of viscosity η and
~ 1000 1400 1800 2200 '" Si0 2 vapour pressure
- t CO
In the present state of high-temperature technology, it is not difficult to attain the
melting temperatures with the use of gaseous, electric or plasma manufacturing
processes. However, special requirements have to be met by the furnace refractories,
particularly those coming into direct contact with the silica glass melt, and especially
regarding their refractory nature and chemical purity. The latter has to be at least
the same as, or superior to, the chemical purity of the quartz raw materials.
It is moreover necessary to use suitable materials for thermal insulation, which
must insulate the high-temperature melting zone from the environment but must not
contaminate the inner atmosphere in the melting furnace.
The high viscosity of the melt at the melting temperature is responsible for the
difficult elimination of bubbles which are formed, either from the impurities present,
or due to inadequate escape of gaseous products from cracking inclusions, or from
gases produced by the reaction of the melt in contact with the refractory material.
As a result of the high viscosity, refining of the melt does not take place and even
increasing the melting temperatures would not affect the melt viscosity to a signifi
cant degree. Moreover, the vapour pressure of Si0 2 would increase substantially
and losses due to vaporization of S i 0 2 become unacceptable. These technological
aspects impair the vacuum technology employed, so that any increase in the melting
temperature would not have the desirable technological effect.
168
The content of bubbles in the melt is therefore decreased by melting under reduced
pressure, exposing the melt to the pressure of an inert gas, etc. Each measure for
decreasing the content of bubbles in the melt, and thus also in the final product,
always involves higher production costs.
The high melt viscosity likewise influences the subsequent processing (forming).
The basic forming methods employed are first of all the melting of a silica glass block,
the pressure moulding of shaped ware, and drawing. The working of the melt by
drawing is the most widely used technology. It is employed to manufacture tubes,
rods, strips and other sections, e.g. square, rectangular or oval sections.
Let us first deal briefly with the drawing of tubes, which is the technology en
countered most frequently in the manufacture of silica glass ware.
Tube manufacturing can be divided into single-stage and two-stage processes,
according to the number of heat treatments required.
Single-stage manufacture: the melted silica glass in the furnace is directly drawn
into tubes by a discontinuous or continuous method.
Two-stage manufacture: the melting of silica glass and cooling of the melt yield
a hollow or full cylinder of silica glass (block, ingot) whose surface is first treated
to remove impurities and obtain ä precise geometrical shape; the semiproduct is
then placed in a drawing furnace, heated, and tubing is drawn from the melt.
The subsequent technological operations to process a silica glass include cutting,
grinding, polishing, welding, glass-blowing, etc.
With respect to technological criteria, the basic manufacturing process can be
divided according to the way the raw material is fused and drawn into tubes, the
name of the technology usually being derived from a characteristic of the manufac
turing process. Thus the melting methods can be divided according to the mode of
heating into gaseous, electric or plasma melting, according to the way the raw
material is fused into rotary (contact-free) or crucible (contact) melting, and according
to the atmosphere used in the course of melting into atmospheric, vacuum, vacuum-
atmospheric or vacuum-compressive melting, etc.
The basic characteristics of the main melting methods can be briefly described as
follows:
(a) Gas melting
This process is suitable only for melting high-grade rock crystal free of gas-liquid
inclusions and ground to fine grains, preferably a single size range. Synthetic silicon
compounds are also processed in this way for special purposes, as described in
a separate Section below.
The melting proceeds under normal atmospheric pressure. The fuel gases used are
hydrogen, propane-butane or natural gas, together with oxygen. The melting proceeds
so that either cool or, more often, preheated quartz grains are gradually fused by
169
thin layers onto a pad or mandrel, in a crucible, etc. The melted glass blocks are
several tens of kilograms in weight. Gas melting has the disadvantage of producing
silica glass with a high content of OH groups, which show characteristic absorption.
(b) Electric melting

This technology is used to melt rock crystal, vein quartz, purified quartz sands
and, for special purposes, also Si0 2 gels, as described below in a special Section.
The raw materials are melted in electric resistance or induction furnaces. The
furnaces are mostly made of Zr0 2 , tungsten, molybdenum or, particularly, graphite.
The entire charge of quartz raw material is either fused by gradually increasing
the temperature until the grains fuse and form the melt, or by gradually fusing pre
heated or premelted quartz grains in a thin layer on the melt surface (continuous
method).
Rotary method. A steel cylinder filled with the quartz raw material rotates around
a fixed resistance-heated electrode which is not in contact with the raw material.
The temperature is gradually increased under reduced pressure and the raw material
fuses and produces a hollow cylinder of silica glass whose surface is then ground
off; several such cylinders are welded together and used to draw tubes by the contact-
free process.
Crucible method. The quartz raw material, usually placed in a graphite crucible,
is gradually heated in a resistance or induction electric furnace under reduced
pressure until the quartz grains fuse and form the melt. Numerous reactions take
place at the areas of contact between the melt and graphite, and the product may
contaminate the melt as described in Sec. 3.2.4. It is therefore necessary to use graph
ite materials of specially superior purity. The crucibles may either be provided with
Fig. 84 — Examples of a set of graphite

crucibles for electric melting of silica glass:
/"Ό"\ ,/ΌΛ /'cf\

(a) — the crucible is a single cylinder,
(b) — the crucible consists of two cylinders,
ίθ#θ) ίθ#ο; ίο#θΐ (c) — the crucible consists of several
νο / \oy \oy cylinders and a perforated central

tubular element
170
a central element (to obtain hollow cylinders) or without it (to obtain full blocks).
The blocks melted in this way are surface treated and mostly used to draw tubes
over a centering mandrel. The crucibles are of either one or more parts, the multi-
component type or perforated central elements being advantageous with respect
to degassing of raw materials containing larger amounts of gas-liquid inclusions
(e.g. vein quartzes). The types of crucibles used in the melting are shown in Fig. 84.
(c) Plasma melting

High-grade quartz raw material of fine grain size is melted in a special plasma
burner and allowed to condense on a refractory pad, mandrel, etc. Gradual deposition
yields a block of silica glass. The plasma burner is mostly used in special manufac
turing processes, as are the synthetic silicon compounds dealt with in a separate
Section.
The following melting methods are distinguished, according to the pressure in the
furnace:
(a) Atmospheric melting

This is carried out under the normal pressure; it covers all gas and continuous
procedures for the manufacture of clear silica glass.
(b) Vacuum melting

A low pressure is maintained throughout the time of melting until the melt has
solidified. It is generally used in the electrical methods of crucible melting.
(c) Vacuum-atmospheric melting

This is carried out under reduced pressure, and towards the end of the heating
the furnace is filled, mostly with an inert gas, to a pressure corresponding to normal
atmospheric pressure. The melt is allowed to solidify under these conditions; this
technology is applied for example in the rotary melting method.
(d) Vacuum-compression melting

This is effected under reduced pressure; gas under a certain pressure (of 2 to
3 MPa) is forced into the furnace at the end of melting. The method is used to melt
silica glass of optical quality. However, it is not suitable for the manufacture of
tubing, as secondary bubbles tend to form on reheating glass under normal pressure
(in the course of drawing).
171
Basic characteristics of the tube drawing methods:
(a) Contact-free drawing
A hollow cylinder of silica glass of precise dimensions is gradually inserted into
the heat zone of the drawing furnace (usually a graphite resistance electric furnace);
a tube of the required dimension is then drawn from the cylinder while controlling
the drawing speed, temperature and the speed at which the cylinder is inserted. The
tube geometry is adjusted by means of compressed air supplied into the tube through
the hollow cylinder in the course of drawing. Neither the silica glass cylinder nor
the tube are therefore in contact with the furnace material (Fig. 97). The drawing
method is suited to producing tubing about 100 mm and more in diameter; the tubes
have a satisfactory surface quality. The drawing proceeds either vertically or, less
often, horizontally.
(b) Crucible drawing over a mandrel

Silica glass melt is drawn from the bottom of the crucible over the so-called
forming system consisting of a nozzle, a mandrel and a "calibre". Figures 85 and 86
show a schematic diagram of the forming system. The method allows tubing about
250 mm in diameter, and in some instances even more, to be manufactured. In some
variations of the technology, the position of the "calibre" can be adjusted with
respect to that of the nozzle to achieve a uniform wall thickness. When graphite
forming systems are used, the surface quality of the tubing depends on the quality
a b
Fig. 86 — Detail of the forming assembly for the drawing of rods
(a) and lubes (b)
Fig. 85 — Detail of the forming assembly:

1 — crucible body; 2 — nozzle (eye);
3 — "ponson", 4 — pipe; 5 — flowing melt;
6 — drawn tube
172
of the graphite, particularly on its purity, refractoriness and antifriction properties.
Undesirable reactions usually take place at the point of contact between the glass
and graphite, the glass surface is contaminated, the bubbles formed are drawn into
capillaries, and the glass copies the surface of the graphite material.
The manufacturing technology therefore influences a number of physico-chemical
properties of the melted and formed silica glass, and has a decisive effect on its
applicability. The most important properties of silica glass in this respect are the
content of impurities, OH groups, coloured inhomogeneities, length and frequency
of bubbles, surface quality, geometry of the tubing, etc.
3.4.2.2 Methods and plant for gas melting
Gas melting is the oldest and technologically the least demanding way of
producing silica glass. Hydrogen, propane-butane or methane are used with oxygen
in the heating.
The oldest method is based on manual fusion on a graphite blowpipe, to whose
end a silica glass bulb is fused. This is again heated above the melting temperature,
dipped in the quartz raw material (rock crystal of 0.3 to 3.0 mm grain size), and melted
in the flame. The procedure is repeated until the flask is about 4 kg in weight. Fol
lowing thorough heating of the entire material to the plastic state, a tube about
5 m in length and 30 to 50 mm in diameter is drawn manually, with the use of com
pressed air and pliers. The process is time consuming and the dimensional tolerances
of the tubing are considerable.
Mechanization of this principle of gas melting yielded a number of efficient techno
logies.
Fig. 87 - Schematic diagram of gas

melting of silica glass: 1 - hopper
with quartz raw material; 2 — metering
device; 3 — metering controls;
4 — preheating of the quartz raw
material; 5,6 - burners; 7 - pad;
8 - muffle; 9,10 - heating gases;
11, 12 — reduction valves
Figure 87 shows a schematic diagram of the gas method of melting silica glass.
Quartz raw material supplied from a bin is deposited and gradually fused onto
a pad of preheated clear silica glass fitted to the end of a revolving tube. The tube
revolves at about 10 to 40 r.p.m. and can be shifted horizontally. The raw material
173
can be preheated up to about 800 °C or fed directly into the burner. The blocks of
silica glass melted by this technology reach several kilograms in weight.
With the use of a special propane-butane-oxygen burner, a silica glass cylinder
can be melted by the technology shown in Fig. 88.
Fig. 89 — Schematic diagram of continuous gas

melting of silica glass in a Z r 0 2 furnace:
/ — burner with raw material feeder; 2 — melt;
3 — drawing device
Fig. 88 - Schematic diagram of
apparatus for gaseous melting of silica
glass in cylindrical form: 1 - raw
material hopper; 2 - metering device;
3 - raw material feeders; 4 - burner
(propane-butane-oxygen); 5 - gradually
fused-on silica glass cylinder; 6,7 - gas
supply
A special circular burner 180 mm in diameter is provided with a series of openings

(nozzles) along its circumference, and also openings for supplying quartz raw ma
terial from a storage bin. A cylinder of clear silica glass, placed below the burner,
is rotated at a speed of 6. r.p.m. and grains of the raw material are metered onto its
top edge. New layers are thus gradually fused on, while the cylinder rotates along
a helix and moves downwards at a speed allowing the distance between the burner
and the top cylinder edge to remain constant. The cylinder is about 3 to 5 mm thick,
174
according to the width of the annulus of the special burner, and up to about 2.5 m
in length.
The plant has an output of about 1 kg of glass per hour. It is also suitable for melting
silica glass cullet. However, it has the disadvantage of producing inhomogeneous
silica glass and causing a great loss of energy, which is dissipated into the environment.
Full blocks of silica glass can be manufactured continuously by gradual fusing-on
in an oxygen-hydrogen or other flame, in furnaces made of Zr0 2 . A gas burner fuses
the grains of quartz raw material falling onto the surface from above, the melt being
drawn off through the cylinder bottom. A schematic diagram of the equipment is
shown in Fig. 89.
This technology of melting and drawing has the disadvantage of keeping the melt
too long at high temperatures, thus facilitating its crystallization.
3.4.2.3 Methods and plant for electric melting
The melting makes use of either resistance or induction electric heating. The
electric furnaces are mostly of circular shape. In electric resistance crucible melting,
the raw material is placed in a crucible and heated by a resistance heating element
situated around the crucible. In the case of electric induction heating, the heating
element is the graphite crucible proper.
Fig. 90 — Continuous electric resistance melting

and drawing furnace:
1 — protective gas inlet; 2 — water jacket;
3 — electric current supply; 4 — cooling water
inlet and outlet; 5 — thermal insulation; 6 — quartz
raw material; 7 — tungsten heating element;
8 — Mo crucible; 9 — mandrel made of W or Mo;
10 — liner made of W or Mo; 11 — drawn tube;
12 — space filled with protective gas
An electric resistance continuous melting and drawing furnace for single-stage

manufacturing technology is shown in Fig. 90, following Hänlein.
175
In this case, a molybdenum crucible is heated by a tungsten heating jacket;
a drawing system of Mo or W sheet is fitted in the crucible bottom. The melting
section is divided by insulation of compact and granulated Z r 0 2 and by the furnace
water jacket. The entire furnace is kept in a protective atmosphere to prevent oxi
dation of Mo and W. A hydrogen-nitrogen mixture (1:4), or a mixture of helium
with argon or neon ( 1 : 1), or hydrogen alone are used.
The raw material is metered from a storage bin, preheated or pre-fused, and
gradually melted after falling onto the melt surface in the crucible.
The amount of raw material metered is kept in proportion to the amount drawn
off through the crucible bottom. A schematic diagram of the forming system is
shown in Fig. 91.
Fig. 91 — Forming assembly for tube drawing: Fig. 92 — Vacuum electric induction
/ — "ponson"; 2 — eye; 3 — H 2 inlet furnace: 1 — graphite crucible;
2 — inductor; 3 — thermal
insulation; 4 — jacket of opaque
silica glass; 5 — quartz raw material;
6 — water-cooled furnace lids;
7 — connection to a vacuum pump
The system allows inert gas to be supplied into the tube to protect it and adjust
its geometry. The latter also depends on precise adjustment of the annulus between
the mandrel and the nozzle before melting and drawing.
The equipment is capable of producing tubing of comparatively precise geometry.
It has the disadvantage of requiring a high-grade quartz raw material (rock crystal)
and allowing for the production of a limited assortment of ware in the course of one
melting cycle. The quality of tubes decreases with increasing output of the equipment,
while the protective gas penetrates into the melt and leads to increased capillarity
of the tubing. The equipment is capable of producing high-grade tubing about 10 mm
in diameter at an output of about 10 kg per hour. The technology has the advantage
of good economy and low energy costs.
176
A discontinuous melting and drawing furnace for single-stage production of
tubing is shown in Fig. 92.
The quartz raw material is first melted under reduced pressure (6.66 · 101 to
1.99· 103 Pa) in a graphite crucible which simultaneously serves as the heating
element (electric induction heating); the tubes are drawn after evacuation and
opening the bottom part of the furnace. The grain sizes of the quartz raw material
are about 1 to 3 cm. At its centre, the graphite crucible has a mandrel holder adjusted
to the crucible lid. The madrel has to be precisely centred before charging with the
raw material. The equipment therefore comprises an inductor, a cylinder of opaque
silica glass, thermal insulation (e.g. magnesite), a graphite crucible and drawing
equipment.
The charge weight is about 8 kg. The technology has the advantage of allowing
for wide and flexible changes in the product assortment, and melting even lower
grade vein quartz raw materials. Its drawback is an inferior quality of the tubing
drawn over the corroded graphite surface (in the course of melting) and its surface
contamination.
The rotary vacuum resistance furnace used to melt high-grade quartz raw materials
(rock crystal), developed by Thermal Syndicate Ltd., consists of a jacket housing
a rotary cylinder, and a graphite resistance-heated rod placed centrally in the cylinder.
The rod is out of contact with the quartz raw material, as shown in Fig. 93.
The rotary steel cylinder is charged with fine-grained quartz raw material which
is separated by coarse-grained quartz from the steel sheet of the cylinder. The melting
proceeds from the inner surface outwards, i.e. from the centrally situated resistance-
heated graphite bar, under reduced pressure of 6.66 to 1.33 · 101 Pa. The ingot melted
is finally cooled in a nitrogen atmosphere.
Fig. 93 — Rotary vacuum
resistance furnace: 1 — rotary
furnace; 2 — diffusion pump;
3 — rotary pump;
4 - furnace jacket;
5 — rotating cylinder,
6 — quartz raw material;
7 — graphite resistance rod;
8 - drive rollers;
9 - connection to the
vacuum pump
The technology is used to produce hollow cylinders of silica glass 180 to 190 mm
in diameter, 2 m in length, with a wall thickness of about 30 mm. The cylinder surface
is encrusted by sintered quartz raw material and, therefore the surface must be
grinded off before further processing (tube drawing).
177
The electric induction melting furnace used to produce silica glass ingots by
Quartz et Silice is shown in Fig. 94.
The furnace consists of a top and a bottom lid, which are both water cooled, and
a furnace jacket composed of an opaque silica glass cylinder with the inductor wound
around it. The furnace accommodates a graphite crucible charged with fine-grained
quartz raw material; graphite heating elements are arranged around the crucible.
Silicon carbide provides thermal insulation.
The melting is effected under reduced pressure (2.66· 101 to 1.33· 103 Pa), the
charge of quartz raw material being 15 to 40 kg, according to the crucible diameter.
The length of the ingot melted is 0.6 to 0.7 m. The ingot surface, which has come into
contact with graphite in the course of melting, is ground off mechanically before
subsequent processing. The technology has the main advantage of allowing for the
melting of lower grade vein quartzes or purified quartz sand.
Fig. 94 — Induction vacuum furnace: 1 — graphite

crucible; 2 — graphite heating cylinders;
3 — thermal insulation (SiC); 4 — cylinder of
opaque silica glass; 5 — inductor; 6 — connection
to the vacuum pump; 7 - bottom lid; 8 - top lid;
9 - filter; 10 - chimney (stack); 11 - filter;
12 — rotary vacuum pump Fig. 95 - Electric resistance furnace: 1 - connec
tion to the vacuum pump; 2 - graphite crucible;
3 '- resistance heating element; 4 - thermal
insulation; 5 - furnace lids; 6 - furnace jacket;
7 — quartz raw material
A schematic diagram of the electric resistance vacuum furnace is shown in Fig. 95.
The graphite crucibles are placed in the furnace from below, the melting is effected
under reduced pressure, and the thermal insulation is provided by Ζχ0 2 or foamed
coke. The melted ingots are 10 to 50 kg in weight, according to the crucible diameter.
178
The technology is likewise suitable for the processing of lower grade vein quartzes,
and brings about savings in electric power. The ingots are ground before further
working.
Several graphite crucibles can be accommodated in a specially adapted furnace,
thus permitting the productivity to be raised significantly.
3.4.2.4 Methods and plant for single-stage manufacture of tubing
A continuous resistance melting and drawing furnace, and a discontinuous

induction melting and drawing furnace, were described in Section 3.4.2.3.
The continuous method makes use of a silica glass tube, onto which an additional
layer is fused by means of a gas or plasma burner. After this deposition the tube is
drawn into tubing of smaller diameters. The equipment (Fig. 96) consists of four
production stages; in the first (a) the tubes are gradually welded together, in the
second (b) the new layer is fused on while the wall thickness is increased, in the third
(c) the tube is expanded and in the fourth (d) the actual tube drawing takes place.
The additional silica glass layer is fused onto the tube surface by means of an oxygen-
hydrogen, oxygen-propane-butane, arc or induction plasma heater. The quartz raw
fusion of expanding the tube

tubes by overpressure
quartz raw material drawing the tube to

reduce its diameter
fusing on a new silica

glass layer
Fig. 96 — Continuous fusion of silica

glass onto a silica glass tube
179
material (rock crystal) suitable for the fusion deposition should have a maximum
grain size of 250 μιη. The tube is expanded by overpressure inside or underpressure
outside.
3.4.2.5 Methods and plant for two-stage manufacture of tubing
In the two-stage production method, the tubes are drawn from pre-melted
ingots of silica glass.
The contact-free drawing method is based on the principle of narrowing down the
silica glass cylinder by drawing, in the heating zone of the furnace where it passes
into a plastic state. The plant consists of a drawing furnace, a device for placing the
ingot in the furnace, drawing equipment and a device for breaking off the tubes
Fig. 97 - Drawing device for contact-free Fig. 98 - Electric induction crucible furnace for
production of clear silica glass tubes: ) - silica tube manufacture: 1 - inductor; 2 - cylinder
glass ingot; 2 - drawn tube; 3 - drawing furnace of opaque silica glass; 3 - thermal insulation;
(graphite, resistance-heated); 4 - drawing device; 4 - graphite crucible; 5 - silica-glass ingot;
5 - suspension assembly 6 - drawn tube; 7 - drawing equipment
180
(Fig. 97). A silica glass ingot melted by the rotary method is surface-treated by
grinding; three ingots are welded together to a length of about 4 m, leached in HF,
and suspended from the device for passing the ingot into the drawing furnace. The
latter is heated by a graphite resistance element, insulated with Zr0 2 and cooled
with a water jacket. The graphite is protected from oxidation by a nitrogen atmo
sphere blown into the furnace.
The dimensional tolerances of the tube being drawn are controlled by suitable
selection and synchronization of the furnace temperature, the rate of drawing and
the pressure of air supplied into the tube.
The crucible induction drawing furnaces consist of an inductor, a cylinder of
opaque silica glass, a graphite crucible and the drawing equipment (Fig. 98). The
bottom of an induction-heated graphite crucible is provided with the so-called
forming system (Fig. 85) containing a nozzle, a "ponson" and a mandrel. The dimen
sions of the tubes are influenced by the glass temperature, drawing speed and the
dimensions of the forming elements.
The quality of the tubing depends above all on the quality of the graphite employed,
i.e. its antifriction properties and chemical purity. Some furnaces are provided with
a device for adjusting the mandrel position during the drawing. Resistance furnaces
heated directly with an Mo crucible are also used in continuous drawing of tubing.
The tubes are drawn from ingots which have been melted in advance in an inert gas
atmosphere and then placed in the furnace. However, the inert gas atmosphere in
the furnace can be contaminated during the placing of the ingots, and this may result
in contamination of the melt with oxidation products of Mo. The technology is
suitable for drawing tubes up to about 6 mm in diameter, and the quality of the
products depends on that of the silica glass ingots. The operation of the equipment
is not economical.
3.4.3 Optical silica glass
Optical grade silica glass should first of all exhibit a high degree of hom
ogeneity. It is usually manufactured by gas melting, and in some instances also by
electric melting using the vacuum-compression technology.
The raw materials are high-grade rock crystal or synthetic silica materials; in the
latter case, use is made of the special technologies described in Section 3.4.4.
3.4.3.1 Methods and plant for gas melting
The method based on fusing silica raw material onto a rotating rod was
described in Section 3.4.2.2. Another method consists of fusion deposition onto
a rotating pad of opaque silica glass, as shown in Fig. 99.
181
Fine-grained quartz raw material is fed into a gas burner (placed vertically),
fused, and allowed to fall onto the rotating pad. The technology is used to manufacture
silica glass of optical quality; the melted blocks are up to 30 kg in weight. The out
put of the equipment is about 500 g per hour.
1
Fig. 99 — Schematic diagram of the

manufacture of optical glass: 1 — system of one or more
oxygen-hydrogen burners; 2 - raw material metering;
3 — plate of opaque silica glass; 4 — fused-on block of
clear silica glass; 5 — rotating carrier of opaque silica glass
The fusion zone can be extended by increasing the number of burners, thus raising
the output of the equipment. The glass blocks are then cut, ground and polished to
obtain the desired products.
3.4.3.2 M e t h o d s a n d p l a n t for e l e c t r i c m e l t i n g
In view of the inferior technological conditions of electric melting (difficult

elimination of bubbles), the method is usually employed in combination with the
vacuum-compression method in the crucible (Section 3.4.2.1).
The plant is comparatively complex, being connected to both a vacuum system
and a high-pressure system. Towards the end of the melting the melt is compressed
by an inert gas under a pressure of 2 to 2.5 MPa.
3.4.4 Special methods of silica glass manufacture
3.4.4.1 S y n t h e t i c silica glass
During the last decade the production of synthetic silica glass has advanced
greatly, both quantitatively and qualitatively, in all industrially developed countries.
Particularly for the new and prospective fields of technology such as optoelectronics
or laser optics, high-purity silica glass of optical quality has become an irreplaceable
material. It has found these applications thanks primarily to its extremely high
chemical purity and homogeneity. High-purity synthetic silica glass is also made
into tubes, crucibles, ground joints and complete apparatus for special technological
purposes.
182
The subject of the manufacture of synthetic silica glass is extremely broad, differing
in character from the traditional procedures used in the manufacture of silica glass
from natural quartz raw materials.
In view of the limited scope of the present monograph, only a brief account of the
fundamental technologies and manufacturing procedures will be given.
Classification of the basic manufacturing methods
All the technological methods for the production of synthetic silica glass are based
on silicon halogenides or hydrides, or on organic silicon compounds, which can be
prepared and isolated in a high degree of purity. Virtually all these technologies
process the same semiproduct, pure amorphous Si0 2 , either in anhydrous form
(aerogels, xerogels) or in hydrated form (sols, gels).
According to the way this semiproduct is prepared, the methods for the manu
facture of synthetic silica glass can be divided into the following three groups:
(a) thermic oxidation of Si compounds in an anhydrous atmosphere (plasma,
laser);
(b) hydrolysis of Si compounds in a flame;
(c) hydrolysis of Si compounds in an aqueous medium (sols, gels).
The first two methods can be arranged as single-stage ones, i.e. the process yields
directly melted Si0 2 . However, in order to achieve a superior quality of the product
also in the case of flame hydrolysis, use is made of the multi-stage manufacturing
process; the stages are usually modified according to the demands on the content
of OH groups.
A more detailed classification of the basic manufacturing methods is based on the
arrangements used, for example, in the manufacture of semiproducts (preforms) for
optical communication fibres (see [73], a paper which mentions the following
methods).
Outside Vapour Phase Oxidation (OVPO)\ the preform is produced by applying
pyrolytic synthetic Si0 2 (possibly containing doping admixtures) onto the outer
core surface. With a suitable material used for the manufacture of the core (e.g.
graphite, ceramics) the method is also used to manufacture tubing.
Inside Vapour Phase Oxidation method (IVPO): this differs from the previous
method in that the synthetic Si0 2 is applied to the inner side of a tube of clear silica
glass. The method is almost exclusively used in the manufacture of preforms for
fibre optics.
Vapour Axial Deposition method (VAD): the preform is produced by applying
synthetic Si0 2 in the direction of its axis and without any central cavity. The method
has the important advantage of allowing for continuous production of the preforms,
including its drying and sintering.
183
Thermal oxidation in an anhydrous medium
These methods are used to prepare synthetic sihca glasses of the highest quality,
as the entire arrangement ensures a minimum content of OH groups and other
impurities in the melted glass.
The basic raw metal is usually SiCl4 of semiconductor purity, and pure dried
oxygen. The thermal oxidation proceeds according to the equation
SiCL + 0 2 SiO, + 2C12 (32)
An induction plasmatron is normally used as the burner [74]. The reaction tem
perature ensuring a satisfactory rate of fusion exceeds 1600 °C, and the theoretical
degree of conversion of SiCl4 reaches up to 100% [75, 76].
t
8 Ί
<^6
7 •
•
•
1^5
JS
13
Fig. 101 — Plasma induction burner:

Fig. 100 — Assembly for the manufacture of silica glass by 1 — oxygen plasma; 2 — jacket
plasma oxidation: 1 - stock of liquid SiCl 4 ; 2 - pump; (tube) of clear silica glass;
3 — SiCl4 vaporizer; 4 — burner entry chamber; 3 — water-cooled jacket; 4 — inlet
5 — burner; 6 — high-frequency inductor; nozzle; 5 - inlet of gases ( 0 2 or Ar);
7 — high-frequency source; 8 — fused-on ingot of silica 6 — injection nozzles; 7 — supply of
glass; 9 — ingot holder; 10 — holder displacement; SiCl4 + 0 2 ; 8 — outlet burner
11 — positioning device; 12 — liquid SiCl 4 ; 13 — gaseous nozzle; 9 — fused-on ingot of silica
0 2 to vaporizer 14 — gaseous 0 2 to burner; 15 — gaseous glass; 10 — holder (revolution and
Ar to burner downwards movements)
184
However, although a conversion efficiency of more than 99% has been attained
in the preparation of anhydrous silica [75], the overall efficiency of single-stage
production of ingots decreases to about 34% as a result of losses in Si0 2 due to fly
over and volatilization [74].
An example of a system for single-stage production of ingots by means of the
induction plasmatron is shown in Fig. 100 [77].
An induction plasma burner (Fig. 101) works with oxygen plasma, whose initiation
and stabilization are provided by means of Ar [74]. The raw material, SiCl4, is
supplied as vapour into a nozzle below the plasma, together with a proportion of
dry oxygen (burners with a supply lead into the plasma are also used [74]).
Saturation with the SiCl4 vapour is usually effected by passing a stream of 0 2
through the saturator vessel, the content of the vapour being controlled by the
vaporization temperature [74]. The raw material can also be metered into a resist
ance-heated evaporator, where the vapour arising is simultaneously mixed with
oxygen [77].
Similar methods are used to meter the vapours of doping element halogenides,
particularly for fibre optics.
The amorphous Si0 2 produced is fused onto a pad (Zr0 2 , Al 2 0 3 , silica glass)
which is uniformly displaced and revolved with respect to the burner.
Fig. 102 — Arrangement for the manufacture of silica glass

by thermal oxidation with C0 2 laser: 1 — C0 2 laser;
2 — mirror; 3 — chamber (glass); 4 — fused-on ingot of
silica glass; 5 - nozzle; 6 - raw material feed, SiCl4 + 0 2 ;
7 — exhaustion
Methods using lasers as the source of energy for the thermal oxidation are less
frequent. The best results are said to be achieved with the use of C0 2 lasers [78],
as a result of the high absorption of the generated light in silica glass. A schematic
diagram of the arrangement is shown in Fig. 102.
Methods of flame hydrolysis

The procedure for the manufacture of silica glass by hydrolysis of a volatile silicon
compound in a flame has been known for more than 40 years [79], and is being further
developed at present. The initial raw material is usually SiCl4, the use of SiH being
185
also possible [84]. The raw material is fed into a burner combusting hydrogen or
natural gas with oxygen [80]. The hydrolysis yields amorphous Si0 2 according to
the reaction
SiCL + 2 H , 0 SiO, + 4HC1 (33)
The amorphous particles arising settle on a refractory pad (Zr0 2 , graphite, silica
glass) and can be directly sintered into glass in the flame (single-stage manufacturing
process). However, the procedure more frequently employed first yields a porous
preform, from which the OH groups are removed by drying, or to which additional
layers of Si0 2 with doping elements are applied. In the subsequent stage, the preform
is sintered to clear silica glass at 1400 to 1600 °C.
The preform is dried in an atmosphere of Cl2 [82] or SOCl2 [83]; in this way the
content of OH groups is reduced below 1 ppm (in the original preform, this concen
tration is about 1000 ppm).
For less demanding applications, the sintering is effected in an atmosphere of dry
inert gas [81], or the preform is sintered under reduced pressure.
Fig. 103 — Arrangement for the

manufacture of silica glass by flame
hydrolysis (VAD method by
Nippon): 1 — burners; 2 — inlet of
SiCl4 and H 2 + (D2 gases (possibly
with doping substances such as
GeCl 4 ); 3 — fused-on porous ingot
(preform); 4 — liquid SOCl 2 ;
5 — supply of gaseous 0 2 ;
6 — exhaustion; 7 — graphite
resistance furnace (preform
sintering); 8 — clear silica glass
The arrangement of the technological equipment is modified according to the
semiproduct being manufactured (crucibles, fibre optics, etc.). The SiCl4 is supplied
to the burner in the form of vapour, in a mixture with oxygen; the saturation is usually
carried out by passing 0 2 through SiCl4, as has already been described [80, 81].
A modern arrangement of apparatus for the production of preforms and their
continuous sintering (the VAD method) is shown in Fig. 103 (according to [83]).
Methods of preparation from Si02 sols and gels

These methods for the production of clear silica glass are likewise based on the
use of pure synthetic silicon compounds, the amorphous Si0 2 being obtained by
their hydrolysis in the liquid phase.
The hydrated Si0 2 obtained is dehydrated, dried and melted to clear silica glass
in an inert atmosphere or under reduced pressure. There are modifications of this
basic process which allow highly homogeneous glasses of optical quality, glasses
with a low content of OH groups, or glasses containing doping elements to be
produced.
The methods using sols as raw materials (colloidal suspensions of hydrated Si0 2
in water) can conveniently be utilized in the preparation of homogeneous clear silica
glass with a certain content of doping elements. The sol is usually produced by
modified hydrolysis of tetraethoxysilane (C 2 H s O) 4 Si in a water-alcohol solution
[85, 87, 88]; commercially produced stabilized sols can also be utilized (e.g. Ludox
by du Pont [86]). In the subsequent stage, the sol is converted to gel by adding acid,
together with doping ions in the form of nitrates or carbonates. The formation of
a gel creates valency bonds between the dispersed particles and yields a lattice
structure. Following dehydration and drying, the nitrogen oxides or C 0 2 volatilize
and a xerogel is obtained [86].
The methods utilizing direct hydrolysis of Si compounds to gels allow Si0 2 gels
with a very small diameter of particles to be prepared at a certain controlled pH
value [87].
The more recent methods used to prepare gels with doping admixtures employ
solely alkoxysilicon alkoxymetallic compounds as initial raw materials [88].
A number of procedures have been developed for the manufacture of Si0 2 xerogels
with very low contents of OH groups, e.g. that by Heraeus [89] where, after drying,
the Si0 2 gel is heated with liquid SiCl4 under reflux.
The methods according to [90] (where the Si compounds are hydrolysed with
D 2 0 ) likewise yield clear silica glass with a low content of OH groups.
Whereas the xerogels obtained by the standard procedures consist of particles
with sizes of the order of 1 to 100 μιιι, some modified methods produce particles
smaller than 1 μιιι [88].
The last stage of clear silica glass manufacture comprises fusion of the Si0 2 powder
(xerogel). This is carried out in the usual ways, i.e. by melting under reduced pressure
187
or in an inert atmosphere, either in crucibles or on pads (sintering of preforms). In
the production of homogeneous glass, the powdered Si0 2 has first to be calcinated
at 1000 to 1200 °C to remove gases and adsorbed moisture; however, cristobalite
£=^ ■13
■ 1
_i
■ 12
Fig. 105 - Schematic diagram

of a device for melting high-purity silica
glass from powdered S i 0 2 :
1 - powdered Si0 2 charge; 2 - silica
glass; 3 - supply of protective gas;
4 — outlet of protective gas; 5 — silica
glass crucible; 6 — inductor winding;
7 — cooled protective jacket of silica
glass
Fig. 104 — Schematic diagram of apparatus for the melting of silica glass from powdered Si0 2 with
induction plasma burner: 1 — powdered S i 0 2 ; 2 — plasma; 3 — gas for powdered Si0 2 feed;
4 — fused-on ingot of silica glass; 5,6 — burner tubes of silica glass; 7 — burner cover; 8 — cooling
gas; 9 — high-frequency generator winding; 10 — high-frequency inductor; 11 — gas for the plasma;
12 — hopper with sieve; 13 — feeding hammer; 14 — ingot holder; 15 — device for shifting and turning
the ingot; 16 - cooling; 17 — coolant supply
is not yet formed at these temperatures [91]. The temperature interval suitable for
complete sintering is given as between 1200 and 1600 °C. This considerable range
of melting temperatures is due to a number of factors (content of impurities nucleating
the formation of cristobalite, particle size, content of OH groups, etc.).
188
The melting or fusion of the xerogel particles for communication fibre production
is carried out by special procedures, such as with an induction plasma burner (Fig. 104)
[92] or in a special high-frequency electric induction furnace in a crucible of high-
purity Si0 2 [93] (Fig. 105). The powdered Si0 2 is preheated at 1000 °C [94].
3.4.4.2 Melting of silica glass cullet
Cullet is produced in the manufacture of clear silica glass tubing as a result

of the low overall yields (about 30%). Using suitable technological procedures, such
as gas fusion of its fine-grained fractions, the cullet can be remelted to clear silica
glass. Melting of cullet produced in the electric melting of silica glass is particularly
advantageous.
The technological procedure has the disadvantage of a costly and time-consuming
treatment of cullet prior to the melting proper.
3.4.4.3 Silica glass ceramics
Silica glass ceramics (also called sintered silica glass) is made from silica
glass cullet by forming from wet or dry material.
In manufacture using the wet material, the silica glass cullet is first ground in the
presence of a liquid in a ball mill (moisture content 18 to 24%) so as to avoid lami
nation. The material is poured into plaster moulds, where it is also pre-dried. The
moulding is then removed, once more dried at 130 to 150 °C, and then sintered at
1200 to 1250 °C for 2 hours. The product shows a low porosity and high mechanical
strength. After sintering, the surface can be heated, e.g. in an oxygen-hydrogen flame,
thus producing a glassy surface.
The dry material can be moulded under a pressure of about 50 MPa. The dry
material is prepared by mixing ground silica glass with organic binders, and the
pressure moulding is followed by heat treatment which is virtually identical with
that used in the wet technology.
However, the products have a somewhat lower mechanical strength and show
greater porosity.
The sintered silica glass products resist abrupt changes in temperature and show
a comparatively low thermal conductivity. However, they do not resist long-term
thermal loading above 1200 °C, which may lead to crystallization and thus to im
paired physical properties. The materials are used to produce insulators working
at high temperatures, to enclose radio aerials, as linings of spaceships and furnaces,
etc. Their density is 1700 to 2200 kg m" 3 , water absorption by volume 0.5 to 29%,
shrinkage 1 to 4%, a = 5.4· 10"6 °C _1 , bending strength is 18 to 60 MPa, and
softening temperature 1250 °C.
189
3.4.4.4 Surface finishing of t u b e s m a d e of silica glass
Both the outer and inner surfaces of tubes are treated to improve the
stability of the shape of clear silica glass tubing at high temperatures (e.g. in their
application in the manufacture of semiconductors). The treatment is based on
controlled diffusion of substances capable of nucleating the crystallization of cristo-
balite (e.g. A1 2 0 3 , CaO, MgO, C s 2 0 , and others). Before application, the tubes
treated in this way should first be heated for about 12 hours at 1280 °C [95, 96].
These tubes are manufactured for example by the Heraeus Corporation under the
trade name Form Stabil.
3.4.4.5 Silica g l a s s e s with a d m i x t u r e s of d o p i n g s u b s t a n c e s
Doping substances are added in order to achieve certain specific properties

of silica glasses.
Insofar as the substances are introduced directly into the natural raw material,
a very difficult technological process of diffusion into quartz crystals is involved.
Introduction of the doping substances into synthetic silicon raw materials is
a substantially simpler process, which is advantageously utilized particularly in the
manufacture of fibres for optical communication and other special optical purposes.
Doping substances can likewise be introduced into the surface of already melted
silica glass by means of diffusion processes. The glass can be coloured with com
pounds of Cu, V, Cr, Co, Ti, Pr, Nd, Sa, Eu, W, U, Ce and others.
Silica glass containing 9 to 19 wt.% of T i 0 2 exhibits a zero coefficient of thermal
expansion; absorption of light in the ultraviolet region of the spectrum can be raised
by additions of A1 2 0 3 + E u 2 0 3 ; and the thermoelasticity coefficient is reduced
by A1 2 0 3 + S m 2 0 3 .
3.4.5 Manufacture of Vycor type extractable glasses
The manufacture of extractable Vycor type glasses is based on melting an

alkali borosilicate glass having the approximate composition of, for example,
67.6 wt.% Si0 2 , 23.7 wt.% B 2 0 3 and 8.7 wt.% N a 2 0 . The glass is formed by standard
glass technologies into the final shapes (mostly tubes) and heat treated to achieve
separation of the alkali borate phase; the latter is then leached in an acid and the
"skeleton" of Si0 2 is sintered.
The heat treatment, which brings about separation of the alkali borate phase,
depends on the composition of the initial glass and on the wall thickness of the ware.
The time of heating is indirectly proportional to temperature, which varies over the
range of 500 to 600 °C.
190
Forming and heat treatment bring about vaporization of a certain proportion
of B 2 0 3 and N a 2 0 from the glass surface, which then has a somewhat different
composition. This is why the layer has to be removed by means of 5% H F before
the extraction proper.
The extraction is carried out either in dilute HC1 at a concentration of 3 mol Γ \
or dilute H N 0 3 at a concentration of 3 mol Γ 1 at 98 °C, the time of extraction
depending on bath temperature, wall thickness of the ware and concentration of
the acid.
Before sintering, the water remaining in the ware after washing has to be removed
from the pores by drying. This is effected by raising the temperature gradually to
120 °C
The ware is sintered by heating the extracted and dried ware to 800-1200 °C, with
a certain holding time at 600 °C where the last residual water is removed. After
sintering, the ware is annealed.
The technology has the advantage of producing ware (particularly tubes) of
precise dimensions, and the disadvantage of a residual content of non-extracted B 2 0 3
and N a 2 0 which affect the purity of the glass and also its physico-chemical properties.
From the standpoint of its properties, Vycor glass is therefore not a fully satisfactory
substitute for silica glass.
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[4] CHAKLANDER, A.C.D. - ROBERTS, A.L.: J. Am. Ceram. Soc. 44, (1961), 1, p. 35-41
[5] CHAKLANDER, A.C.D.: J. Am. Ceram. Soc. 46 (1963), 1, p. 66-71
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[8] MACKENZIE, J.D.: J. Am. Ceram. Soc, 43 (1960), 12, p. 615-620
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[10] SINELNIKOV, I.I.: Dokl. Akad. Nauk SSSR, 106 (1956), 5, p. 870-872
[11] MORIYA, Y.: Vacuum (1961), 11, p. 158-172
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The Knolls, Schenectady-New York 1961
[13] KOSTYLEVA, E.E.: Nekotorye metody izuchenya rudonosnogo kvarca (Some Methods of Investi
gating Ore-Bearing Quartz). Nauka, Moscow, 1964
[14] CHERENISIN, I.I. - BOGANOV, A.G.: Fizika i khimia stekla, 3 (1977), 1, p. 87-90
[15] SHCHEKOLDIN, A.A. - GLADOV, I.A. - BAZURIN, A.Z. - PRYANISHNIKOV, V.P. - KRIVKO, L.I.:
Steklo Keram., 25 (1968), 11, p. 17-19
[16] ZACHARCHENKO, A.I.: Min. Sv. Lvovsk. Geol. Ob-va (1950) 4
[17] STAVROV, O.D.: Geokhimiya (1961) 6
191
[18] FANDERLIK, I. - DUBSKY, F.: Unpublished report
[19] BRUCKNER, R.: J. Non-Cryst. Solids 5 (1970), 2, p. 123-175
[20] TAMMANN, G.: Der Glaszustand. L. Voss, Leipzig, 1933
[21] LEBEDEV, A.A.: Izv. Optichesk. Inst., Leningrad, 2 (1921) 10, p. 1-18
[22] ZACHARIASEN, W.H.: J. Am. Chem. Soc, 54 (1932), p. 3841-3851
[23] WARREN, B.E.: J. Am. Ceram. Soc, 24 (1941), p. 256-261
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[26] WINTER, A.: Verves Refract., 9 (1955), p. 147-156
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[39] BALASHOV, Y U . S . - CHERNYSHEV, A.V. - SANIN, V.N. - VARSHAL, B.G. - PAVLOVA, G.A.:
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[51] KITAYGORODSKH, I.I.: Technologie skla (Technology of Glass), Vol. II, SNTL, Prague, 1954
[52] ESPE, W.: Technologie hmot vakuove techniky (Materials of Vacuum Technology). Vol. II, SAV,
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PANCZESNIK, T. - SARWINSKI, A. - SWIECKI, J.: Szklo Ceram., 24 (1973), 3, p. 75-77
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FRG Patent No. 1 596971 (1971)
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NASSAU, K. - SHIEVER, J.: Am. Ceram. Soc. Bull., 54 (1975), p. 1004-1009
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FRG Patent No. 2008 653 (1970)
FRG Patent No. 1 596473 (1970)
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Fibropsil Optical Fibres 1980, Prospectus by Quartz et Silice
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FRG Patent No. 2202494 (1972)
French Patent No. 2 194663 (1973)
193
4 PHYSICAL AND CHEMICAL PROPERTIES
OF SILICA GLASSES
4.1 INTRODUCTION
Silica glass is the only single-component glass which has found wide appli
cation in commercial practice. Compared to other glasses, it has the lowest thermal
expansivity, great chemical durability with respect to water, acids, hydroxides and
a number of various chemicals, the highest resistance to thermal shock, great spectral
transmittance in the ultraviolet, visible and infrared regions of the spectrum, out
standing electrical insulating properties, a high softening temperature, etc.
A number of types of clear silica glasses showing various physical properties have
recently been manufactured. The basic types of these glasses are listed in Table 29 [5].
4.2 CHEMICAL PROPERTIES
4.2.1 Chemical composition
The chemical purity of clear silica glass is particularly high. Opaque silica
glass contains more than 99.4% Si0 2 , the remaining 0.1 to 0.6% being mostly A1 2 0 3 ,
CaO, F e 2 0 3 , T i 0 2 and MgO. This glass contains large numbers of closed bubbles,
but is not moisture-absorbing nor permeable to gases. According to analyses [4],
the gases in the bubbles contain about 60% CO, 10% C 0 2 , 8% 0 2 and 22% N 2 .
The chemical purity of clear silica glass depends in the first place on the purity
of the raw material and the manufacturing process employed. The trace impurities
in clear silica glass occur mostly over the range of units or tenths of ppm (1 ppm =
1 · 1 0 - 4 wt.%). There is the exception of the OH groups which attain, particularly
in some special clear silica glasses, up to 1000 ppm. The results of determinations of
trace impurities in synthetic silica glasses frequently lie at the limit of detection of
the respective elements.
Tables 30, 31, 32 and 33 list the chemical compositions or contents of trace im
purities in opaque and clear silica glasses [6, 7, 8, 9].
194
Table 29
Survey of the individual types of clear silica glass
Manufacturer Type I Type II Type III Type IV Type V
Thermal Syndicate Ltd Vitreosil IR Vitreosil 055 Spectrosil A Spectrosil WF

(Great Britain) Vitreosil 066 Spectrosil B
USSR KI KV, KU KVR
Heraeus Quarzschmelze Infralux Heralux Suprasil Suprasil W M 68

GmbH (FRG) Infrasil Normalqualität H M : 84
OHF Zerosil
Normalqualität 0
Herasil
Homosil
Ultrasil
VEB Jenaer Glaswerk Q 1,Q2, Q 3

(GDR) Q4
Quartz et Silice Pursil K Tetrasil Tetrasil SE Germisil

(France) Puropsil
Corning Glass Works Code 7940 Code 7943

(USA)
General Electric Co. 201 101 102 151

(USA) 204 105 104
206 106
Nippon Sekiei Garasu Co. IF UF, SG WF

(Japan)
Heraeus-Amersil Inc., Amersil

Hillside, N.Y. (USA) Optosil
Jablonec: Glass Works. Trasil

C.C., Josefüv Dül at
Jablonec n.N (Czechoslovakia)
Sklo Union-Sklotas Silquarz

Novy Bor (Czechoslovakia)
Table 30 (
Chemical composition of opaque silica glass
Glass type wt. %
Si0 2 Other oxides
Czechoslovak opaque silica glass, manufacturer: 99.5-99.9

Jablonecke sklärny, N.C., Josefüv Dül Works [1]
Opaque silica glass Fondal, manufacturer: about 99.6 about 0.28 A1 2 0 3

Didier-Werke, A.G. Wiesbaden - FRG [2] about 0.08 F e 2 0 3
Opaque silica glass Rotosil, manufacturer: about 99.8 the balance, about
Heraeus Quarzschmelze GmbH Hanau - FRG [3] 0.2 A1 2 0 3 , CaO, F e 2 0 3 ,
T i 0 2 , MgO and others
Translucent Vitreosil about 99.7 groups

Thermal Syndicate Limited, 0.0176 Al, 0.0027 Ca,
Wallsend - Great Britain [8] 0.0042 Fe, 0.0007 Li, j
0.0014 Mg, 0.0003 Na,
0.0065 Ti, 0.0200 OH groups
0.0021 K,
1 J
Table 31
Content of OH groups and chlorine in clear silica glasses
Type of clear silica glass OH Cl

(ppm) (ppm)
Normalqualität H 1 ) 130 25 to 35
Heralux, Herasil, Homosil, Ultrasil, OHF 1 )
Normalqualität 01) 20 to 30 20 to 30
Suprasil1) 1000 to 1300 55 to 100
Suprasil-W1) < 5 up to 100
Infrasil l) < 5
Infralux1) < 0.1
Vitreosil 0552) 5 0.4
Vitreosil 066
Spectrosil 2) 1000 cca 50
Spectrosil WF 2 ) 2 to 5 cca 180
Pursil K 3 ) 10-20 nd
Puropsil 3 ) < 20 nd
Tetrasil3) 1200 nd
Tetrasil 3) < 20 nd
Siliquartz-Czechoslovak manufacture4) up to 5 nd
1
) According to catalogues by Heraeus Quarzschmelze GmbH [6], [7]
2
) According to catalogues by Thermal Syndicate Ltd. [8]
3
) According to catalogues by Quartz et Silice [9]
4
) According to measurements by the State Glass Research Institute at Hradec Krälove
nd — not determined
Table 32
Trace impurities in synthetic silica glasses (the Heralux silica glass melted from rock crystal is given
for the sake of comparison)
1 Element Content (ppm)
Spectrosil Suprasil Tetrasil Heralux

Spectrosil WF Suprasil W Tetrasil S.E.
[8] [6] [9] [6]
Γ Ag < 0.04 < 0.05 not determined not determined

A1 0.02 0.1 < 0.1 10-50
As < 0.001 < 0.001 not determined 0.08
Au 0.000 01 0.000 3 not determined not determined
B 0.02 < 0.01 not determined < 0.1
Ca < 0.7 0.1 <0.1 0.8-3
Cd < 0.02 0.000 2 not determined < 0.1
Co 0.000 1 not determined <0.1 not determined
Cr < 0.02 not determined < 0.1 not determined
Cu < 0.003 < 0.01 < 0.1 0.07
Fe < 0.02 < 0.1 < 0.1 < 3
Ga 0.001 not determined not determined < 0.008
K 0.005 < 0.05 < 0.1 0.8
Mg < 0.1 < 0.1 < 0.1 0.2
Mn 0.006 < 0.01 < 0.1 0.01
Na 0.004 < 0.01 < 0.2 < 3
Li not determined not determined < 0.1 not determined
P 0.03 < 0.1 not determined 0.1
Sb < 0.001 < 0.001 not determined 0.15
Ti < 0.04 < 0.1 < 0.1 0.8
U < 0.01 not determined not determined 0.0003
I Zn 0.02 not determined < 0.1 not determined
Zr < 0.15 < 0.001 not determined < 0.1
Ba < 0.03 not determined not determined not determined
Bi < 0.01 not determined not determined not determined
Br < 0.03 not determined not determined not determined
Cs < 0.007 not determined not determined not determined
Ce < 0.007 not determined not determined not determined
Ge < 0.12 not determined not determined not determined
Hf < 0.04
In < 0.006
I. < 0.007
Ir < 0.03
La < 0.007
Pb < 0.06
Hg < 0.03
Mo < 0.03
Ni < 0.4
Nb 1 < 0.05
Os j < 0.05
_ I
197
Table 32 - cont.
Trace impurities in synthetic silica glass (the Heralux silica glass melted from rock crystal is given
for the sake of comparison)
Element Content (ppm)
Spectrosil Suprasil Tetrasil Heralux

Spectrosil WF Suprasil W Tetrasil S.E.
M [6] [9] [6]
Pd < 0.02
Pt < 0.03
Re < 0.02
Rh < 0.005
Rb < 0.004
Ru < 0.05
Sc < 0.07
Se < 0.17
Sr < 0.04
S < 0.16
Te <0.02
Tl < 0.02
Th < 0.01
Sn < 0.02
W < 0.03
V 0.008
Y < 0.04
Table 33
Chemical analyses of silica glasses
Silica glass Impurities (ppm)
Na20 κ2ο Li20 CaO MgO A1 2 0 3 Fe203 Ti02
Trasil 3 ~) 1 14 10 . 18 3 1 '
(Jablonecke sklärny,
Svedlär raw material)
Silquartz 3 1 1 9 1 22 1 2
iSklotas. C.C., Novy Bor,
Svedlär raw material)
1
Silquartz 4 3 1 4 1 67 1 1
(Detkovice raw material)
Silquartz 5 2 5 3 3 33 1 5
(Kyshtym raw material)
198
Table 33 — com.
Chemical analyses of silica glasses
Silica glass Impurities (ppm)
Na20 κ2ο Li 2 0 CaO MgO Al203 Fe203 Ti02
Silquartz 11 24 ! -> 5 150 2 13

(MBK raw material)
Silquartz 13 3 1 3 1 41 1 1
(Bulgarian raw material)
Pursil 1 1 6 5 6 33 2 2 ■
(22 mm diameter tubing)
Infralux 2 1 17 *) 1 128 3 1
(21 mm diameter tubing)
Kontiglas GDR 6 3 28 24 *> 153 2 3
(Staaken raw material)
Kontiglas GDR 4 6 11 3 1 70 1 2
(TSL raw material)
Rotovak GDR 6 2 ,o ! 5 i ! 60 2 2
1
Schott Jena GDR 8 3 33 1 1 1 1 2
(synthetic)
OHF (Heraeus) 1 ! 11 1 1 53 2 3
Poland (Polam 15 , 5 : 4 12 2 43 4 5
Ozarov - tubing)
Toshiba Ceramics i i 2 1 1 1 15 1 6
(Japan)
Svetotekhnika Saransk 5 5 2 7 6 27 2 6
(USSR)
Bulgaria 9 2 2 2 1 36 1 1
4.2.2 Resistance to water and aqueous solutions of salts
In contrast to other commercial glasses, silica glass has an outstanding

resistance to water. It does not react with water under normal conditions. This high
resistance to water can be explained by the formation of a thin layer (of the order
often molecules thick) of colloidal silicic acid on the surface, which protects the glass
from corrosion. Silica glass does not contain components other than Si0 2 and is
not hygroscopic at the surface. According to Czechoslovak Standard CSN 700531
199
(Resistance of Glass to Water), clear silica glass has the highest resistance of all the
glasses belonging to hydrolytic class I. Table 34 lists the results of measuring the
durability of clear silica glass (according to Czechoslovak Standard CSN 700531)
with respect to water, in comparison with the borosilicate Simax and Pyrex glasses.
For this reason silica glass may be very advantageously applied to the manu
facture of special water stills in cases when the purity of the water is of critical im
portance.
Table 34
Resistance of glasses to water, according to Czechoslovak Standard
CSN 700531
Glass Hydrolytic class mg N a 2 0 / 2 g

of ground glass
clear silica glass I < 0.01
borosilicate glass
type Simax, Pyrex I 0.03-0.04
Some slight dissolving of silica glass in water occurs only at high temperatures
and under very high pressures. Pryanishnikov [10] specifies the solubility of clear
silica glass a s l . l 3 g m " 2 after three-hour heating at 310 °C in water under a pressure
of 10.13 MPa.
Silica glass also well resists aqueous solutions of salts, except that alkaline aqueous
solutions of salts attack it mildly. Table 35 gives experimental values for the dis
solving of silica glass exposed to the effects of aqueous solutions of various salts.
The chemical durability of opaque silica glass is substantially lower than that of
clear silica glass [11].
Table 35
Durability of clear and opaque silica glass with respect to aqueous solutions of salts [11]
Solution of Time Temperature Loss in weight (gm~ 2 )

(h) (°c)
silica glass
clear opaque
NaCl (10%) 2 102 0.14 0.34

CaCl 2 (20%) 2 103 0.06 0.40
N a 2 C 0 3 (10%) 2 102 1.20 4.99
C u S 0 4 (10%) 24 102 0.29 0.70
200
4.2.3 Durability with respect to acids
Silica glass resists both dilute and concentrated acids comparatively well,
even at elevated temperatures (up to about 100 °C), relative to other current commer
cial glasses. There are the only exceptions of hydrofluoric acid (which already reacts
at room temperature) and phosphoric acid (at temperatures above 200 °C).
Table 36
Loss in weight of clear and opaque silica glass due to the effect of concentrated acids
1
Acid Time Temperature Loss in weight (g m~2)
(h) (°c)
silica glass
clear opaque
H2S04
density = 1.84 24 205 0.06 0.13
HN03
density = 1.40 24 115 0.11 0.15
HC1
density = 1 . 1 9 24 66 0.14 0.33
acetic acid, 70% 24 108 0.01 0.03
oxalic acid, 30% 24 108 - 0.15
phosphoric acid 15 300 58.0

15 700 230.0 -
Table 36 lists, according to [11], the values for the dissolving (corrosion) of silica
glass in some acids on heating.
At room temperature and prolonged times of direct contact (240 hours) of the
acids given in Table 36 (with the exception of phosphoric acid), the loss values in
glass decrease down to the limit of measureability; no discernible corrosion of glass
by these acids occurs.
According to Czechoslovak Standard CSN 700532, clear silica glass belongs to
class I of durability with respect to acids and shows loss values smaller than
0.1 mg d m - 2 of surface area. However, silica glass is attacked by hydrofluoric acid
even at room temperature. Among others, this effect is utilized to clean chemically
contaminated surfaces, particularly those of vessels and tubes of clear silica glass.
201
Heraeus Quarzschmelze GmbH [6, 7] recommend degreasing the glass surface and
then etching off the contaminated glass layer at room temperature, either (a) for
1 to 2 minutes with about 75% HF, or (b) for 3 or 4 minutes with about 45% HF,
or (c) for 10 minutes with about 25% HF. This etching will remove a silica glass
layer about 6 μιη in thickness (cf. Fig. 106). The glass ware should then be thoroughly
rinsed in distilled water (up to 20 times in extreme cases) and dried in an oven at
100 °C.
1:20
i 10
-5
Fig. 106 - The rate of etching the surface

4 6 8 of clear silica glass with HF [6, 7]
». t (min)
It was also found [12] that dissolving of clear silica glass in HF proceeds about
three times as fast as that of quartz (rock crystal). In this test, the sample in powder
form (particle size 0.04 mm) in an amount of 1 g was heated while stirring continuously
in 100 cm3 of HF solution (Table 37).
Table 37
Solution of Si0 2 phases in HF [12]
Si0 2 phase Percent of dissolved Si0 2 sample in HF
5% HF 1% HF
(for 0.5 h) (for 1 h)
Quartz 30.1 5.2

Tridymite 76.3 20.3
Cristobalite 74.3 25.8
Clear silica glass 96.6 52.9
4.2.4 Durability with respect to alkalis
Silica glass shows only a limited resistance to alkaline solutions, particularly

at elevated temperatures. Clear silica glass is especially sensitive to even trace con
tamination of its surface by alkalis, as even these traces are capable of accelerating
202
crystallization of silica glass at an elevated temperature. This is why it is recommended
to remove thoroughly (using a nylon cloth wetted in pure ethyl alcohol) even finger
prints (containing traces of alkalis) from the surface of silica glass before heating it
to temperatures above 700 °C. In contrast to acids, alkaline solutions attack the
surface of silica glass quite markedly. Compared to corrosion by water and acids,
that by alkaline solutions shows a considerable difference, with respect both to the
amount of glass dissolved and the chemical effects of these agents. Alkalis directly
impair the Si—O—Si bonds, and no protective surface silica gel is formed. For
this reason, the effect of alkaline solutions on silica glass is much stronger than that
of water and acids.
Table 38
Dissolving of clear silica glass in alkaline solutions [7]
Solution Time Temperature Loss in glass
(h) TO
^ cmv
NH 4 OH 10".. 100 20 0.019

NaOH I/o 100 20 0.031
NaOH '10% 100 18 0.0095
KOH 1% 100 20 0.019
KOH 30% 100 18 0.027
Na2C03 5% 100 18 0.0015
NaOH 5% 10 100 1.50
NaOH 8% 10 100 1.21
KOH 10.2% 10 100 1.13
N a 2 C 0 3 10% 10 100 0.37
According to Czechoslovak Standard CSN 70 0533 (Determination of the Resist

ance of Glass to Alkalis), clear silica glass belongs to class I of durability. The losses
in the weight of the glass are about 50 mg per 100 cm2.
Table 38 [7] illustrates the dissolving of clear silica glass in various alkaline
solutions, at room and elevated temperatures.
4.2.5 Durability with respect to other agents
In contrast to other commercial glasses, silica glass resists the effects of

a number of melts of both metals and non-metals, various oxides and gases, as well
as vapours and salts. Tables 39, 40, 41 and 42 [5, 7] specify the resistance of silica
glass to metals, non-metals, oxides, gases, vapours and salts.
203
Table 39
Resistance of silica glass to oxides [7, 8, 14]
Oxide Reaction with silica glass
Alkali oxides accelerated crystallization of silica glass above 800 °C

A1 2 0 3 reacts at temperatures above 1000 °C
BaO reacts above 900 °C
Bi203 does not react up to 955 °C
CaO reacts above 900 °C
CuO reacts above 950 °C
FeO, F e 2 0 3 react above 900 °C
MgO reacts above 900 °C
PbO reacts above 800 °C as PbO melt
Sb203 does not react up to 888 °C
Te02 does not react up to 938 °C
v2o5 does not react up to 964 °C
ZnO reacts above 800 °C
Table 40
Resistance of silica glass to metals and non-metals
Element Reaction with silica glass
Ag does not react

Al reacts vigorously at 700-800 °C
Au does not react
Br does not react
C reacts significantly at temperatures above 1500 °C
very slightly above 1000 °C [8]
Ca reacts only above 600 °C
Cd does not react; Cd vapours react at high temperatures and on long-term contact
Ce reacts above 800 °C
Cl does not react even at elevated temperatures and in the presence of H 2 0
F reacts in moist environment only
Ga does not react up to 1100 °C [14]
Ge does not react up to 1100 °C [14]
Hg virtually does not react [13] 1 )
I does not react
Li reacts at temperatures above 250 °C
Mg reacts vigorously at 700-800 °C
Mn does not react2) [13]
Mo does not react
Na Na vapours react at elevated temperatures
P reacts
Pb does not react
Pt does not react 2 ) [13]
|_S reacts slightly at temperatures above 1000 °C
204
Table 40 - com.
Resistance of silica glass to metals and non-metals
Element Reaction with silica glass
Sb does not react up to 850 °C [14]

Si reacts slightly
Sn does not react
Tl does not react
w does not react
Zn does not react
*) Reacts at high temperatures only in the presence of H2 (according to [13])

2
) According to [13], Hg reacts with silica glass on low-pressure discharge of Hg vapours (dark staining
of glass)
Table 41
Resistance of silica glass to gases and vapours [7, 8,13]
Gas Reaction with silica glass
H2,N2,02 do not react

N02, S02 do not react ι
CO does not react
I 2 ,S,Cl 2 ,Br 2 do not react
HC1 does not react
F2 reacts
Table 42
Resistance of silica glass to salts [5, 7]
Salts Reaction with silica glass
BaCl2 BaCl2 melt reacts

BaS0 4 reacts above 700 °C
Borates react as melts
Nitrates react as melts
KC1 reacts as melt; promotes crystallization of silica glass
NaCl, KF react as melts
AgCl does not react up to 630 °C [14]
AgBr does not react up to 600 °C [14]
Alkali phosphates react strongly
Na2S04 does not react; promotes crystallization of silica glass at higher
temperatures
(NH 4 ) 2 PtCl 4 reacts above 900 °C
ZnCl2 reacts as melt
Zn 3 (P0 4 ) 2 reacts slightly at 200 °C, strongly at 1000 °C
ZnSi0 3 reacts above 1000 °C
Na2W04 promotes crystallization of silica glass
205
4.3 MECHANICAL PROPERTIES
4.3.1 Density
The density of clear silica glasses at room temperature varies over the range
of 2200 to 2210 kg m" 3 . Opaque silica glass shows somewhat lower values (2020 to
2080 kg m" 3 ) as a result of its content of about 5 vol.% of closed bubbles.
Table 43
Density of clear silica glass in terms of "water" content
Glass made by Content of H 2 0 Density Time of heat treatment at 1000 °C

W.C. Heraeus in wt.% (kgm-3) (elimination of "water")
Homosil 0.0060 2203.60 0

0.0056 2203.71 500
0.0052 2203.82 1000
0.0048 2203.94 2180
Suprasil 0.0660 2201.80 0

0.0310 2202.54 500
0.0230 2203.19 1000
0.0120 2203.79 2180
Compared to multicomponent silicate glasses and borosilicate glass, the density

of clear silica glasses shows a minute decrease with increasing content of OH groups
in the structure [15]. The phenomenon is exemplified by Table 43, which gives the
density of clear silica glass melted from rock crystal (type Homosil by Heraeus) and
of that made from a synthetic raw material (SiCl4 — type Suprasil by Heraeus) in
terms of the content of OH groups in the glasses [15]. Before the density measure
ments the glass specimens, in the form of platelets 1 mm in thickness, were heat
treated for 1 hour at 1300 °C and then rapidly quenched. From the basic glasses,
the OH groups were removed by long-term (500, 1000 and 2180 hours) heat treat
ment at 1000 °C. The reproducibility of the method of density measurement (double
weighing in water and in air) was ±0.03 kg m" 3 [15].
The density of clear silica glasses was also found to depend on their heat treatment
(so-called Active temperature) over the region of 1000 to 1800 °C [16]. Figure 107
demonstrates the effect of Active temperature on density, for three types of clear
silica glasses (cf. Table 29).
4.3.2 Modulus of elasticity and Poisson's ratio

Glass is not an ideally elastic material according to the physical definition;
however, in technical practice it can be regarded as a substance capable of returning
to its original state within a negligible period of time after loading, and to exhibit
206
only minute subsequent elastic recovery [17]. In terms of the values of its elastic
properties, glass behaves as a normal technical material under all types of mech
anical loading as well as during changes in temperature, which bring about internal
stresses due to temperature gradients. Generally speaking, the moduli of elasticity
(£, G and Poisson's ratio μ) can be regarded as values characterizing the resistance
,,-° · i
2205.0
m \ >
2204.0 l V \
v
/
22030 . /
2202.0 / // \ \ B Fig. 107 — The density of clear silica glasses vs.

fictive temperature: glass type I (cf. Table 29):
C - Vitreosil IR;D - Infrasil;
2201.0 . / / A'
■'/ A glass type II: E — Herasil; F - Ultrasil;
glass type III (synthetic silica glasses with a high
oofm? Ls:" ■ ■ ■ ^_ content of OH groups): A — Suprasil,
1000 1200 1400 1600 1800 B - Spectrosil
t CO
of a solid body to various kinds of deformation. The elastic properties of silica glass
are thus also among its significant material constants; they should be well known
to all technologists working with this material. There are relationships between the
modulus of elasticity in tension E (also known as Young's modulus), the modulus
of elasticity in shear G (the torsion modulus) and Poisson's ratio μ, which allow the
third quantity to be calculated from the other two [17]:
E = 2G(1 + μ) (34)
E
G= (35)
2(1 + μ)
E - 2G
(36)
2G
The moduli of elasticity E and G of silica glass increase with temperature, contrary
to those of other glasses. According to Gillod [18] and Spinner [19], the mean
207
coefficient of temperature change in Young's modulus E for silica glass over the
temperature range 0 to 900 °C is within the following limits:
/ A £ \ 900 °C
— = 10.198 to 13.600 MPa °C~l (37)
\Δί/0ο0
The temperature coefficient of change in the torsion modulus G is given by Spinner
[19] by the equation:
/ A G yoo°c
— = 3·098 MPa
°C (38)
\Δί/οοα
Figure 108 shows the temperature dependence of the modulus of elasticity E for
clear silica glass. The minimum values of the moduli of elasticity E and G [23] were
found at -208 °C: 70 020 MPa (for E) and 30 400 MPa (for G).
8600
g r
at
£ 8200
5 7800
♦ 7400
Fig. 108 - Temperature dependence of the
I 7000 modulus of elasticity E of clear silica
-200 0 200 600 1000 1400 glass [7]
6600
- f CO
Table 44 lists the experimentally established values of the moduli of elasticity E

and G and those of Poisson's ratio μ for clear silica glass according to various authors.
With regard to the values taken mostly from the literature [8, 7,20], the E and G
values are also given in kp mm" 2 for the sake of comparison. Even though it is almost
Table 44
Moduli of elasticity E and G and Poisson's ratio μ of clear silica glass at room temperature
Value according to E G μ
(MPa) (kp mm 2) (MPa) (kp mm 2
)
Thermal Syndicate Limited [8] 72 568.8 7400 - - 0.17
Botvinkin and Zaporozhski [21] 73 549.5 7500 31 381.1 3200 -
W.C. Heraeus [7] 70 607.5 7200 30 204.3 3080 0.17
Mallinder and Proctor [20] 71 882.4 7330 31 381.1 3200 0.15

Hradec Krälove [17] 73 088.6 7453 31 508.6 3213 0.16
208
negligible, there is a certain small dependence of the moduli of elasticity and Poisson's
ratio on the density of silica glasses [22]. The modulus of elasticity G decreases
with increasing density of silica glasses, while Poisson's ratio μ increases (cf. Figs
109 and 110). The various density values for the individual silica glasses (A, B, C)
were achieved by heat treatment at various temperatures (the effect of Active tem
peratures on the density of glass).
31400
O 31 300
31 200
31 120
2201 2203 2205 2201 2203 2205
3
f> (kg i - ^ f (kg m- )
Fig. 109 — Modulus of elasticity in torsion G as Fig. 110 — Poisson's ratio μ as a function
a function of density of clear silica glasses [22]: of density of clear silica glasses [22] :
A - Vitreosil IR; B - Corning 7940; A - Vitreosil IR; B - Corning 7940;
C — Spectrosil C — Spectrosil
4.3.3 Strength of silica glass
The strength of silica glass is above all affected by the quality of its surface.
Its strength is substantially reduced by surface imperfections, even in the form of fine
microfissures (of the order of several tens of μιιι), surface contamination, inhom-
ogeneity, crystallization, etc. The theoretical tensile strength of silica glass, calculated
from its structure, is approximately 22 065 MPa (2250 kp mm"2). The maximum
theoretical tensile strength should correspond to l/5th of the modulus of elas
ticity E (Young's modulus), i.e. for silica glass to about 14 023 MPa (1430 kp mm"2).
Similar values have been achieved with very thin fibres of clear silica glass (of the
order of μιη) with undamaged surfaces; the measurement was carried out in vacuo
at -196 °C [22]. The values obtained, 13 533 MPa (1380 kp mm"2), therefore closely
approach the theoretical tensile strength of silica glass. The strength is also influenced
by the environment (air, moisture, vacuum, etc.), as demonstrated by Fig. 111.
A certain small decrease of the glass strength with time was also determined; however,
this appeared only when the glass was kept in an air atmosphere. The decrease can·
209
thus be attributed to the effect of moisture and other impurities on the surface of the
silica glass measured. No similar change was observed when measuring the strength
in vacuo at -196 °C (Fig. 111).
The tensile strength decreases considerably as a result of increasing the diameter
of clear silica glass fibres (Fig. 112).
1500
Ά
.9.8066)
I
I" ■
4 500
1 1 1 1 1
ΚΓ 10u 10z IT 10°

-»- f (min)
Fig. 111 - Strength of Vitreosil IR silica glass (in the form Fig. 112 — Tensile strength of clear
of fibres 20 to 40 μπι in diameter) in terms of time [22]: silica glass fibres in terms of their
/ - measured at room temperature in air; / / - measured diameter [13]: 1 - measured in
at room temperature in vacuo; / / / — measured at — 196 °C moist atmosphere; 2 — measured
in vacuo in dry atmosphere; 3 — measured
in vacuo after heating
The actual strength of clear silica glass in tension, determined on current ware
(rods, tubes, crucibles, flasks, etc.) shows values between 50 and 70 MPa (5 to
7 kp mm"2).
Table 45
Strength of clear and opaque silica glass [4, 5, 7, 8, 23]
Strength at 20 °C Clear silica glass Opaque silica glass

MPa (kp mm" 2 ) MPa (kp mm" 2 )
Compressive strength 490-1960 196-304

(50-200) (20-31)
Tensile strength 50-70 5-40

(5-7) (0.5-4)
Bending strength 66-108 44-58

(6.7-11) (4.5-6)
Strength in torsion 30 -
(about 3)
210
Table 45 [4, 5, 7, 8, 23] lists the values of tensile strength, bending strength and
compressive strength for clear and opaque silica glasses.
Silica glass exhibits a certain variation of mechanical strength values similar to
those of other technical glasses; the variation depends on the state of the surface, the
manufacturing technology and the geometrical shape, as well as the respective
measuring method. In structural designs (for applications of silica glass ware) it is
therefore recommended to calculate with a safety factor of 10 to 15. The British
Standard B.S. 2598/1955 even stipulates a safety factor of 20.
The effect of temperature on the strength of silica glass has not yet been fully
elucidated [17]. According to Kitaigorodskii [23], both the bending and tensile
strengths of opaque silica glass increase slightly with temperature. Clear silica glass
shows an even greater increase in strength with increasing temperature (cf. Fig. 113).
18
16 •
14 A ^
£ 12
y
~ 10 c •
.,·
A
| 8
<^>-
6 B _ >-i--- .·
.t — X - . ■· - — Fig. 113 — Temperature dependence of the mechanical
A D strength of silica glass [23]: A — bending strength of clear
, L.- silica glass; B — bending strength of opaque silica glass;
2
C — tensile strength of clear silica glass; D — tensile
1 1 1 L_
200 600 1000 strength of opaque silica glass
- f CO
4.3.4 Hardness
Hardness is the ability of the surface of the material to keep its shape under
concentrated mechanical loading [17]. Hardness cannot be defined explicitly as
a physical characteristic of a substance. It is a complex property of a material, which
depends on the measuring conditions. There are various methods for hardness
measurements; however, the results obtained are difficult to compare. There is no
unified method of hardness measurement, nor has absolute hardness been defined.
Thus the hardness values of a material are specified in various ways without any
exact mutual relationship. Table 46 lists the values [7, 24, 25] of measured hardness
of clear silica glass in comparison with the hardness of other minerals.
Clear silica glass shows the highest hardness among all technical glasses
(Table 47) [25].
211
Table 46
Hardness of materials [7, 24, 25]
Material Mohs hardness Identation microhardness

(MPa) according to
Vickers Knoop
Talc 1 460
Gypsum 2 588 314
Calcite 3 1 334 1 324
Fluorite 4 1 961 1 598
Apatite 5
Parallel to the optical axis 3 530
Perpendicular to the optical axis 4 119
Orthoclase 6 7 002 5 492
Clear silica glass 5.5-6.5 6 960-8 920 6 080
Quartz
Parallel to the optical axis 7 12 356 6 963
Perpendicular to the optical axis 10817 7 741
Topaz 8 16 161 12 258
Corundum 9 20 447 16 230
Diamond 10 68 156
Table 47
Hardness of clear silica glass and other technical glasses [25]
Glass Identation Vickers hardness

(MPa)
Clear silica glass 6963

Pyrex borosilicate glass 5835
Sheet glass 5296
Lead crystal 4854
4.3.5 Propagation of sound waves
Knowledge of the speed of sound propagation and especially of ultrasound

in clear silica glass is important, particularly for the designers of delay lines. The
speed of sound in silica glass depends directly on its homogeneity. Clear silica glass
of optical quality and with the highest possible homogeneity has therefore been
chosen for the manufacture of delay lines. For example, Heraeus Quarzschmelze
GmbH manufactures clear silica glasses of the types Homosil, Ultrasil, Infrasil I
and Suprasil I for these purposes (cf. Table 29).
212
The speed of sound propagation for longitudinal waves (frequency, up to 20 kHz)
in clear silica glass amounts to 5720 m s _ 1 [7]. The same value, 5720 m s" 1 , was
found for synthetic silica glass (the Suprasil type). In contrast to this, somewhat higher
values of ultrasound propagation speed (frequency above 20 kHz) were established
for clear silica glass. The values published [7, 8, 9] are listed in Table 48.
Table 48
Speed of ultrasound propagation in clear silica glass
Silica glass made from
rock crystal synthetic raw material
Speed of ultrasound propagation lt at 50 °C (m s l) 5750 [8]

1 for longitudinal waves 5968 [7] 5944 [7]
for transverse waves 3774 [7] 3769 [7]

3760 [8]
Temperature coefficient of ultrasound propagation

speed (°Cr M O 6 )
for longitudinal waves 71 [7] 81.4 [7]
90 [8]
for transverse waves 70 [8]
Deg [26] specifies the dependence of sound propagation speed on temperature

in clear silica glass (Fig. 114). The speed was found to increase over the temperature
range of 20 to about 750 °C. A mild decrease was established at a higher temperature
(over the interval of about 750 to 850 °C).
~ 6OO0L-
i 5 900L· ■ ■
5 800h ^ ^ ^ ^ ^ Fig. 114 — The rate of sound propagation v

(at 12 kHz) in clear silica glass in terms of
5 700l ' ' ' ' « · 1 « " L
0 200 400 600 800 1000 temperature t [26]
t CO
4.4 THERMAL PROPERTIES
4.4.1 Thermal expansivity
Thermal expansivity of glass is a result of nonharmonic vibrations of atoms
around their equilibrium positions in the solid silicate network. The vibrations
increase with temperature. The particles have the smaller vibration amplitudes the
213
greater the bond strength between the cation and oxygen [27]. Expansivity is there
fore an indirect measure of the inner network strength, because the stronger the bond
(the greater the attraction between the ions) the more they resist the vibration motions.
Q5|
_ 0.4
E
J§ 0L3
02
0.1
•0.1
300 500 -200 0 200 400 600 800 1000 1200
- t CO - t CO
Fig. 115 — Thermal expansion of silica glass Fig. 116 — Thermal expansion of 1 m rod of
and three technical silica glasses in terms of clear silica glass in terms of temperature [7]
temperature t [24]: A — silica glass;
B — Pyrex-type borosilicate glass;
C — borosilicate glass for sealing to W; 6.8 -
D — soda-lime glass for bulbs
6.0
52 - /4
4.4
3.6
2.5 3
3 / S
2.0
1.2 S 2
v //
AV
Q4
0
i. i .1 i
-200 0 200 400 600 8001000 1200 -200 200 400 600 800 1000
*~ t CO - ^ t CO
Fig. 117 - The mean coefficient of thermal Fig. 118 — Thermal expansitivity of type I /11 silica
expansion y. of clear silica glass vs. temperature / glasses (cf. Table 29) in terms of their fictive
[23]: / - measured at GOI Leningrad; 2 - after temperatures / [22]: 1 — fictive temperature
Sosman [12]; 3 - after Otto and Thomas [28] 1000 °C; 2 - fictive temperature 1720 °C;
3 - fictive temperature 1000°C;4 - fictive
temperature 1530 °C
Various elements have various effects on expansivity; the smallest is shown by net
work-formers and the greatest by freely bound alkalis. As silica glass contains almost
exclusively the stronger Si—O bonds, its thermal expansion is the lowest among all
214
conventional technical glasses. Still lower thermal expansivity is exhibited only by
some special glassy-crystalline materials and by the so-called zero expansivity special
clear silica glass, e.g. of the Heraeus-Zerosil type (Fig. 120).
7 0.80h
- 0.72]
I /
Q64
1000 1A00 1800

- — f CO
, 1.20
l·-
,- -N
ö
- 1.00 11/
/
V\ Fig. 119 — The coefficient of thermal
1
\\ expansion a of clear silica glasses in terms
/ \\
/ of their fictive temperatures t [22]:
s
s
\\ A — type I /11 clear silica glass melted from
Q80l·^v"„
rock crystal; B — type III clear silica glass
1 1
1000 1400 1800 melted from synthetic raw material
— t CO
Compared to conventional technical glasses, the thermal expansion of silica glass

is shown in Fig. 115. Figure 116 shows the thermal expansion of a clear silica glass
rod 1 m in length in terms of temperature, and Fig. 117 shows the temperature
dependence of the coefficient of thermal expansion of silica glass.
Table 49
Mean coefficient of thermal expansion of clear silica glass
[28] for various temperature ranges
x
o-ioo°c ' 10 (°C ) 0.51
a
o-2oo°c ' 10 (°C ) 0.58
ô-ioox ' 10 ( C j 0.59
~A>-4oo °c ' 10' (°C ) 0.58
^ 0 - 5 0 0 °C ' 10 ( C ) 0.56
Xo-eoo-c.lO6^"1) 0.54
^-.oooc'lO6^-1) 0.48
Thermal expansivity of clear silica glass also depends on the fictive temperature
of the heat treated glass. The relationships determined according to measurements
by Bruckner [22] are plotted in Figs 118 and 119.
215
The thermal expansivity of clear silica glass increases slightly with increasing fictive
temperature (over the range from about —100 °C up to about 1500 °C). Similarly,
at temperatures below —100 °C, the expansivity of silica glass is higher with glasses
heat treated at a higher fictive temperature (Fig. 118). This is in agreement with the
stabilizing changes in annealed silica glass. The less a silica glass is stabilized (e.g.
after rapid cooling from high temperatures) the relatively greater expansivity it
exhibits than perfectly stabilized glass.
Stabilized silica glass should therefore be preferred for the construction of various
measuring instruments, especially dilatometers. The course of stabilization of clear
silica glass can also be followed by measuring the values of its viscosity (cf. Sec
tion 4.4.3) and refractive index (cf. Section 4.6.2). Otto and Thomas [28] recommend
stabilization of clear silica glass for 8 hours at 1080 °C in an electric furnace.
The values of the mean coefficient of thermal expansivity of clear silica glass
listed in Table 49 are those normally used to correct thermal expansion measure
ments carried out on quartz dilatometers.
The thermal expansion of silica glass exhibits an anomaly. Up to about 300-400 °C
it increases with temperature, but it decreases above this temperature (Fig. 117,
Table 49).
For practical purposes, the thermal expansion of clear and opaque silica glasses
can be regarded as identical. This is why clear silica glass can quite safely be fused
to opaque glass without any danger of fracture being involved. For example, trans
parent inspection windows of clear silica glass were fused into large reaction vessels
of opaque silica glass with good results.
0.5 /
//
04 //
0.3 - /
B /
P 02
V
/
^ 01 - / A
/ /-._
0- Λ- .... Fig. 120 — Relative thermal
' -0.1 . •
/ expansion of Zerosil (A) clear silica
I I I glass compared to that of Suprasil
-02 I I
-100 0 100 200 300 clear silica glass (B) [29]
- f CO
Additions of some oxides (e.g. Ti0 2 ) into synthetic silica glass result in clear silica
glar -s with the so-called zero expansivity. The Zerosil type made by Heraeus Quarz-
sthmelze [29] can be given as an example. Figure 120 shows the thermal expansivity
216
of the Zerosil silica glass relative to that of the Suprasil type clear silica glass. The
mean coefficient of thermal expansion of Zerosil for various temperature ranges is
listed in Table 50.
Table 50
Mean coefficient of thermal expansion
of the Zerosil type silica glass [29]
α2ο_ιοοχ·106 (0C~l) 0.02 (±0.03)

a2o_2oo°c · 106 ("CT1) 0.00 (±0.05)
«20 3oo°c-io 6 {°c-1) -0.02 (±0.05)
«20 4 0 0 X - 1 0 6
rC"1) -0.05 (±0.10)
«2O6OOX-10 6 r C " 1 ) -0.15 (±0.10)
4.4.2 Resistance to thermal shock
The resistance to thermal shock is the ability of glass to resist abrupt changes
in temperature over certain temperature ranges; it depends on the glass proper (its
material), and on the type (shape) of the ware [27]. It is specified as the largest
difference in temperature over which the heated ware can be quenched without
cracking. The critical temperature difference is that which the ware still withstands
without cracking.
The resistance to thermal shock, otherwise called the thermal endurance, is des
ignated Δί (i.e. the difference between the upper and lower temperatures), and given
in °C.
Each change in temperature is responsible for the creation of stress in the wall of
the ware. Increasing temperature differences (heating and cooling of glass and
vice-versa) may create stresses exceeding the strength of the glass (in tension) and
the glass will fail. The resistance to thermal shock depends on several factors. The
greatest effect is that of thermal expansivity. The lower the thermal expansivity of
the glass, the smaller its shrinkage and the higher its thermal endurance. As a result
of very low thermal expansivity, silica glass shows a high resistance to thermal shock.
The other factors influencing the thermal endurance are the tensile strength and
Young's modulus of elasticity. As already mentioned (Section 4.3.3), the tensile
strength depends primarily on the quality of the glass surface. Young's modulus
of elasticity for silica glass shows no great difference from that of other glasses. The
resistance of silica glass to thermal shock is therefore largely a function of its thermal
expansivity, and for this reason is the highest of all the conventional technical glasses.
The literature [30] specifies the resistance of clear silica glass to thermal shock,
under normal conditions and for a wall thickness of 1 to 2.5 mm, as Δί = 1000 to
1100°C
217
A silica glass tube [23] 10 to 30 mm in diameter will withstand repeated heating
up to 800-900 °C and rapid quenching in water at 20 °C. Thin-walled ware of clear
silica glass (dishes, crucibles, flasks, etc.) will resist rapid quenching in water at
a temperature difference At = 800 to 1000 °C and rapid cooling in air by
At = 1300 °C. Plates of clear silica glass 20 to 30 mm in thickness will survive repeated
quenching in water after previous heating at temperature differences At = 450
to 500 °C. For clear silica glass up to 3 mm in wall thickness, Espe [13] reports
a resistance to thermal shock at temperature differences At up to 1250 °C. As the
heating above 1000 °C involves a danger of crystallization and subsequent cracking
on cooling down below about 300 °C, it is recommended no to exceed the tempera
ture range of 600 to 1000 °C in technical applications of silica glass. For the sake
of comparison it should be noted that the resistance to thermal shock of standard
borosilicate glasses of the Pyrex and Simax types does not exceed Ar = 200 to 250 °C.
4.4.3 Viscosity
Viscosity is one of the most important properties of silica glass which has
to be taken into account during its manufacture and working, as well as its appli
cation. In the course of melting, other contemporary glasses have a viscosity of about
102 dPa s; during the melting process, silica glass is much more viscous (η = 105 to
10
-^ 3
10U|
io 12
Jr 10
» 10'
10'
10'
800 1000 1200 1400 1600 1800 2000 2200 2400
f CO
Fig. I2l — Temperature dependence of viscosity of clear silica glass melted from natural raw material
(curve /) and from synthetic raw materials (curve //). The synthetic silica glass (Suprasil) contained
about 1500 ppm of OH groups. Measurements according to: / — Chacklander et al. [31]; 2 and 4 —
Volarovich et al. [32]; 3 and 7 — State Glass Research Institute, Hradec Krälove; 5 — Corning Glass
Works [33]; 6 - Bacon et al. [34]
218
106 dPa s). It does not deform on heating unless its viscosity attains the value of
about 1014 to 1013 dPa s. This corresponds to a temperature of about 1200 °C [4].
Thus it is not recommended to expose clear silica glass to long-term effects of tem
peratures exceeding about 1100°C. Short-team heating at higher temperatures is
possible, but at the risk of deformation of the ware and its surface crystallization.
Silica glass begins to deform under the effect of gravity at temperatures of about
1200 °C. The deformation is very rapid at 1400 to 1500 °C, and the glass surface
begins to crystallize extensively. Silica glass can be bent readilly and formed in other
Table 51
Viscosity of clear silica glasses according to various authors [39]
Author Type of silica glass Measuring Viscosity Activation

interval at 1200°C energy E
(°c) (dPa s) (kJ Ι Ϊ Ι Ο Γ 1 )
Volarovich et al. [32] not specified 1160-1450 io13·2 611.2
,Q13.2
Inuzuka [40] clear silica glass 1130-1430 611.2
Yovanovich [41] glass free of OH groups 1000-1440 io13·7 653.1
Hagy [42] Corning 7940 1070-1220 io11·7 448
JQ12.6
Fontana [43] Amersil 1200-1340 531.7
Hlaväc [37] 1. electrically melted from

JQ12.6
Brazilian crystal 1050-1240 670
2. electrically melted from
JQ12.8
vein quartz 640.6
3. Heralux 1 0 1 2 l) 569.4
Kimura [44] Spectrosil 1000-1100 io114 515
Hetherington et al. [36] 1. IR-Vitreosil 1000-1400 io 1 2 - 8 711.7

2. O.G. Vitreosil 644.8
(270 ppm OH) io12·3
3. O.G. Vitreosil 548.4
(400 ppm OH) I O 1 17
4. Spectrosil 510.8
(1200 ppm OH) io114
5. Spectrosil WF 625
(5 ppm OH)
Broukal [5] Vacuum melted from vein

quartz 1140-1240 1013 607
219
Table 52
Viscosity of clear silica glasses made in the USSR [39]
Glass Manufacturing method Raw material log ç (dPa s)

mark
°c
1100 1200 1300 1400 1500 1600 1700 1800 1900 2000
KI Vacuum melting in graphite Brazilian rock crystal 14.7 13.2 11.8 10.6 9.5 8.6 7.7 6.9 6.2 5.6
crucible Synthetic quartz crystals 14.3 12.9 11.6 10.5 9.5 8.7 7.9 7.2 6.6 5.9
Synthetic cristobalite 14.2 12.8 11.5 10.3 9.4 8.4 7.6 6.9 6.3 5.7
Kyshtym granulated quartz 14.5 13.0 11.7 10.5 9.5 8.6 7.8 7.1 6.4 5.8
Aktas vein quartz 14.4 13.0 11.7 10.5 9.6 8.7 7.9 7.1 6.5 5.8
7 9< i)
KI Melting in rotary vacuum Synthetic quartz crystals 14.5 12.8 11.3 10.0 8.9(1) 6.9(1> 6.1(1) 5.3(1) 49<n
furnace
KI Melting in vertical bar Kyshtym granulated quartz 12.3 11.2 10.2 9.4 8.5 7.8 7.2 6.6 6.1 5.7
vacuum furnace
KI Melting in low-temperature Synthetic quartz crystals 14.5 12.9 11.5 10.3 9.2 8.2 7.4 6.5 5.9 5.2
plasma burner Kyshtym granulated quartz 14.4 13.0 11.7 10.6 9.5 8.6 7.8 7.1 6.5 5.8
KV Melting in gas burner Brazilian rock crystal 14.5 13.0 11.7 10.5 9.5 8.6 7.8 7.1 6.4 5.8
Synthetic quartz crystals 14.1 12.7 11.4 10.3 9.3 8.4 7.6 7.0 6.4 5.7
KV Melting in the U N D type Kyshtym granulated quartz 13.8 12.3 11.1 10.0 9.1 (1) 8.2(1> 7.5(1) 6.8(1) 6.2(1) 5.6(1>
of furnace
KU Flame hydrolysis SiCl4 12.7 11.5 10.5 9.5 8.7 8.0 7.3 6.7 6.2 5.7
KVR
Two-stage manufacture of SiCl4 13.4 12.1 11.1 9.9 9.0(1) 83 d) 7.5(1> 6.9(1> 6.3(1) 5.8(1)
synthetic glass with a content
of 170 ppm OH
Data obtained by extrapolation

ways at about 1700 °C. The main region of blowpipe working of silica glass is at
1850 to 2100 °C, where its viscosity attains values of about 106 to 105 dPa s. How
ever, it should be noted that Si0 2 volatizes at temperatures above 1800 °C (cf.
Fig. 83). Silica glass is generally known to be very difficult to work in a flame. It
solidifies rapidly on a relatively small cooling down, and cannot be worked without
reheating. The basic factors influencing the viscosity of silica glass are temperature,
thermal history of the glass, content of hydroxyl groups and trace impurities and the
degree of reduction of the glass. Figure 121 shows the temperature dependence of
viscosity for clear silica glass, according to measurements by various authors and
laboratories.
Viscosity measurements on silica glass by a number of authors indicated that the
temperature dependence of the logarithm of viscosity η = /(1/Τ) is linear at tempe
ratures exceeding 1000 °C; values quite satisfactory for technological practice are
given by the simple equation
Ig η = lg rj0 + ^ (39)
where η is the viscosity (dPa s),

η0 is the viscosity at T -> oo,
T is the absolute temperature (K),
E is the activation energy (kJ mol" 1 ),
R is the molar gas constant ( = 8.31 J mol" 1 K" 1 ).
Table 51 lists the values of viscosity and activation energy E of clear silica glasses
according to measurements by various authors, and Table 52 a survey of viscosity
values of clear silica glasses obtained by various technologies.
10
3
V
s \
' s \ \
1 N \ \ ■Y
121
io \ \
\
10
Fig. 122 — Temperature dependence

of viscosity of opaque (curve 1) and
clear silica glass (curve 2 and 3),
10°
1000 1200 1400 1600 according to Pryanishnikov [10]
f CO
221
The pattern of the temperature dependence of viscosity for silica glass is affected
particularly by the purity of the raw material and the manufacturing method em
ployed. For example, opaque silica glass made from quartz sand (containing various
impurities such as A1 2 0 3 , F e 2 0 3 , T i 0 2 , etc. — cf. Table 30) exhibits a lower viscosity
than silica glass melted from rock crystal (Fig. 122).
Virtually all impurities (even below the order of 0.1 wt.%) present in clear silica
glass generally decrease its viscosity. Various trace impurities (e.g. OH groups, Fe,
Ca, Na, K, Li, Ti, Al, etc.) penetrate the structure of silica glass already during the
course of melting and impair the strong O—Si—O bonds, which among other effects
also brings about a decrease in the viscosity of silica glass. Unassociated OH groups
were found to be one of the most significant impurities in the structure of silica glass.
t CO«
10is [ -K0O
i l l
1200
--r
1000 900
1—
t CO 1
1400 1200 1000
if) 10
/ /
/ %
10" - / #
· —r(*-'f (!*')
Fig. 123 - Temperature dependence of viscosity Fig. 124 — The effect of admixtures on the
of clear silica glasses made by Thermal Syndicate viscosity of synthetic silica glasses [36]:
Ltd. with various contents of OH groups [36]: / - Spectrosil; 2 - 0.12 wt.% T i O : ;
I - I.R. Vitreosil (about 3 ppm OH); 2 - O.G. 3 - -O.l w t . % B 2 0 3 ; 4 - 0.014 wt.%
Vitreosil (270 ppm OH); 3 - O.G. Vitreosil C r 2 0 3 ; 5 - 0.67 wt.% T i 0 2
(400 ppm OH); 4 - Spectrosil (1200 ppm OH)
The content of these OH groups in silica glass may reach 1500 ppm (0.15 wt.%),
according to the raw material used, the melting method and the heat treatment
employed. An elevated content of OH groups in clear silica glass may therefore sub
stantially reduce its viscosity (Figs 121, 123). The effect of OH groups is often com
bined with the presence of additional impurities in glass, or with a certain non-
stoichiometry. In a reduction medium (e.g. hydrogen in the oxygen-hydrogen flame,
melting graphite crucible, etc.) the so-called reduced (non-stoichiomeiric) silica glass,
S i 0 2 - A is produced. This non-stoichiometry of silica glass is revealed by an ab
sorption minimum at 242 nm, by the glass showing fluorescence, by its crystallization
222
rate differing from that of stoichiometric silica glass, etc. This non-stoichiometry of
silica glass was also found to affect its viscosity [35].
Hetherington, Jack and Kennedy [36] specify the values of equilibrium viscosity
of clear silica glasses with various contents of OH groups (Fig. 123).
A significant effect in reducing the viscosity of silica glass is exhibited by various
metallic oxides, as well as B 2 0 3 and others. Hetherington, Jack and Kennedy [36]
describe the effect of small admixtures of Ti0 2 , Cr 2 0 3 and B 2 0 3 in synthetic silica
glass on decreasing the viscosity of the original glass (Fig. 124).
The viscosity of silica glass over the transformation region is further influenced by
the degree of glass stabilization. The stabilization effects appear only at viscosities
exceeding 1013 dPa s. In comparison with silicate glasses, stabilization of silica glass
is faster [37]; its course is well described by the kinetic equation of Winter [30]. The
differences in the viscosity values for stabilized and non-stabilized glasses were found
to exceed even one order of magnitude. In measuring the viscosity of silica glass at
a given temperature, the glass has to be heated for a certain time before the so-called
equilibrium viscosity for thegiven temperature is attained. For example, it was found
that clear silica glass manufactured in Czechoslovakia has to be stabilized at 1150 °C
for about 10 hours to attain the equilibrium value of viscosity [38]. The equilibrium
viscosity of silica glass is reached more quickly at higher temperatures; at 1183 °C
(cf. Fig. 125), an equilibrium viscosity was achieved within about 7 hours. Hethering-
138
10 " \-3
v13,6
10
/
s5
10
v13A h1
-i
i
10,«
13
10) -t
^1-
1
1
i i i 1
20 40 60 80 100 120
—»- fi
Fig. 125 — Time dependence of stabilization of clear silica glasses melted from vein quartz [38]:
1 - made from vein quartz by vacuum melting in a graphite crucible by the two-stage method -
measured at 1150 °C; 2 - the same glass as in 1, but measured at 1183 °C; 3 - made from vein quartz
by vacuum melting in graphite by the single-stage method - measured at 1150 °C; 4 - made in the
same way as 3, but from Brazilian crystal - measured at 1150 °C; 5 - Heralux glass made in an
oxygen-hydrogen flame from Brazilian crystal — measured at 1150 °C
223
ton, Jack and Kennedy [36] specify still longer times of stabilization for clear silica
glass Vitreosil IR; for example, for 1100 °C they specify a stabilization time of up to
170 hours, and for 1200 °C about 24 hours. However, some authors report shorter
times of stabilization [47]; Douglas, for instance, 20 hours at 1100 °C and 1 hour
at 1200 °C.
The equilibrium viscosity of clear silica glasses made by the single-stage technology,
either by the vacuum method or in the oxygen-hydrogen flame (Fig. 125), was reached
much later (only after 40 to 50 or even more hours at 1150 °C). The time course of
stabilization for clear silica glasses therefore depends on the manufacturing tech
nology employed, of course with regard to the Active temperature of the finished
glass. When the same manufacturing technology was used, the raw material employed
had no apparent effect on the course of stabilization of the silica glass (e.g. Brazilian
crystal compared to vein quartz) [38].
4.4.4 Specific heat
Knowledge of the specific heat values can be utilized in resolving thermal

technical balances in the manufacture and working of silica glass. The specific heat
also affects the process of annealing. The various discontinuities in the variation of
specific heat with temperature are indicative of changes in the structure of the glass,
800 1200 1600 -200 0 400 800 1200 1600

f CO f CC)
Fig. 126 - The course of the true specific heat Fig. 127 — The mean specific heat cp in terms
cp (curve 1) and the mean specific heat of temperature: / — clear silica glass measured
cp (curve 2) for clear silica glass in terms of at the Institute for Refractories (USSR);
temperature (according to Sosman [45, 46] 2 — opaque silica glass, measured at the same
institute; 3 — according to Sosman [45, 46]
e.g. in the transformation or crystallization regions [27]. From the standpoint of

theory, knowledge of the specific heat is indispensable for thermochemistry and
thermodynamic calculations.
The specific heat, i.e. the amount of heat required for heating 1 g of substance by
1 °C, is expressed in the units J g" 1 K" 1 .
224
The first values of specific heat for silica glass were reported by Sosman in 1927
[45,46]. The values established for the true cp and mean cp for clear silica glass, which
are still in use, are listed in Table 53. The specific heat value for silica glass increases
with temperature somewhat steeply at first and more slowly later on. In the region
of extremely low temperatures, the specific heat decreases almost to zero (Fig. 126).
Minute differences in the values of specific heat for clear and opaque silica glass
were found at the Institute for Refractories in the USSR [23]. The results of their
measurements, compared to the values for clear silica glass given by Sosman, are
plotted in Fig. 127 [46].
Table 53
Specific heat of clear silica glass, according to Sosman [45]
Temperature t Specific heat of clear silica glass

(°c) (Jg-'K-)
true cp mean cp
(°c - t)
-200 0.1817 0.4609

-100 0.4722 0.5903
0 0.6937 0.6937
100 0.8415 0.7745
200 0.9504 0.8373
300 1.0257 0.8876
400 1.0886 0.9295
500 1.1304 0.9671
600 1.1513 0.9965
700 1.1765 1.0216
800 1.1974 1.0425
900 1.2100 1.0592
1000 1.2225 1.0760'
1100 1.2309 1.0886
1200 1.2686 1.1011
1300 1.3230 1.1179
1400 1.3732 1.1304
1500 1.4193 1.1514
1600 1.4486 1.1681
1700 1.4737 1.1848
It is interesting to note that at about 1100 °C, a distinct discontinuity in the depen
dence of the specific heat of silica glass on temperature occurs (Fig. 126). This is
attributed by Bruckner [22] to structural changes depending on the thermal history
of the glass; it is just this region (the transformation region of silica glass) where the
glass is stabilized [39].
225
Kondratev, Kornev and Leko [39] describe the measurement of specific heat for
five samples of clear silica glass of various origins, namely synthetic silica glass
KSSh-2 of high purity, type KI silica glass melted from crystalline quartz, cristobalite,
028 _
2 ^■.rr::--·^
0.24
- ,.,-ίίι--'""
.<?·>■ 1
lo 4 0.20 - /■■>■ , - " ' T
0.16 ;>'I I I I I
200 400 600 800 1000 200 400 600 800 1000
*- t CO - f CO
Fig. 128 — Temperature dependence of the true Fig. 129 — Temperature dependence of the
specific heat cp of clear silica glass compared to mean specific IK it cp of clear silica glass
technical silicate glasses [24]: 1 — clear silica compared to selected silicate glasses [24]
glass; 2 — soda-lime glass, 3 — borosilicate (designation of the glass is the same as in
glass of the Pyrex type; 4 - alkali-lead-silicate Fig. 128)
?lass (22.3% PbO)
type KV silica gla^s from crystalline quartz and cristobalized quartz from the Aktas
deposit. The values of true specific heat cp were found to be identical, within the limits
of accuracy. For the temperature range 90 to 600 K, the values are listed in Table 54.
Compared with technical silicate glasses, clear silica glass has lower specific heat
values than, for example, the conventional soda-lime glass (Figs 128 and 129) and
higher values than alkali-lead-silicate glass with a content of 22.3% PbO [24].
Ag
Au:
-Al
BeO- W -Mo
Fe- -Τα Ε
o 10 D
Al 2 0 3 -
Mg-
10
E Fig. 130 — Comparison of the

C
thermal conductivity values λ at
10" -l· : G
20 °C) of clear silica glass with other
substances: x — clear silica glass;
H21
A — technical glasses; B — mica;
Ne- F C — silicate ceramics; D — oxidic
10
air ceramics; E — metals; F — gases;
Ar ; CO 2 G — plastics
226
Table 54
True specific heat of silica glass, according to [39]
Temperature 7 True specific heat cp Temperature T True specific heat cp

(K) (Jg-K- 1 ) (K) (Jg-'K-1)
90 0.2339 230 0.6092

95 0.2499 240 0.6283
100 0.2658 250 0.6463
105 0.2817 260 0.6639
110 0.2975 270 0.6826
115 0.3131 273.15 0.6889
120 0.3284 280 0.7026
125 0.3436 290 0.7227
130 0.3586 300 0.7433
135 0.3732 320 0.7764
140 0.3876 340 0.8070
145 0.4018 360 0.8350
150 0.4158 380 0.8602
155 0.4295 400 0.8830
160 0.4431 420 0.9034
165 0.4564 440 0.9216
170 0.4697 460 0.9380
175 0.4827 480 0.9527
180 0.4955 500 0.9660
185 0.5081 520 0.9782
190 0.5204 540 0.9894
195 0.5326 560 0.9999
200 0.5444 580 1.0100
210 0.5673 600 1.0197
220 0.5889
Fig. 131 — Thermal conductivity of glasses

in terms of temperature [24]: 1 — clear silica
glass according to Fucken [48]; 2 — clear silica
glass according to Luck [49]; 3 — clear silica
glass according to Kingery [50]; 4 - clear silica
glass according to Knapp [51];
5 — borosilicate glass (Pyrex)
according to Luck [49]; 6 — soda-lime glass
according to Luck [49]; 7 - borosilicate glass
(Pyrex) according to Stevens [52];
8 - alkali-lead-silicate glass (69% PbO)
J I I I I I I I I L
according to Eucken [48]; 2A — clear silica glass
-200 0 200 400 600 800 according to Luck [49] with a tin sheet
f CO on the glass surface
227
4.4.5 Thermal conductivity
The thermal conductivity is a measure of the heat transfer through a ma

terial [27], and shows considerable differences for various materials. The best con
ductors are metals, among which silver has the highest conductivity (Fig. 130).
Technical glasses are considered more as heat insulators than thermal conductors.
This is also why glass can be worked in the flame with a part heated to a temperature
above 1000 °C while another part can still be held in the hand. Clear silica glass has
the highest thermal conductivity of all technical glasses (Fig. 131). At 20 °C, its
thermal conductivity is higher by about 20% than that of borosilicate glasses and
about 50% above that of high-lead glass (69% PbO) [24]. However, the thermal
conductivity of clear silica glass is substantially lower than that of oxide ceramics
(Fig. 130).
Heat is transmitted only by conduction through substances non-transmissive for
thermal radiation [27]. However, radiation is also responsible for heat transfer
through substances transmissive for it, clear silica glass being an outstanding rep
resentative of such substances. The total effective thermal conductivity Aef is the sum
of conduction thermal conductivity Ak and radiation thermal conductivity As:
Ki = K + k (40)
With clear silica glass and conventional clear silicate glasses generally, the share
of radiation thermal conductivity As is very small at temperatures lower than 400 °C.
Below 300 °C, the heat is transmitted by conduction only. The proportion of radiation
increases progressively with increasing temperature. At high temperatures (glass in
the form of melt) the heat is additionally transmitted by convection of the individual
mass particles from the hotter points to the cooler. The share of convection increases
with decreasing viscosity and thus with increasing temperature, and may attain
comparatively high values in melted glass.
Measurements of thermal conductivity of glasses are concerned with determining
the amount of heat passing through a certain volume of a body of simple shape
(usually a thin plate or a hollow cylinder) during a certain time; the temperatures
of the heated and cooled sample surfaces are measured simultaneously [53, 54].
Losses of heat into the environment during the measurements have to be prevented.
The measurement proper involves numerous experimental difficulties; it is not easy
to rule out losses due to dissipation or to measure precisely the temperatures of the
sample surfaces, while the effect of radiation interferes at temperatures above 300 °C.
Figure 131 demonstrates the effect of radiation transmission on the temperature
dependence of thermal conductivity λ at temperatures above 400 °C (curve 2);
a comparison is provided by thermal conductivity values for which the radiation
heat transmission was not considered (tin foil placed on a silica glass specimen,
curve 2A).
228
Table 55
Thermal conductivity λ of clear silica glass
Temperature T Thermal conductivity Temperature T Thermal conductivity

(K) (Wm^K-1) (K) (Wm^K"1)
90 0.627 220 1.214

95 0.654 230 1.236
100 0.684 240 1.257
105 0.716 250 1.277
110 0.749 260 1.295
115 0.782 270 1.313
120 0.814 280 1.329
125 0.845 290 1.345
130 0.875 300 1.361
135 0.904 320 1.392
140 0.931 340 1.421
145 0.957 360 1.450
150 0.982 380 1.479
155 1.005 400 1.509
160 1.026 420 1.536
165 1.047 440 1.564
170 1.067 460 1.539
175 1.085 480 1.662
180 1.102 500 1.650
185 1.119
190 1.135
1
The thermal conductivity of transparent glasses is obviously one of the most

diffucult physical properties to measure. Particular difficulties are encountered in
measuring the thermal conductivity at higher temperatures, namely from about
400 °C upwards, where the radiation heat flux begins to contribute. The radiant
thermal conductivity is not purely a material constant, as its value depends also on
the body geometry (shape and thickness) and on the outer heat transmission con
ditions, as well as on temperature. This is why the generally applicable thermal
conductivity values for silica glass are most frequently specified for temperatures
up to only about 400 °C. Table 55 lists the thermal conductivity values for type KV
clear silica glass [39] for the temperature range 90 to 500 K.
Compared to the conductivity of clear silica glass, that of opaque silica glass is
somewhat lower. Heraeus Quarzschmelze specify [7] the thermal conductivity
λ = 1.3816 W m _ 1 K _ 1 for clear silica glass at 20 °C, and λ = 1.0885 W m _ l K " 1
for opaque silica glass.
The thermal diffusivity a [27] is a mesure of the formation or equalization of
temperature differences in the glass object proper [27]. It is defined as the increase
in the mean temperature of a cube with unit length edge per unit time when the
229
temperature gradient between the opposite walls is decreased by 1 °C. The dimension
of specific thermal diffusivity is m2 s~ *.
The mutual relationship between the thermal diffusivity a and the thermal con
ductivity λ is given by the equation
where cp is the specific heat and ρ is the density.

Table 56 lists the values of thermal diffusivity a for clear silica glass, for the tem
perature range 90 to 500 K [39].
Table 56
Thermal diffusivity a of clear silica glass
Temperature / Thermal dilTusmtv Temperature 7

Thermal 6 diffusivity
(K) a · 106 (m-s ') (K) a · 10 ( m 2 s _ 1 )
90 1.218 200 0.972

95 1.190 210 0.953
100 1.171 220 0.937
105 1.155 230 0.922
110 1.144 240 0.909
115 1.135 250 0.898
120 1.126 260 0.877
125 1.118 270 0.866
130 1.109 273.15 0.862
135 1.101 280 0.853
140 1.092 290 0.842
145 1.083 300 0.832
150 1.073 320 0.815
155 1.063 340 0.800
160 1.052 360 0.789
165 1.042 380 0.782
170 1.033 400 0.776
175 1.022 420 0.773
180 1.011 440 0.771
185 1.001 460 0.772
190 0.991 480 0.774
195 0.981 500 0.776
4.4.6 Permeability to gases

The permeability of clear silica glass to gases is virtually zero at room
temperature. A certain diffusion of gases occurs, only at higher temperatures, to
a greater extent than in the case of silicate glasses. The diffusion of gases, particularly
230
Table 57
Temperature dependence of the permeability of silica glass for gases
Temperature
(°c) i CriIlCd.Diiiijr ν^ι ^ιιιν^α g lass
Q r\i l i t vr ΛΤ Ρ ΐ Ι ΐ π
Pi*t*rvi£fc Λ et
V
10
for gases • ( io~ — 2
cm 3 mm
_Λ
s cm · 1.333 · 102 P a /
1
He H2 Ne Ar N2 o2
150 0.73 — _ — — —
200 0.10-1.53 0.022 - - - -
300 0.46-4.13 - - - - -
400 0.90-8.25 0.275-0.500 - - - -
500 1.72-13.80 0.580-1.25 0.139
600 3.0-19.3 0.810-2.160 0.282 - - < 0.1
650 - - - - 0.065 -
700 4.25-21.9 1.70-3.90 0.500 0.132-0.146 -
750 - - - - 0.161-0.271 -
800 5.5-28.5 2.53-6.00 0.81 - 0.39-Ό.43 -
850 - - 0.016 0.64-0.80 -
900 6.7-36.2 3.6-7.0 1.18 0.580 0.95-1.19 -
950 - - - 0.600 0.65-1.44 -
1000 8.4-45.4 5.1-10.0 1.63 - - -
those with a small atomic diameter (He, H, Ne), probably occurs through the un
occupied gaps in the structure of (Si04)4~.
Helium permeates through silica glass at temperatures from 180° upwards.
Hydrogen was found to begin to diffuse at about 300 °C, whereas discernible amounts
of Ne, N2, 0 2 and Ar pass through silica glass only at temperatures above 900 °C.
The permeability for gases is proportional to the difference of pressure in front of
and behind the silica glass wall, and inversely proportional to its thickness. It is
expressed as the volume of gas V (cm3) that would pass during 1 second through
a wall, 1 mm thick and with an area of 1 cm2, at a pressure difference of 1.33 · 102 Pa
(previously 1 torr). Table 57 shows the variation with temperature of the permeability
for gases through clear silica glass under normal pressure [5, 7, 13, 21].
The permeability of gases through silica glass has some practical consequences,
for example for vacuum technology. Thus evacuated electron tubes of clear silica
glass must not be heated (degassed) in gas-heated furnaces or by gas burners, only
electrical furnaces being suitable for this purpose. For the same reason, following
the evacuation of silica glass electron tube envelopes, the exhaust tubes must not be
sealed with an oxygen-hydrogen flame but instead a carbon arc, for example, must
be used for this purpose.
Oxygen has been found to diffuse through silica glass at temperatures above
1000 °C. The heating of silica glass in 0 2 is therefore utilized in a special technology
to prepare the so-called purely stoichiometric silica glass, by oxidizing so-called
231
reduced or non-stoichiometric silica glass. The silica glass obtained in this way does
not show any absorption minimum at 242 nm, exhibits less fluorescence, has a dif
ferent crystallization rate and some other different physical properties, compared
with the original "reduced" glass.
4.4.7 Surface tension
Surface tension affects the melting of silica glass and influences its forming
and working. It has an important effect, for example, on fusion-rounding of glass
edges, blow-pipe work, etc. The surface tension is designated y and defined as a force
acting in the surface plane perpendicular to a unit length. The dimension mN m " 1
is used in glass technology to express surface tension. Table 58 lists the values of
surface tension for clear silica glass compared to other substances [27].
Table 58
Surface tension of silica glass compared to that of other substances
Substance Surface tension At the temperature

(mN m" 1 ) (°c)
Clear silica glass 260 to 320 [23] 1850 to 2000
Simax glass 305 to 317 1000
Neutral glass 298 1000
Sheet glass 302 1000
Bulb glass 293 to 303 1000
Container and pressed glass 310 1000
Lead optical glass SF-4 218 1000
Aluminium 840 700
Mercury 500 20
H20 72 23 1
Glycerol 29 20
Ethyl alcohol 22 20
Pryanishnikov [23] measured the surface tension of clear silica glass at 1850 to
2000 °C and found the values 260 to 320 mN m" 1 . The surface tension of melts is
comparatively little affected by temperature, decreasing very slightly with increasing
temperature. These changes in surface tension due to temperature are of no basic
significance for the technology of silica glass.
4.4.8 Crystallization properties
Gradual surface crystallization of silica glass takes place at temperatures

above 1050 to 1100 °C. The cristobalite layer being formed has the disadvantageous
property of cracking on recooling below 272 °C, as a result of the different thermal
232
expansivity of its low-temperature crystalline phase (Fig. 132). However, if the de-
vitrified silica glass is kept permanently at temperatures above 272 °C, no dilation
changes of cristobalite occur and the silica glass object is capable of further use. This
Fig. 132 — Surface

crystallization of clear
silica glass. The cristobalite
formed has cracked on
cooling down, and so has the
tube wall. The picture shows
a cross-section through a heat
treated tube 12.7 mm in
diameter with a wall
thickness of 0.85 mm
(according to [55])
unfavourable property of silica glass is even turned to advantage in some instances,

as in the use of furnace blocks of silica glass to melt technical glasses at temper
atures of 1550 to 1600 °C. The cristobalite formed has a high melting temperature
(1723 °C); silica glass, insofar as it has not yet crystallized, should soften and deform
at these temperatures.
233
Crystallization of clear silica glass is slight compared to that of silica glass already
containing minute admixtures of alkalis. At temperatures above 900 °C, traces of
N a 2 0 are responsible for the reaction
Na
II III
—Si—O—Si— + N a 2 0 -► — Si—O O—Si— (42)
{
II III '
Na
4
This reaction promotes mobility of the [ S i 0 4 ] " tetrahedra, causing their re
arrangement and local crystallization (Fig. 133). For this reason, the crystallization
rate of opaque silica glass is significantly higher that of clear silica glass. The most
important factors are the purity of the silica glass (content of trace impurities), its
0.7
/ V*
I \
06| I \
*T 0.5
0.4 / \
I \
I I
0.3 / \
I
Q2
0.1
I Il
Fig. 133 — Temperature dependence of the crystallization
rate of clear silica glass compared to silica glass with a low
i content of alkalis [56]:) — clear silica glass; 2 — silica
800 1200 1600 glass containing 0.32wt.% N a 2 0
f CO
temperature, its oxidation-reduction state and the ambient atmosphere. The literat
ure [7] specifies typical values for crystallization of clear silica glass at 1280 °C in
the pure atmosphere of an electric furnace, namely 0.001 μιιι per hour. At the same
temperature (1280 °C) but in a furnace atmosphere containing vapours of alkaline
salts, the crystallization rate increases up to 1.0 μιτι per hour. In a clean air atmosphere
at about 1100 °C, the crystallization rate established was about 1000 times lower than
that at 1280 °C.
The time dependence of the growth of the crystalline layer on clear silica glass is
also affected by the oxidation-reduction state of the glass [57, 58, 59, 60, 61].
The time dependence of the thickness of the cristobalite layer formed in reduced
glass in an oxidizing atmosphere is at first linear, later becoming parabolic (oxidation
of non-stoichiometric glass by diffusion of oxygen, curves 2 and 3 in Fig. 134),
according to Wagstaff et al [57, 59].
234
The curve finally becomes linear again, corresponding to "reduced glass" (beyond
the range of oxidation). Both in neutral and reducting atmospheres, "reduced"
glasses have an almost constant crystallization rate over the entire range (curves 2
and 3 in Fig. 135).
Fig. 134 - Crystallization of clear silica glasses in terms of time, in an 0 2 atmosphere at 1486 °C.
The thickness of the cristobalite layer formed was measured in pm (according to [57, 59]):
1 - stoichiometric silica glass (free of OH groups); 2 - type GE 204 A silica glass (reduced glass);
3 — type GE 201 silica glass (reduced glass)
A similar constant crystallization rate is exhibited by stoichiometric glass heated

in oxidizing and neutral atmospheres (curve / in Figs 134 and 135). The activation
energy of crystallization in a neutral atmosphere (argon) amounts to 210-240 kJ mol" l
for non-stoichiometric (reduced) silica glasses [58, 61], being higher for stoichio
metric glasses, namely about 500 kJ mol" 1 .
It was found [5] that clear silica glass of Czechoslovak manufacture, vacuum
melted in an induction graphite furnace, obviously begins to crystallize on a surface
100 l·
80
E
3 60
40 Fig. 135 — Crystallization of clear

silica glasses in a neutral atmosphere
20 (N 2 ) at 1486 °C. Designation of the
glasses and measurement of the
100 200 300 400 500 600 700 800 900 cristobalite layer is the same as in
[min) Fig. 134 (according to [57, 59])
235
pre-treated by etching (3 to 4 minutes in 40% HF) within 6 hours at 1160 °C ± 10 °C.
The crystallization of clear silica glass is promoted by impurities in the glass, par
ticularly by alkali oxides and especially by surface contamination with alkaline earth
oxides, alkalis, SiC, graphite, Fe 2 0 3 , etc. The crystallization of silica glass is also
accelerated by carbon monoxide and by the vapours of NaCl, Na 2 C0 3 and other
salts. Under these conditions, surface crystallization takes place at lower tempera
tures than mentioned above. The formation of the crystalline surface layer proceeds
much faster.
Crystallization is also accelerated by substances contained in the dust present in
air and, especially, by salts from finger-prints on the surface of silica glass. It is there
fore necessary to clean the surface of silica glass thoroughly with water and with pure
ethyl alcohol or methyl alcohol before the heat treatment. A strongly contaminated
surface of silica glass should first be degreased with some suitable agent, then washed
with water and immersed for 3 to 4 minutes in 40% HF; the glass surface should then
be dried after thoroughly rinsing with distilled water. The chemical cleaning of
silica glass was described in Section 4.2.3. Direct touching of the cleaned surface
with fingers before subsequent heat treatment should be avoided. The method
described can also be employed to clean silica glass samples used to measure surface
crystallization. The specimens are heated in an electric furnace, mostly for 8 hours
(even longer when necessary) at the desired temperature (over the range of 1100
to 1300 °C). To eliminate the effects of impurities from the furnace atmosphere on
the glass surface, the samples have to be placed in a tube or flask or muffle of clear
silica glass. After a given time, the samples are removed from the furnace. The sample
surface is periodically compared with a standard specimen of clear silica glass, which
has been heated simultaneously. To measure the crystallization rate, the thickness of
the cristobalite layer formed is evaluated in terms of time on a transverse section
through a heat-treated glass specimen (Fig. 132).
In view of the possible crystallization, clear silica glass should not be permanently
exposed to temperatures exceeding 1000-1100 °C, the maximum short-term tem
peratures being about 1300 °C.
4.5 ELECTRICAL PROPERTIES
Clear silica glass is one of the best electrically insulating substances, suitable
particularly for applications at higher temperatures. Its surface electrical conduc
tivity is very low, since it is not hygroscopic and no water film layer containing eluted
alkalis is formed on its surface, as happens with conventional silicate glasses. Clear
silica glass also has a high electrical disruptive strength and low dielectric losses,
even at elevated temperatures.
236
4.5.1 Electrical resistivity
Compared to conventional technical silicate glasses, clear silica glass shows

the highest values of electrical resistivity in terms of temperature (Fig. 136).
The values of electrical resistivity of opaque silica glass are somewhat lower
(Tables 59 and 60) according to [7, 8].
Fig. 136 — Electrical resistivity ρ of Corning Glass Works

glasses vs. temperature: 1 — clear silica glass;
100 300 500 700 2 - Vycor 7900; 3 - Pyrex (7740); 4 - bulb glass (0080)
— - f CO
Table 59
Electrical resistivity of clear and opaque silica glass
- 1
Temperature Electrical resistivity ρ · 10 2
(°c) (Ohm m) of silica glass [7] made by Heraeus
clear opaque
20 1018 3.2 · 1015

100 1016 3.2 · 1014
200 4-1013 1013
400 1010 2-10 9
600 8· 107 2 · 107
soo 6.3· 10(1 6.3 · 105
1000 10" 6.3 · 104
1200 1.3· 105 104
The temperature dependence of electrical resistivity ρ of clear silica glass over the
temperature ranges of 1200 to 1800 °C and 1600 to 2100 °C is shown in Figs 137
and 138.
The surface electrical resistivity of silica glass is also at least 10 times higher than
that of the best electrically insulating silicate glasses. The temperature dependence
of electrical surface resistivity of clear and opaque silica glasses for the temperature
range 200 to 700 °C is shown in Fig. 139.
237
Table 60
Electrical resistivity of the Vitreosil clear and the opaque silica glass
Electrical reisistivity ρ · \0~2

Temperature (Ohm m) of Vitreosil silica glass made by
(°c) Thermal Syndicate Ltd. [8]
clear opaque
15 - 2-1014
20 1.8· 10 19
-
150 - 2-1014
200 5.0· 10 12 -
230 - 2-1013
250 - 2.5· 10 12
350 - 3.0· 10 10
400 1.3· 10 9
-
450 - 8 · 108
600 6.3 · 106 -
800 1.6· 106 2 · 107
1000 2.5 · 105 -
1200 3.2· 104 -
Fig. 137 — Temperature

dependence of electrical
resistivity ρ of clear silica
1600 1800 2000 2200 glass (according to [62]) over
— r CO the range 1200 to 1800 °C
238
The electrical surface resistivity of clear silica glass depends on the ambient relative
humidity (Fig. 140).
106
Fig. 138 — Temperature dependence

of electrical resistivity ρ of clear
silica glass (according to [62]) over
the range 1600 to 2100 °C
10"
§ 10*
<fio1
Ίθ1
108
20 40 60 80 100
^ <%>
Fig. 139 — Surface electrical resistivity ρρ of Fig 140 Electrical surface resistivity ρρ of
clear silica glass and opaque silica glass in terms clear silica glass at 20 °C vs. ambient relative
of temperature (according to [23]): / — clear humidity Frcl (according to [63])
silica glass; 2 — opaque silica glass
4.5.2 Electrical disruptive strength
The electrical disruptive strength is given in the units V m _ 1 (previously

1
kV cm" ). The disruptive strength is so high for technical glasses that, for example
in the case of metallic seals, the disruptive discharge occurs in air between the elec-
239
trodes rather than through the glass proper. Clear silica glass has the highest electric
discharge strength relative to the other technical glasses; at 20 °C, the value is
2-4· 107 V m " 1 (200-400 kV c m - 1 ) and at 500 °C, 0.3-0.5· 107 V m " 1 (30 to
50kVcm"1).
These values hold for glass 5 mm and more in thickness. For thinner sheets, the
electrical disruptive strength of the glass is still higher. The electrical disruptive
strength of clear silica glass also depends on its homogeneity (content of bubbles,
cords, inclusions of impurities, etc.), on the content of trace impurities in the structure
of the glass, the surface state of the glass object and the way the strength is measured.
4.5.3 Permittivity
Permittivity (previously called the relative dielectric constant) of clear silica

glass for the temperature 20-25 °C at a frequency of 100 to 10 10 Hz is given by the
values ε = 3.70 to 3.81.
Ql 1 1 I i ' '
100 300 500 200 400 600
—- f CO - f CO
Fig. 141 — Temperature dependence of permit Fig. 142 — Temperature dependence of the
tivity ε of several selected technical glasses loss factor tan δ of clear silica glass at
made by Corning Glass Works (according to [24]) 1 MHz, compared to technical silicate
in comparison with clear silica glass: glasses from Corning Glass Works
/ - high-lead glass (8870); 2 - soda-lime glass (according to Shand [24]): 1 — soda-lime
(0080); 3 - aluminosilicate glass (1710); glass (0080); 2 - Pyrex (7740); 3 - borosilicate
4 — borosilicate glass for sealing to Kovar (7052); glass for seals to Kovar (7052); 4 — high-
5 — borosilicate glass Pyrex (7740); 6 — clear lead glass (8870); 5 — clear silica glass
silica glass
240
The values of permittivity for opaque silica glass are somewhat lower (cf. Table 61,
after [7]).
The temperature dependence of permittivity for clear silica glass, in comparison
with that for some silicate glasses by Corning Glass Works, is shown in Fig. 141.
Table 61
Permittivity of silica glass
Glass Temperature t Frequency / Permittivity ε

(°c) (Hz)
clear silica glass 20 up to 106 3.70

23 9 · 108 3.77
23 3· 1010 3.81
opaque silica glass 20 up to 106 3.50

23 9 · 108 3.58
23 3 · 10 10 3.62
4.5.4 Loss factor tan δ
The dielectric loss factor tan δ expresses the losses of electrical energy,
resulting in an increase in glass temperature, due to the passage of a high-frequency
current [64]. These dielectric losses are a complex function of glass composition,
the frequency and temperature, and are determined by losses due to conductivity,
Table 62
Loss factor tan δ of silica glass at 20 °C
Frequency / Loss factor tan δ · 104 at 20 °C of silica glass

(Hz)
clear opaque
according to [8] according to [7] according to [7]
1· 102 8.5 — —
1· 103 7.5 5.0 6 to 20
1 · 104 6.0 - -
1· 105 4.0 - -
1 · 106 2.0 1.0 5 to 15
1· 107 1.0 1.0 4 to 12
1-10 8 1.0 1.0 4 to 12
1-10 9 0.6 1.0 4 to 12
1 · 10 10 1.0 4.01) -
2.5· 10 10 2.5 -
') at 3· 10 1 0 Hz
241
relaxation, vibration and deformation [13]. The dielectric losses of current technical
glasses, e.g. the soda-lime type (Fig. 142), are comparatively large and increase rapidly
with rising temperature. However, clear silica glass is among those technical glasses
with the lowest tan δ factor (Fig. 142). The values of tan δ for clear silica glass at room
temperature are given in terms of frequency in Table 62 (according to [7, 8]).
The tan δ values for opaque silica glass are somewhat higher (Table 62).
The loss factor δ of clear silica glass at a frequency of 1 MHz remains almost
constant up to about 200 °C (Fig. 142). It increases rapidly with further raising of the
temperature, reaching the value tan δ = 500· 10" 4 at 500 °C, according to Shand
[24] (Fig. 142).
At a frequency of 109 Hz, clear silica glass shows a minimum value of tan δ
(Table 62). According to Shand [24], it attains the value tan δ = 0.68 · 10"4.
The dielectric loss of clear silica glass is therefore lower at elevated temperatures
[13] than that of all other known materials, with the exception of mica and rutile.
4.6 OPTICAL PROPERTIES

The interaction of radiation with glasses may have the following effects:
(a) reflection at the phase boundary from which the radiation is incident onto the
glass, if the two media differ in refractive indices;
(b) refraction at the boundary of the two media, if these differ in their refractive
indices; the refracted beam passes through the glass at a certain refractive angle;
(c) absorption of radiation passing through the glass, which reduces its intensity
and spectral distribution according to the absorptive properties of the glass;
(d) scattering of radiation due to scattering centres present in the glass.
Other phenomena that can be observed are birefringence (depending on the
structural arrangement and thus on the degree of isotropy), polarization (resulting
from the interaction of radiation with glass under the effect of reflection, refraction,
absorption, scattering, etc.), interference, spontaneous emission (luminiscence), photo
chemical phenomena and a number of additional physico-chemical phenomena
[65, 66, 67, 68].
In the simplest case, the incident radiation flux Φ is divided into the respective
radiation fluxes of reflected, transmitted, absorbed and dispersed radiation:
Φ Φ Φ
= 1 + ^ + , + ^ + Φα (43)
where Φ is the total incident radiation flux,
ΦρΓ is the directly reflected radiation flux,
Φρά is the diffusely reflected radiation flux,
ΦΧτ is the radiation flux transmitted directly,
Φτά is the radiation flux scattered,
Φα is the absorbed radiation flux.
242
Then
Φ Φ Φ Φ Φ
V ;
Φ Φ Φ Φ φ
Φ
where - ^ = ρΓ is the coefficient of specular reflection,
Φρά
—jr = Qd is the coefficient of diffuse reflection,
— £ = τΓ is the coefficient of direct transmission,

Φ
Φτ
—^ = Td is the coefficient of scattered transmission,
—- = a is the absorption coefficient.
Then
{Qr + ßd) + (τΓ + τα) + α = 1 (45)
and
ρ + τ -f a = 1 (46)
where ρ is the coefficient of reflection (total reflectivity),

τ is the coefficient of transmission (total transmittance),
a is the coefficient of absorption.
4.6.1 Reflection of radiation by silica glass
If a beam of monochromatic radiation passes from a medium having re

fractive index n (e.g. from air) onto the boundary separating it from a medium with
refractive index n (silica glass), it is generally divided into two beams. One remains
in the medium with refractive index ri and is called the reflected beam, the other is
refracted into the medium with refractive index n and may pass through this medium,
as explained below, or may be absorbed, dispersed, etc.; this is shown schematically
in Fig. 143.
The angle Θχ between the incident beam and the normal constructed at the point
of incidence, is the angle of incidence, Θ2 is the angle of refraction and Θ\ is the angle
243
of reflection. The directions of the refracted and reflected beams are defined by
Snell's law of refraction,
n sin Θ2 = ri sin Θχ (47)
or the law of reflection,

θ\ = Θ, (48)
If a beam passes from an optically thinner medium into an optically denser one,
i.e. ri < n, then Θ2 < Θ1 and the beam is refracted towards the normal. On the other
hand, if it passes from a medium of higher optical density into a thinner one, i.e.
ri > n, then Θ2> Θχ and the beam will refract away from the normal. In the latter
case angles 0U &u and 0m are equal for a certain angle of incidence, <9m being the
marginal, or critical angle. At angles of incidence in the denser medium greater than
the limit angle <9m, all the radiation will be reflected from the boundary and the
phenomenon is called total reflection.
Fig. 143 — Schematic representation of

phenomena involved in the interaction of
radiation with glass
If a monochromatic beam of light passes perpendicularly from medium ri into

the glass surface n, the coefficient of reflection at the surface can be calculated from
Fresnel's equation
Q = (49)
n + ri
where ρ is the coefficient of reflection on one surface,

ri is (usually) the refractive index of air (ri ~ 1),
n is the refractive index of glass.
244
For perpendicular incidence of light and several surfaces, with absorptivity
equalling zero, the coefficient of reflection can be calculated from the equation
= 1 - 1 - (50)
n + 1
where rri is the number of boundary surfaces.

On considering the refractive index of silica glass ne (for a wavelength of 546.07 nm)
of 1.0460 079, the reflective coefficient ρ for this wavelength without absorption on
one surface is ρ = 0.0349, i.e. 3.49%. Equation (50) can be used to calculate reflection
on two surfaces; for the same reflective coefficient ρ = 0.0687, i.e. 6.87%.
The reflected beam is polarized, and oscillates in a plane perpendicular to the plane
of incidence. The degree of polarization depends on the angle of incidence. The beam
will be completely polarized when the angle of incidence corresponds to the so-called
Brewster polarization angle <9p. For more detailed information on the matter, the
reader is referred to [65].
4.6.2 Optical refraction and dispersion by silica glass
Refraction of a light beam by glass can be defined by Snell's law, which if

n' = 1, can be written in the form
sin Θγ c t .
nx = - ^ = - 51
sin Θ2 νλ
where c is the velocity of light in vacuum,
νλ is the phase velocity of light in glass.
The speed of passage of a light beam through a material medium (silica glass) and
thus also the respective refraction index n depend on the mutual effects of the field
strength on the passing beam and the outer electron envelopes of atoms which
represent the material content of the medium. Electrons perform forced harmonic
oscillations under the effect of light energy, so that the outer electrons can be regarded
as harmonic oscillators. The phase velocity of the light beam νλ then decreases the
more the outer electrons are polarizable. Absorption would result from perfect
resonance of electrons with the frequency of the passing light beam. The subject
matter is dealt with in more detail in Section 4.6.3.
The relationship between the refractive index and wavelength (frequency, energy)
of radiation is described by the so-called dispersion equation
ΐ^-^.^-Σ-π (52)
245
where n is the refractive index of the glass,
JVf is the n u m b e r of particles (molecules) in a unit volume,
e is the electron charge,
m is the electron weight,
fi is the so-called oscillator strength,
v is the light frequency,
vf is the frequency of electrons.
If, according to Maxwell's theory, the following relation holds for infinite wave
lengths (in a static electrical field)
£
"A-* = (53)
where ε is the permittivity, and the relation takes no account of the dispersion of
light (dependence of the rate of propagation on wavelength), then a similar dispersion
equation holds for the permittivity
ε - 1 e2 _ /,
(54)
ε + 2 3nm T
The particular frequencies of materials vf which do not absorb in the visible part of
the spectrum lie in the region of shorter wavelengths (in the ultraviolet region of the
spectrum), and vf > v. The denominator in equation (52) increases with decreasing
frequency v, and the refractive index decreases. At v = v0 (v0 being the frequency
in the absorption region), the refractive index would increase beyond all limits, which
would of course be physically impossible. On taking into consideration the absorption
taking place during resonance of the electron frequency with that of the incident
radiation, the course of the refractive index according to [65, 68] can be explained
by means of Fig. 144.
Fig. 144 - The variation of refractive index

with radiation frequency over the absorption
band range
The values of n therefore change in the proximity of the absorption band; the
phenomenon is called anomalous dispersion.
246
Electrons as well as atomic nuclei are displaced under the effect of an electrical
field, the shifts being much smaller than those of the electrons. The nuclei exhibit
their own vibrations, belonging to the infrared region of the spectrum.
According to the dispersion equation (52), the refractive index thus depends on
the wavelength of the radiation.
As in the case of reflection, refraction of a light beam also results in polarization.
The beam is partially linearly polarized, the oscillation plane being parallel to the
plane of incidence. The degree of polarization again depends on the angle of incidence.
The polarizing effect increases with the number of refractions, i.e. if the refraction
occurs at several boundaries. The subject is described in detail in [65, 66].
Table 63
Designation of the refractive index and the corresponding wavelength
Refractive index Wavelength λ Discharge lamp

designation (nm) filled with
«i 365.01 Hg
"h 404.66 Hg
n 435.84 Hg
%
nF , 479.99 Cd
n¥ 486.13 H
"e 546.07 Hg
"d ' 587.56 He
nD 589.29 Na
WC' 643.85 Cd
«c 656.27 H
nr 706.52 He
"A 769.90 K
ns 852.11 Cs
nt 1013.98 Hg
The refractive index is mostly defined for wavelengths λ = 546.07 nm and λ =

587.56 nm, and designated ne and nd. Table 63 lists the wavelengths of radiation
and their sources, for which the refractive index is usually measured.
The so-called Abbe numbers ve and vd are further determined for the given wave
lengths by means of equations
247
Table 64
Refractive index ηλ of silica glasses
Άχ λ (nm) Glass designation
Puropsil Trasil SE Spectrosil C o d e 7940 SQ 1 Suprasil
. wF, 479.99 1.463 64 1.4636 1.463 54 _ 1.463 50 _

n¥ 486.13 1.463 24 1.4632 1.463 17 1.463 131 1.463 12 -
"* 546.07 1.460 20 1.4601 1.460 11 1.460 079 1.460 08 1.460 07
«Id 587.56 1.458 57 1.4585 1.458 50 1.458 462 1.458 46 -
"c 643.85 1.456 75 1.4567 1.456 74 1.456 708 1.456 71 -
nc 656.27 1.456 45 1.4564 1.456 41 - 1.456 36 1.456 37
The additional quantity to be determined is the so-called mean dispersion
nF> - nc (57)
nF — nc (58)
and a number of relative dispersions calculated from the equation
- n2 (59)
1
where
λ1 < λ < λ2 .
The so-called partial dispersions are also used.
Figure 145 shows the dispersion curve of Suprasil silica glass, and Table 64 gives
the most important refractive index values for other types of commercially manu
factured clear silica glasses.
1.55
1.50
1.A5
Fig. 145 — Dispersion curve

1.40
200 400 600 800 1000 2 3 4 of silica glass (Suprasil)
— *- λ (nm, μπι)
248
In agreement with theory, the refractive index increases rapidly in the ultraviolet
region of the spectrum, as a result of resonance of the radiation frequency with that
of electrons in the Si—O bonds; on the other hand, the refractive index decreases
in the close infrared region as a result of resonance with the vibrations for the Si—O
bonds.
The refractive index of silica glass depends on temperature. To explain the tem
perature dependence of the refractive index of glass, Prod'homme [69] considers
two mutually opposite physical phenomena:
(a) the refractive index decreases as a result of increasing the specific volume with
increasing temperature,
(b) the refractive index increases in consequence of increasing polarizability with
increasing temperature.
1.472
1.4590
1.468 88
86
1.464 84
82
1.460 1.4580
200 400 600 800 1200 1600 2000
- f CO — t CO
Fig. 146 — Temperature dependence of the Fig. 147 - Dependence of the refractive index
refractive index of silica glass of silica glass on fictive temperature
In the case of silica glass, the specific volume increases only slightly with increasing
temperature (even in the transformation interval) so that the polarization phenomena
prevail. Figures 146 and 147 demonstrate the temperature dependence of the re
fractive index of silica glass.
4.6.3 Absorption of radiation by silica glass
The wave function of the atom describes all the possible energy states of
the atom whose changes control transitions in the electron envelope. The molecular
wave function is more complex. The internal energy of a molecule, Eb can be divided
into the following 4 parts:
E { = Ee + £ v + E r + W (60)
where Ee is the energy of the electrons,
Ey is the energy of the vibrational motion,
Er is the energy of the rotational motion,
W is the interaction energy.
249
Then
£ e > Ev > Er (61)
An atom or molecule can then radiate or absorb only those photons whose energy
hv equals the difference in energy levels, i.e. for a molecule
hv = £" -E' = {E: - E;) + (E: - E:) + {E; - E'r) (62)

where E' is the energy in the basic state and E" in the excited state.
It is thus possible to investigate electron, vibration and rotation spectra or their
combinations. Bohr's results indicate that the electron transitions result in radiation
or absorption in the ultraviolet and visible parts of the spectrum, the vibration in the
close infrared region and the rotational transitions in the remote infrared region
of the spectrum and even longer wavelengths. The rotational spectra do not arise
in silica glass.
The spectral transmission of very pure silica glasses in the short-wave region of
the spectrum (ultraviolet region) ceases approximately at λ = 160 nm. In this case,
silica glasses do not absorb in the visible part and the transition in the infrared part
of the spectrum is limited up to about λ = 5 μιη.
30l·
1.0 1 8
Y-pJ
σ
0.8 Ü
ω
Q6
fc. ID
A
I Q2
04
- J
/ I l 1
150 200 250 300
»- λ ( nm)
Fig. 148 — Spectral transmission curves for

silica glass: 1 — Tetrasil SE, 2 — Pursil K
Fig. 149 — Reflectance of silica glass (a) and of

S i 0 2 crystal (b) in terms of radiation energy
The position of the absorption edge in the ultraviolet region of the spectrum is
affected by the strength of the Si—O bonds, as well as by impurities, defects in
structural arrangement, coloured centres, etc. As already mentioned, the absorption
edge of relatively pure silica glass (Tetrasil SE) in the ultraviolet region of the spec
trum lies at λ = 160 nm ( ~ 8 eV); this is demonstrated by Fig. 148.
250
This, comparatively pure silica glass (Tetrasil SE — curve 1 in Fig. 148) contains
the following impurities (in ppm):
K, Li, Ca, Mg, AI, Fe, Ti, Na, Cr, Ni, Cu, Mn, Co, Zn < 0.1
Philipp [70] measured the reflectivity of high-purity silica glass and established
absorption peaks at 10.2 eV, 11.7 eV, 14.3 eV and 17.2 eV, as shown in Fig. 149.
Table 65
Reflection maxima of quartz, silica glass, binary and ternary glasses
Substance Reflection maximum (eV)
Si0 2 -crystal 10.2 11.5

Si0 2 -glass
(Corning 7940) 10.2 11.5
N a 2 0 - 2 Si0 2 8.5 9.3 11.5
N a 2 0 - C a O - 5 Si0 2 8.5 9.3 11.5
Table 65 lisU []ic reflect ion maxima of high-purity crystalline Si0 2 and of the
synthetic silica glass Corning 7940, compared with the binary glass Na 2 0—2 Si0 2
and the ternary glass Na20—CaO—5 Si0 2 , according to Sigel [71].
It may be assumed that the small differences in the positioning of absorption peaks
specified by various authors are due to different degrees of purity of the glasses and
the Si0 2 crystal.
Curve 2 in Fig. 148 illustrates the spectral transmissivity of silica glass Pursil K,
containing the following impurities in ppm:
Al = 50 Li = 2 Cu < 0.1 K = 0.2
Fe = 0.5 Ca = 2 Mn < 0.1 Ni < 0.1
Ti < 0.8 Mg = 0.1 Co < 0.1
Na = 1.0 Cr < 0.1 Zn < 0.1
The presence of impurities therefore shifts the absorption edge towards the near
ultraviolet region of the spectrum. The introduction of additional components in
greater concentrations will impair the relatively strong bridge-type Si—O bonds,
producing non-bridging weaker bonds of prevailingly ionic character. The electrons
are therefore bound less strongly. With regard to the energetic nature of the radiation,
the absorption edge will consequently shift towards the visible part of the spectrum.
On the basis of the study by Sigel [71, 98] it may be assumed that the absorption
of silica glasses in the ultraviolet region of the spectrum is due to:
(a) impurities present in the glass and affecting the wavelength range of 200 to
350 nm,
(b) induced absorption, resulting from the impaired bridging bonds Si—O and
affecting the wavelength range 150 to 200 nm,
251
(c) the relatively strong Si—O bridging bonds of the basic structure of silica glass,
affecting the wavelength range shorter than 150 nm.
Under reducing conditions on melting in a graphite crucible, the actual structure
of silica glass differs from the theoretical structure in the non-stoichiometric coordi
nation of silicon, namely in a lower degree of oxidation. According to the reaction
SiO, + C SiO + CO (63)
which proceeds at temperatures higher than 1350 °C, the gaseous SiO and CO
arising can further reduce Si0 2 to SiO and Si, or Si 2 0, Si 2 0 3 , S i 3 0 4 (mixtures of
S i 0 2 + SiO + Si) can be formed. According to Garino-Canina [73], this so-called
reduced non-stoichiometric silica glass corresponds to the formula Si0 2 _ x , revealed
by the characteristic absorption band at λ = 242 nm, as shown by curve 2 in Fig. 148.
As already mentioned, clear silica glasses melted from pure quartz or synthetic raw
materials exhibit high spectral transmittance in the visible part of the spectrum.
Reduced spectral transmittance in the visible part of the spectrum compared to
theoretical values (cf. Fig. 148, 153) is due to reflection of radiation at the two func
tional planes. The presence of impurities, the introduction of components absorbing
radiation in the visible part of the spectrum, the effect of irradiation, etc., will reduce
the spectral transmittance of radiation in the visible part of the spectrum, either
generally or selectively. The phenomenon is made use of for some special purposes.
100
80
. 60
: 40
; 20 80
: 60
40
20 80
v
if
εΑο, o * ^
60
40
20
3 4 5 6 8 10 15 20 30 40 '
»- A ( pm)
Fig. 150 — Curves of spectral transmittance in the Fig. 151 — Schematic diagram of vibrations
infrared region of the spectrum: 1 — silica glass; in the [ S i 0 4 ] 4 _ tetrahedron
2 — tridymite;3 — a-quartz
The transmission of radiation in the infrared region of the spectrum is restricted

to a wavelength of approximately λ = 5 μηι with clear silica glasses. This is at the
short-wave edge of an absorption band showing a peak at 9-9.5 μιη, which corres
ponds to resonance of the radiation frequency with vibrations of the Si—O bonds
(asymmetrical vibrations *- Si—O -*· Si).
The symmetrical vibrations {<- Si—O—Si -► and Si -> O <- Si) correspond to the
absorption band at 12.5 μιτι, and vibrations of the type Si—O—Si and. O—Si—O
252
to the band at 21 μηι. The spectral characteristics according to [74] are plotted in
Fig. 150; a schematic diagram of vibrations in the [ S i 0 4 ] 4 " tetrahedron is shown
in Fig. 151.
In front of the absorption band corresponding to the resonance of radiation fre
quency with the vibrations of the Si—O bonds, silica glass exhibits three characteristic
absorption bands, an intense one at 2.7-2.85 μιη and two more feeble at 3.5 and 4.3 μηι
respectively, The positions of each absorption band correspond to various structural
arrangements of OH groups in the structure of silica glass [75, 76].
The concentration of OH groups (in ppm) in silica glasses can be calculated,
according to Yovanovich [77], from the intensity of the absorption band at λ =
2.7-2.85 μιη. According to Lambert-Beer's law,
Φ = Φ0 e" c d (64)
where c is the concentration,
ε is the molar exponential absorption coefficient,
/ is the thickness of glass;
and it then holds for the base 10 logarithm that
log Φ = log Φ0 - (ce'J) (65)

and
Φ Φ0
-log--ce'J-log- (66)
where ε' = 0.4343ε.
Then we can write
c=
^l08¥ = W 0 g ¥ m 0 i r l < 67 >
and for MoH = 17.01 (g mol" 1 )
ε' = 77.5 (1 m o l - 1 c m " ' ) = 77 500 (cm3 π ι ο Γ ' cm" l ) =

77 500 · 2 2
= 77 500 -2.2 g m o r ' c m " ' = -(cm'1) (68)
Thus
C+=
77500^2 ' 7 1 ° 8 T ( g g " 1 ) <69)
17 000 1 Φ0
Cl = l0g (ppm)
77^12 " 7 ~Φ ( 7 °)
253
and
100 Φ0
c, = — l o § -φ (PPm) (71)
where cx is the concentration of OH groups in ppm,

Φ0, Φ are the values read from the graphical plot of the absorption band at
λ = 2.7-2.85 μιη (cf. Fig. 152)
Fig. 152 - Plot for the determination of Φ0 and Φ in the

calculation of the concentration of OH-groups in silica
glass
Figure 153 shows the spectral characteristics of some types of commercially manu
factured clear silica glasses.
I.U
/"\ ^~
/ 1
0.8 /
1
/ / 2
Q6- \
\
1
i
\ i
\ 1
0Λ 1
"/ //
0.2
1 1 i
0.16 0.20 0.30
λ (μπι)
Fig. 153 - Spectral transmittance of commercially manufactured clear silica glasses:

- Spectrosil (1), Vitreosil (2) - I = 10 mm; (b) - 101 Quartz (1), 105, 106, 204, 206 Quartz
2) - I = 10 mm; (c) - 102, 104, Quartz (7), 151 fused silica (2) - / = 10 mm; (d) - Tetrasil SE -
= 10 mm; (e) - Tetrasil - / = 10 mm; (f) - Puropsil - / = 10 mm; (g) Pursil K - / = 10 mm;
h) - Pursil - / = 10 mm; (i) - Heralux (1), M 62 (2), M 84 (3) - / = 2 mm; (j) - Infrasil I, II -
= 10 mm; (k) - Suprasil I, II - / = 10 mm; (1) - Infralux - / = 2 mm; (m) - Suprasil W -
= 10 mm; (n) - Homosil, Herasil I, II, III, Herasil Special, Heralux - / = 10 mm; (o) - Ultrasil
OHF - Z = 10 mm; (p) - Code 7940: (l) UV Grade, (2) for optics; (q) - - Q 1 , Q2 (1), Q3, Q4 (2) -
/ = 10 mm; (r) - SQl - / = 10 mm; (s) - Silquartz - / = 5 mm (1 = fused from MBK quartz,
2 - from Svedlär quartz); (t) - Trasil - / = 5 mm
254
Fig. 153 — Spectral transmittance of commercially manufactured clear silica glasses — cont.
1.0 r 1.0
08 08
06|
0.4 0.4
02 02
016 020024028 1 2 253 354 4.5 016 020 024 028 1 2 2.5 3 35 4 4.5
»- λ (μπη) »* λ (μηη)
Q16 020 024Q28 1 2 25 3 3,5 4 4,5 0.16 020 024 028 2 2.5 3 3,5 4 4.5
»- λ (pm) ^ Λ ( μπι)
b
255
0.2 0.3 04 05 0607080910 2 3 A 5 6

- A ( Mm )
0.8 l·
QAh
Q15 0.2 Q3 04 Q5 06 07 0ß 091.0 5 6

— — » - λ ( μιη ]
257
1.0 r
200 250 300 1 2 3

- » - λ ( nm, μπι)
258
1.0 r
0.16 0.20 0.24 0.28 0.32 0.36 0.40 1 2

*~ λ (μηη )
P
1.0
0.8
0.4
A'
' 2
Q2
200 240 280 320 1200 3000 3800

— λ ( nm )
160 200 240 280 2200 2600 3000 3400

-*- λ (nm)
259
I.U
--^Λ.
Q8 J SI
w
0.6
* 04 1
1
1
Q2
1
1
1
1
1
w
/
y
0.2 0.25 Q30 0.35 1.0 2.0 3.0 4.0 5.0
-λ(μπη)
'I.U
0.8 //
/
0.6
0.4
0.2
.... i ... I i
0.20 0.25 0.30 0.35 1
-»► λ ( μιτη )
260
4.6.4 Scattering of radiation by silica glass
As explained theoretically in more detail in Section 2.4.8, scattering of light

in silica glasses can be defined as the change in the propagation of radiant energy
arising from an interface between two media, or in passing through a medium. By
measuring the intensity of light dispersed by microheterogeneous scattering centres
in silica glass it is possible to assess the size, concentration and character of scattering
centres in terms of the measuring angle. The measuring method is described in detail
in [78] and in Section 2.4.8 of the present book; the glass specimen is cylindrical
(15 mm in diameter and about 30 mm in length), and its surface is optically polished.
Figure 154 shows the indicatrix curve of the Soviet optical clear silica glass KI melted
from Brazilian crystal.
2.0 p
1.8 L
1.6
U
1.2
*■ 1.0
* 0.8
0.6
I;
0.4
0.2 h ^
30 60 90 120 150
— Θ C)
Fig. 155 — Brillouin's spectra of
scattered light flux (at various
Fig. 154 - Intensity of scattered light flux Φτά vs. measuring measurements sensitivities) for
angle Θ of Soviet silica glass KI: 1 - λ = 436 nm; 2 - λ = 546 nm crystalline Si0 2 (a) and silica
2 — λ = 546 nm glass (b)
Detailed study of the scattering of light in various substances by Mandelshtam,

Brillouin and Gross [79, 80] showed that in its spectral composition, the scattered
light was not identical with the incident light. The original frequency of incident
radiation is scattered in crystals into 6 frequencies, in glasses into 4 frequencies and
in liquids into 2 frequencies. The result of measuring Brillouin's scattering in crystal
line quartz and silica glass are plotted in Fig. 155, following Shapiro, Gammon and
Cummins [80].
Theoretical interpretation of the measurement results is based on the assumption
that the scattering occurs at the points of fluctuating concentrations; they are real
acoustic waves of high frequency, so that acoustic vibrations are involved.
261
4.6.5 Luminescence of silica glass
Luminescence processes are generally divided into several groups, according

to the type of excitation and the duration of luminescence (after excitation ends).
From the standpoint of the type of excitation, luminescence phenomena are
divided into photoluminescence, thermoluminescence and radioluminescence; from
the standpoint of duration into fluorescence (which only occurs during excitation)
and phosphorescence (the luminescence persists after excitation).
In order to produce fluorescence, glass must absorb a certain amount of energy;
quantum theory shows that the radiation causing luminescence has a higher fre
quency than the luminescence it produces.
If a short interval of time elapses between the excitation process (absorption of
radiation) and the emission (fluorescence), of the order of 10~7-10~9 s, so that the
two processes occur almost simultaneously, the phenomenon is called fluorescence.
However, if excitation takes the electron into an orbit from which transition into
the basic state is prohibited, this produces a so-called unstable state whose duration
is limited by collisions with other atoms, so that radiation proceeds after the exci
tation has stopped. The phenomenon is called phosphorescence.
Silica glasses made by various technologies from natural and synthetic silica raw
materials show luminescence bands at the following wavelengths:
280 nm, 396 nm violet luminescence,

505 nm green luminescence,
575 nm yellow-orange luminescence.
600
500
5 Ann
c
300
H
A
A 200
100
7 7' w ^-'V \ \
' i i ^ S . N J
-— E (eV)
200 300 400 500
Fig. 157 — Luminescence spectra of silica glasses:
-*A(nm)
Suprasil WF (1); laboratory-melted group IV
Fig. 156 Luminescence spectra of silica glass (2); Corning 7940 (3). Excitation energy
glass 7.9 eV, T = 90 K
262
Glass melted in oxygen-hydrogen burners contains luminescence centres whose
spectra are shown in Fig. 156 (after Botvinkin and Zaporozhskii [81].
Long-term heat treatment at 700-1000 °C in an atmosphere free of H 2 will ex
tinguish the centres of violet luminescence and create centres of green luminescence.
The transition of the green luminescence centres into yellow-orange takes 40 to
50 hours at 1100-1200 °C in synthetic silica glasses. The centres are then thermally
stable.
There is some controversy in the theoretical interpretation of luminescence centres
at 4.4 eV (280 nm) and 3.1 eV (396 nm). Amosov et al [82] consider an oxygen vacancy
model for the luminescence centre at 3.1 eV, Garino-Canina [83] and Cohen [84]
attribute it to an admixture of germanium, Hetherington et al [85] to the presence
of aluminium and Chalikov and Pivovarov [86] to the presence of iron.
The luminescence centre at 4.4 eV is explained by Jones and Embree [87] and
Amosov and Chalikov [82] by the oxygen vacancy model, while Silin et al [88]
assume it to be due to internodular oxygen bound by an ionized silicon atom.
Trukhin et al [89] studied in detail the principle of luminescence centres at 3.1 eV
and 4.4 eV. Figure 157 shows the luminescence spectra of Suprasil WF silica glasses,
a laboratory-melted glass and the Corning 7940 glass.
Figure 158 shows the luminescence spectra of glasses with 0 2 defects.
— E (eV)
Fig. 158 — Luminescence spectra of Fig. 159 — The structure of a luminescence centre at 4.4 eV
silica glass containing: 1 — 1 to Excitation energy: 1 — 4.95 eV, 2 — 5.05 eV; luminescence
3 · 1 ( Γ 3 wt.% of 0 2 defects; excitation spectra: 1' - 4.3 eV, 2' - 4.05 eV, 3' - 4.55 eV,
2 - 1.5 · 1(Γ 2 wt.% of 0 2 defects; T = 90 K
3 — type I glass
The results of the studies indicated that the luminescence centre at 3.1 eV is due
to an admixture of germanium in the silica glass, and the centre at 4.4 eV to a struc
tural (molecular) defect. The latter luminescence centre is responsible for colouring
263
silica glasses irradiated by neutrons. Its structure is composed of partial bands at
4.05 eV, 4.30 eV and 4.55 eV (cf. Fig. 159). According to Trukhin [89], the centre
consists of an intermodular SiO molecule.
4.6.6 Resistance of silica glasses to the effect of radiation
Photons (y-radiation, X-radiation), electrons (ß-radiation), charged atomic

particles and neutrons are the most frequent types of radiation rich in energy that
may come into contact with silica glasses in their special applications.
As a result of Compton processes, interaction of y-radiation of adequate energy
with silica glasses causes ionization and the photoelectric phenomenon. Atoms of
glass are ionized by y-radiation. Similar effects are produced by charged atomic
particles (/J-particles, protons, fission products). The resulting effects of a proton,
an electron or a charged atomic particle are therefore similar, the only difference
being in the penetrating power of the effect. Photons penetrate relatively deeply into
the glass, but the intensity of their effect is small. Electrons reach smaller depths but
have a more intense influence. Atomic particles have very intense effects but prac
tically only at the surface; neutrons act on atomic nuclei [65].
— λ (nm)
, 600 400 300 200
*» | 1 ΓΠ 1 7!
T 1
3
Γ
J ,2 i<
/ V Fi
-rl-i-^ , , , 8 - 1 6 ° - Absorption spectra of irradiated silica glasses:
1 2 3 4 5 6 7 1 - Ultrasil, Infrasil; 2 - Homosil, Amersil;
»- E (eV) 3 - Corning 7940, Spectrosil, Suprasil
In silica glasses, y- and jS-radiation liberates electrons which are retained at the
structural defects and produce coloured centres. This occurs particularly when the
silica glass contains impurities, OH groups, etc. Irradiation may also result in the
so-called displacement processes, during which atoms or ions are shifted from their
equilibrium positions into interstitial ones; their displacement brings about a change
in the energy state of the electrons. If an anion gives up its equilibrium position, the
vacancy affects the electrons liberated by the effect of radiation as if a positive charge
were present. The moving electron is easily retained at this point, producing a new
centre which shows typical absorption. If this absorption is situated in the visible part
of the spectrum, a coloured centre is formed.
264
The three most intensive characteristic absorption bands formed by irradiation
of silica glasses are those at 215 nm, 300 nm and 550 nm, as demonstrated in Fig. 160
after Levy [90] and Cohen [91].
The absorption band at 215 nm occurs in all irradiated silica glasses regardless
of their method of manufacture. Conversely, in glasses resistant to radiation (high-
purity silica glasses prepared by various technologies) there are either no absorption
bands at 300 nm and 550 nm, or they show only minute intensity. From the stand
point of irradiation and the presence of impurities, silica glasses can therefore
be divided into three groups (according to Bjurganovskaya, Vargin, Leko and
Orlov [92]).
The first group (curve 1 in Fig. 160) comprises glasses with a higher concentration
of impurities (10~3-10~2 wt.%), melted in contact with graphite.
The second group (curve 2 in Fig. 160) consists of glasses melted in an oxygen-
hydrogen flame from natural raw materials or synthetic SiCl4. The structure of the
absorption spectrum and the intensity of the absorption bands varies over a wider
range, depending on the purity of the initial raw materials and the method of
melting. The group is characterized by a low intensity of the absorption band at
550 nm- after low-level irradiation. The band starts to form on irradiation at
258 C kg" 1 and higher.
Table 66
Allowable irradiation of silica glasses
Type of Type of silica glass Irradiation at which

spectral curve absorption at 550 nm
is low (negligible)
(Ckg-)
First group Vitreosil IR, Infrasil,

Pursil, Ultrasil 2.58-12.9
Second group Vitreosil OG, OH, Homosil,
Amersil, Herasil 129-1290
Third group Corning 7940, 7943,
Suprasil, Spectrosil 25 800
The third group (curve 3 in Fig. 160) is that of glasses melted from high-purity raw
materials, or glasses treated additionally by special technologies. The absorption
spectrum consists of an absorption band at 210-215 nm and very faint bands at
240-260 nm.
The classification of silica glasses according to [92] is shown in a comprehensive
form in Table 66.
The absorption spectra of glasses over the wavelength region up to 200 nm
(measured in vacuo) are shown in Fig. 161 (according to Nelson and Weeks [93]).
265
The main factors to be considered, from the standpoint of the resistance of silica
glasses to irradiation, are therefore the purity of the glass, the presence of OH groups
and the method of melting. Lell [94] investigated the effects of Na, Li, AI, K, Rb
and Cs on the character of the absorption spectra of silica glass irradiated by y-radi-
ation. The results are plotted in Fig. 162.
-* A(nm)
A\/Cs
220 200 180 160 0.5
/ n
0Λ / »
4
m
Na
i/ / / .v^Rb
0.2 1 '-\^1/J *'\
K
0.1 Zu //ja
5.0 5.8 66 U 8.2 £ϊ>< . Α*Ί ι 1
- E (eV) 4 5 6
- E (eV)
Fig. 161 — Absorption spectra of Corning 7940
silica glass: 1 — irradiated by y-radiation of Fig. 162 - Absorption spectra of silica glass
2 064 000 C k g - *; 2 - glass irradiated as (/) and doped with 0.2 wt.% Na; 0.5 wt.% K, Rb, Cs, Li;
heated at 250 °C (30 min.); 3 - glass 2 mol % Al. Glass thickness 3 mm, irradiated
irradiated as (1) and additionally heated at with y-radiation, 2580 C kg" *; the glasses doped
450 °C (30 min.); 4 - glass irradiated as (1) and with Li and Al were irradiated by a dose of
additionally heated at 620 °C (30 min.) 1548C kg" 1
The effect of a combination of Al impurities, alkalis and hydrogen in irradiated

silica glass was also studied by Lell [95].
A number of low-intensity absorption bands were found in silica glasses after
irradiation. The subject was surveyed in detail by Lell, Kreidl and Hensler [96].
4.6.7 Photoelasticity constant
Homogeneous and annealed silica glass behaves as an amorphous optically

isotropic material [17]. However, under mechanical stress, the glass becomes aniso-
tropic and shows temporary birefringence. The photoelasticity constant is a coefficient
specifying the relationship between mechanical stress and the resulting birefringence
in the glass. This constant is characteristic of a given glass composition.
The value of the photoelasticity constant of clear silica glass is very close to the
value of this constant for borosilicate glasses of the Simax and Pyrex type (cf. Table 67).
The temperature dependence of the photoelasticity constant of glasses is very small
(about 2 to 8%) over the temperature range 20-400 °C. These differences vary within
the limits of the measuring accuracy, and are of no practical significance over the
temperature range 20-100 °C.
266
Knowledge of the value of the photoelasticity constant allows the internal stress
in the glass to be assessed, according to the path difference measured in a polarimeter.
The relationship between stress in glass and the intensity of the birefringence
(measured as the path difference of polarized light) is described by Brewster's equation
where p is the compressive or tensile stress in MPa,

R is the path difference in nm,
/ is the glass thickness in mm,
B is the photoelasticity constant (Pa 10 12 )~ l
Table 67
Photoelasticity constant
Glass Photoelasticity constant

(Pa-1012)-1
clear silica glass 3.5-3.7

Vycor 3.6-3.7
Simax, Pyrex borosilicate glass 3.7-3.8
soda-lime glass 2.4-2.6
drawn sheet glass 2.5-2.6
Tensile stresses in the glass ware which do not exceed l/20th of the mean tensile
strength of the glass are allowable. If the tensile strength of silica glass (Sec. 4.3.3)
is taken to be 50-70 MPa, the admissible stress amounts to 2.5-3.5 MPa.
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Zh. Prikl. Spektrosk., 25 (1976), 5, p. 817-822
[83] GARINO-CANINA, V.: Comptes Rendus, 42 (1956) 16, p. 1982-1987
[84] COHEN, A.J.: Phys. Rev., 105 (1957), 4, p. 1151-1155
[85] HETHERINGTON, G. - JACK, K.H. - RAMSAY, M.W.: Phys. Chem. Glasses, 6 (1965), 1, p. 6-15
269
[86] CHALIKOV, V. Ch. - PIVOVAROV, S.S.: Proc. Conference on Optical and Spectral Properties of
Glasses, Riga, 1977, p. 56-57
[87] JONES, C.E. - EMBREE, D.: J. AppL Phys., 47 (1976), 12, p. 5365-5371
[88] SILIN, A.P. - SKUYA, L.H. - LAPENAS, A.A.: In: Fizika i chimia stekloobraznych sistem (The
Physics and Chemistry of Glass-Forming Systems). Riga, 1977, p. 93-105
[89] TRUKHIN, A.N. - BOGANOV, A.G. - PRAULINSH, A.M.: Fizika i chimia stekla, 5 (1979) 3, p. 346-353
[90] LEVY, P.W.: J. Chem. Phys., 23 (1955), 4, p. 764^-765
[91] COHEN, A.J.: J. Chem. Phys., 13 (1960), p. 321-325
[92] BYURGANOVSKAYA, G.V. - VARGIN, V.V. - LEKO, N.A. - ORLOV, N . F . : Deistvie izlucheniy na
neorganicheskie stekla (The Effect of Radiation on Inorganic Glasses). Atomizdat, Moscow, 1968
[93] NELSON, C M . - WEEKS, R.A.: J. AppL Phys., 32 (1961), 5, p. 883-886
[94] LELL, E.: Phys. Chem. Glasses, 3 (1962), 3, p. 84-94
[95] LELL, E.: J. Am. Ceram. Soc, 43 (1960), 8, p. 422-426
[96] LELL, E. — KREIDL, N.J. — HENSLER, J.R.: Radiation Effects in Quartz, Silica and Glasses. In:
Progress in Ceramic Science, Vol. 4. Pergamon Press, London, 1966
[97] TOMOZAWA, M. — DOREMUS, R.H.: Treatise on Materials Science and Technology. Radiation
Effects in Glass, Vol. 17, Glass II (FRIEBELE, E.J. - GRISCOM, D.L.), Academic Press, New York-
London-Toronto-Sydney-San Francisco, 1979
[98] TOMOZAWA, M. — DOREMUS, R.H.: Treatise on Material Science and Technology. Optical Absorp
tion of Glasses, Vol. 12, Glass I (SIEGEL, G.H.). Academic Press, New York-San Francisco-London,
1977.
270
5 APPLICATION OF SILICA GLASSES IN PRACTICE
5.1 INTRODUCTION
There are very widespread uses of clear and opaque silica glass.
Clear silica glass is used in the manufacture of mercury discharge lamps, intended
particularly for communal lighting (Figs 163, 164, 165), tubing for the production
Fig. 163 — Components of

a Tesla high-pressure
mercury discharge lamp
(250 W), made of clear silica
glass, including the burner
271
-^
Fig. 164 - Mechanical

processing of burners -
degassing of silica glass
Fig. 165 - Halogenide discharge

lamps Tesla
RVI 400 W, RVI 1000 W and
RVI 3500 W (made by Tesla
Holeso vice, Concern
Corporation [1])
of semiconductors, tubing for gas lasers, optical instruments and apparatus, delay
lines, various thermally stressed light bulbs and electronic valves; opaque silica glass
finds .applications, for example, in the manufacture of apparatus for the chemical
industry (Fig. 166).
In recent years, clear silica glass has found considerable application in space
technology (Fig. 167). It is used in the manufacture of some parts of spaceships and
satellites, covers of some batteries, various windows, outer covers of spaceships, etc.
In these applications, use is made of the high softening point of silica glass, its
resistance to thermal shock, resistance to radiation and advantageous spectral
transmission.
Fig. 166 — Part of an

industrial chemical apparatus
for synthetic production of
hydrochloric acid [2] (made
of opaque silica glass)
273
Silica glass is nowadays one of the more important materials indispensable for the
further rapid development of high technology.
Fig. 167 — Components of clear silica glass were used in the structural elements of the control system
of the Soviet lunar vehicle Lunokhod I (landed 17. 11. 1970). The special optical laser reflector [3]
contained several so-called corner prisma (cf. Fig. 181) made of Homosil glass: 1 — heating and
cooling control system; 2 — solar cells; 3 — optical laser corner reflector; 4 — reflectors and
TV cameras; 5 — hermetically sealed instrument compartment; 6 — undercarriage of the lunar
vehicle; 7 — TV and photographic scanning cameras; 8 — instrument for the determination
of physico-chemical properties of lunar soil; 9 — whip antenna; 10 — ninth wheel; 11 — radioisotope
thermal source for heating the gas in the instrument compartment during the lunar night;
12 — electrical installation for the moving directional antenna; 13 — directional antenna for
telemetric data transmission; 14 — mobile directional antenna
5.2 LIGHTING TECHNOLOGY
Clear silica glass is used in the construction of many types of light sources
(Figs 163, 164, 165).
Its advantageous properties which are utilized in these applications include par
ticularly the suitable spectral transmission, high softening temperature, excellent
electrically insulating properties, resistance to diffusion of gases and good chemical
durability.
Clear silica glass shows a very good transmission for ultraviolet radiation, and
above all the type I glasses (cf. Section 1.4) exhibit a relatively high spectral trans
mission, even in the infrared region of the spectrum (compared to current technical
glasses). The optical properties of silica glasses depend not only on the manufacturing
technology employed, but also on the content of impurities. Non-associated OH
groups are one of the main impurities present in silica glass. An elevated content
of OH groups also tends to reduce the viscosity of silica glass.
The so-called reduced (non-stoichiometric) silica glass can be formed in a reducing
medium (e.g. an H 2 atmosphere, oxygen-hydrogen flame, in graphite melting cru-
274
cibles). Long-term heat treatment of this glass at about 1000 °C in an oxidizing
atmosphere will bring about gradual oxidation, the non-stoichiometric glass slowly
converting to a stoichiometric type, and the absorption minimum of the spectral
transmission curve at 242 nm will gradually disappear.
Fig. 169 - Linear halogenide discharge lamp

HGITS 250 W [1] made by Osram
Fig. 168 — Halogenide discharge

lamp with a short arc stabilized by
clear silica glass electrodes [1]
(Osram Corp.)
275
The diffusion of hydrogen and oxygen into silica glass is closely associated with
its oxidation or reduction.
If silica glass contains a certain quantity of OH groups its heating, e.g. in the
operation of a light source, can bring about oxidation according to the equation
—Si 4 + —OH + Si 3 + — ^ —Si 4 + —O—Si 4 + — + 1/2 H 2 (73)
thus producing stoichiometric glass and liberating hydrogen, which can also affect
the performance of the light source. The reverse reaction, i.e. reduction of stoichio
metric glass by penetration of hydrogen and formation of OH groups, is likewise
possible.
Fig. 170 — High-pressure mercury discharge lamps by Tesla: (a) — type RVLX 125 W, 250 W and
400 W, with the outer bulb coated with phosphorus from the inside; the halogenide discharge lamp
of the RVIL type has the same appearance, (b) — type RVI 400 W halogenide discharge lamp for
220 V. (c) - type RVI 1000 W halogenide discharge lamp (220 V), 2000 W (380 V), 3500 W (380 V), [6]
276
Silica glasses free of OH groups can undergo slow oxidation according to the
equation
—Si 3 + + —Si 3 + + 1/2 0 2 -»· —Si 4 + —O—Si 4 + — (74)

I I ' I I
The processes mentioned above may also be involved in the so-called ageing or
browning of light sources [1].
Fig. 171 - Tunnel equipped

with silica glass IR radiators,
used to dry and bake car body
paint
Figure 168 shows a halogenide discharge lamp with an electrode-stabilized short

arc, made of silica glass, and Fig. 169 a linear halogenide discharge lamp.
Some light sources produced by the Tesla Holesovice Concern Corporation, using
silica glass or Vycor glass [6], are shown in Fig. 170. In all cases, the burner is made
of clear silica glass or of Vycor type glass.
Figure 171 demonstrates the application of silica glass infrared radiators.
5.3 SEMICONDUCTOR TECHNOLOGY
The manufacture of semiconductors makes use of equipment, instruments,

vessels and tubes that are subject to considerable thermal and chemical stresses.
Under these conditions, the material employed must not react with the semiconductor
and on heating, should not liberate even traces of substances which could invalidate
the semiconductor. Clear silica glass has proved to be a very suitable material for
these purposes.
277
Fig. 172 - Silica glass ware used in semiconductor technology [7]: 1 - spherical ground joints;
2 — conical ground joints; 3 — terminals; 4 — flasks; 5 — beakers; 6 — cocks; 7 — rods and capillary
tubes; 8 — silica glass wool; 9 — threads on clear silica glass tubes
In the production of semiconductors, clear silica glass is used in the form of various
flasks, beakers, cocks, rods and capillaries, ground joints, crucibles, various holders,
etc., as shown in Figs 172 to 174.
In selecting a suitable type of silica glass, it is therefore necessary to consider
primarily its purity (the content of trace impurities) and its viscosity, taking into
account the temperature conditions of its application. Chapter 4 presents examples
of the content of trace impurities in clear silica glass melted from natural raw ma-
278
Fig. 173 — Crucibles of clear and
opaque silica glass for the drawing
of silicon crystals [7]
Fig. 174 — Holders of silica glass in

which silicon wafers are kept during
the diffusion processes [7]
Fig. 175 — Vacuum drying chamber

for intermediate drying of wafers [8]
279
terials (the Heralux and Silquartz glasses), and from synthetic raw materials (the
Suprasil glass).
For the application in semiconductor technology, it is also necessary to consider
the temperature dependence of viscosity or the softening point of the silica glass.
In consequence of their higher content of OH groups, synthetic silica glasses
(type III — Suprasil) show temperatures corresponding to the viscosity η = 10 13 to
1011 Pa lower by about 50 to 100 °C than silica glasses melted from natural raw
materials. Synthetic silica glasses are also more rapidly fused in a semiconductor
melt (e.g. in the drawing of silicon monocrystals from melt by Czochralski's method —
Figs 173 and 176).
Fig. 176 - The drawing of a silicon monocrystal from melt

by the Czochralski method [10]: 1 - clear silica glass
crucible; 2 - graphite crucible; 3 - melted silicon;
4 - high-frequency heating; 5 - silicon monocrystal;
6 - nucleation crystal; 7 - drawing rod; 8 - protective
gas or vacuum
Tubes of clear silica glass of relatively large diameters (50-100 mm) are currently
used in diffusion processes. Holders of semiconductive materials (Fig. 174), such as
silicon wafers, are likewise made of clear silica glass.
On heating at temperatures of about 1150 °C (or about 1050 °C with synthetic
silica glass of type III, cf. Section 1.4) the clear silica glass products will gradually
deform, so that silica glass tubing, for example, has to be replaced periodically.
Apparatus made of clear silica glass (Fig. 177) is frequently used to prepare high-
purity distilled water for semiconductor technology.
Figure 178 exemplifies another application of clear silica glass, namely in the zonal
refining of germanium.
A new type of clear silica glass tubing has recently been developed for long-term
service at 1150-1300 °C without undergoing any deformation. Figure 179 shows its
application in the production of semiconductors: the tubes were heated at 1280 °C
for 720 hours. The standard type of clear silica glass (types I and II, cf. Section 1.4) is
liable to deform, while the new type of silica glass, called shape-stabilized, virtually
resists deformation at this temperature. This property is due to an artificially produced
cristobalite layer several tens of μιη in thickness, which reinforces the tube at high
temperature. The controlled formation of cristobalite is a result of a special diffusion
process, during which ions of some elements such as Al, Ge, Sn and Zn diffuse into
the surface of silica glass [7, 12]. The ions promote uniform crystallization of the
outer tube surface on heating above 1150 °C. The silica glass strengthened in this
way cannot, of course, be cooled below the temperature of cristobalite conversion,
280
Fig. 177 - Water distilling
apparatus for the processes
of semiconductor
technology [7]
as the layer would crack and the entire tube would break down. It may be assumed
that this new way of treating clear silica glass used to improve its resistance to de
formation on heating will also find advantageous applications in other fields of
industry.
Fig. 178 - Zonal refining of germanium [11]:

1,3 — boat and tube of clear silica glass;
2 - germanium; 4 - melted germanium;
5 — protective atmosphere or vacuum;
6 - high-frequency coil; 7 - direction of boat
movement
281
A new method of manufacture of semiconductor components, based on the use
of special ampoules made of clear silica glass, has recently been introduced.
86.50
Fig. 179 — Application of clear silica glass tubes in the diffusion processes used in semiconductor
technology (dimensions are specified in mm) [7]. The heating temperature is 1280 °C, the time
of heating 720 hours. The original tube diameter is 80 mm. To the left, a tube of OHF-ST glass
(stabilized), on the right, one of O H F glass (unstabilized): 1 — heating furnace; 2 — ceramic tube;
3 — clear silica glass tube; 4 — holder for semiconductive material
*;f^fft?> *
Fig. 181 — Special prismatic

reflector of optical clear silica glass
Suprasil W [3], designed for the
corner laser reflector placed on the
Moon
Fig. 180 — Ground and polished prisms, cubes and

cylinders of clear silica glass Vitreosil [2]
282
5.4 OPTICAL INDUSTRY
Clear silica glasses are widely used in the optical industry because of their
outstanding physico-chemical properties. It is their high degree of homogeneity,
excellent transmission in virtually all spectral regions of the visible part of the
spectrum, high resistance to thermal shock and other properties (cf. Chapter 4) that
make silica glass irreplaceable by other materials (current types of optical glasses).
Figure 180 shows some shapes of products made of clear silica glass for optical
purposes.
Optical silica glass has therefore found wide application in the design of a number
of demanding instruments, even in cosmic research, for example in the investigation
of the Moon by Soviet scientists or in the construction of the laser reflector installed
by the first man to step on the Moon (cf. Section 5.9); the laser reflector contained
100 pieces of smaller corner reflectors (Fig. 181) made of the Suprasil W type of
optical silica glass.
5.5 GLASS INDUSTRY
In the technological processes, the glass industry uses a number of products

made of opaque silica glass.
This is particularly the case of various melting crucibles and pots (Fig. 182) with
capacities ranging from 0.2 to 300 litres [8], suspended plates (Fig. 183) used in glass-
making tanks, rings for glass melt working, floats, etc.
Tank furnace blocks, rings and floats of opaque silica glass resist contamination
by melted glass owing to their relatively high purity (Si0 2 content higher than
99.6 wt.%) [14]. Opaque silica glass has found its main application in the melting
Fig. 182 — Glassmaking pots made

of Rotosil opaque silica glass [8]
283
of the Simax or Pyrex types of borosilicate glass; excellent results have also been
obtained in the melting of low-alkali glasses, some optical glasses and special glasses
for electronics.
Fig. 183 — Suspension plates of

opaque silica glass for glassmaking
tanks of Quartz et Silice
These are all the so-called acidic glasses with a high content of Si0 2 and B 2 0 3 .
Silica glass is also used as a lining of melting furnace burners, as blocks with
windows for pyrometers, furnace vaults, and the like.
The crystallization of silica glass, which takes place at high temperatures, is made
use of in its application as a building material for melting furnaces. In this way, it is
possible to increase significantly its resistance to deformation at high temperatures.
On long-term heating, opaque silica glass begins to crystallize at temperatures above
1150 °C. After a certain time, the amorphous phase is converted to crystalline high-
temperature α-cristobalite throughout the entire ware volume, and the phase trans
formation does not involve any distinct changes in volume [14].
While tank blocks of opaque silica glass already tend to deform under mild loading
at about 1400 °C, the softening temperature increases up to about 1720 °C as a result
of the complete conversion to high-temperature α-cristobalite. The transformation
of silica glass to high-temperature α-cristobalite is therefore of great significance
from the standpoint of resistance of the material to high melting temperatures.
At a temperature of about 1470 °C, high-temperature α-cristobalite is the thermo-
dynamically stable modification of Si0 2 .
To ensure long life of the furnace blocks, the product should be allowed to crys
tallize throughout its volume. This is why new glass furnaces with silica glass blocks
should be tempered for 10-14 days at temperatures of about 1500-1600 °C. Only
then can the tank be put into operation. Crystallization of the blocks throughout
their volume is ensured by providing adequate thermal insulation of the furnace.
The crystallized blocks can be both cooled and heated, but their temperature must
not decrease below 272 °C. At this temperature, the high-temperature a-cristobalite
converts to low-temperature β-cristobalite, and the large changes in volume lead
to cracking of the blocks.
284
5.6 CHEMICAL INDUSTRY AND INSTRUMENTS
Silica glass is an irreplaceable material in the manufacture of instruments

and apparatus employed in chemical research and production.
A number of chemical technologies, particularly those processing various corrosive
substances such as mineral acids, and especially at high temperatures, would not be
possible without reacting vessels and equipment made of silica glass. The excellent
chemical durability of silica glass is the primary reason for its application in the
production of pure or high-purity chemical substances. Its outstanding resistance
to thermal shocks makes it possible to apply this material whenever chemical re
actions and processes have to be carried out at high temperatures and the reaction
products be then rapidly cooled. Silica glass also permits the reaction vessels to be
heated directly with gas burners or superheated steam or liquids [9, 11, 14]. It is
likewise possible to fuse together clear and opaque silica glass in sealing various
viewing windows of clear silica glass into vessels of opaque silica glass (Fig. 184).
Fig. 184 - Apparatus for the reclaiming of selenium from solutions of acids in reaction vessels
of opaque silica glass. The inspection windows are made of clear silica glass
285
Piping and tubing of both opaque and clear silica glass are significant elements
in the design of industrial and pilot-scale plant, as well as laboratory equipment
(Figs 185 and 186).
Piping and tubing of clear (Fig. 187) and opaque (Fig. 188) silica glass can be
worked in the flame of burners, mostly of the oxygen-hydrogen type.
In addition to welding, joining of piping and tubing can also be done mechanically,
as shown in Fig. 189. Industrial apparatus of extremely high complexity can thus
be constructed.
Opaque silica glass is used in the construction of apparatus for the evaporation
and drying of solutions of various salts in chemical factories, as well as in laboratories
(Fig. 190).
286
Laboratory flasks and other small laboratory vessels, dishes and crucibles of clear
silica glass have found wide application in chemical laboratories (Fig. 191).
Fig. 187 — Blowpipe forming of clear silica

glass pipes [18]
Fig. 188 — Manufacture of

a heat exchanger of Vitreosil
opaque silica glass for service
with corrosive media [16]
287
Clear silica glass is also used in the design of various instruments, because of its
advantageous physico-chemical properties. Figure 192 shows a special laser made
of clear silica glass.
Fig. 189 — Flanges on pipes of opaque

silica glass and metallic couplings [8]
Fig. 190 — Surface

evaporators of opaque silica
glass [8]
288
Fibres of clear silica glass formed into a spiral helix are almost free of elastic
recovery. Such springs are advantageously used as suspensions of the so-called
quartz balances, as shown in Fig. 193.
Fig. 191 — Laboratory ware of clear and opaque silica glass made by Quartz et Silice [15]
Clear silica glass fibre is manufactured in diameters from 1 to 15 μιη [14]. It is

supplied either in the form of free filaments, or in the form of felt or mats (Fig. 194).
It is used as thermal insulation for high temperatures, in thermally stressed fil
tration apparatus, as reinforcement for plastics, and as reinforcement for thermal
shields of space ships.
289
Fig. 192 — Special laser of clear silica glass [20]
Fig. 193 - Spiral coil

of clear silica glass
Fig. 194 — Mat of clear silica glass fibres
290
5.7 METALLURGY
In metallurgy, silica glass is used particularly in the form of various crucibles
and dishes for melting special metal alloys.
The properties appreciated in these applications are the resistance to thermal
shocks, chemical durability, and others. In some cases, advantageous use can be
Fig. 195 - Pouring molten brass into a Vycor glass

crucible [21]
High-temperature vacuum furnaces for melting special metals and alloys [8]
291
made of the transparency of crucibles and dishes to check the course of the melting
and the casting of metals and alloys.
Figure 195 shows the pouring of molten brass into a crucible of Vycor type glass
(96 wt.% Si0 2 ).
Cylinders of opaque silica glass are used as protective tubes during induction
melting of metals and alloys under reduced pressure or in a controlled protective
atmosphere (Fig. 196).
Opaque silica glass is likewise employed in the constructions of plant for the
degassing or distillation and sublimation of metals.
12 3 4 5 6 7 8 9
Fig. 198 — Schematic diagram of the measuring

head of the TSO-3 Universal thermoprob'e:
/ — paper cartridge; 2 — metallic cartridge;
3 — PtRh 10 thermocouple in a clear silica glass
tube; 4 — concentration cell; 5 — metallic element
coming into contact with the melt; 6 - insulating
ceramic material; 7 - polythene head; 8 - ceramic
sheath of the paper cartridge; 9 - paper cartridge
Fig. 197 — Poldi thermoprobes. designed for measuring temperature and determining free
oxygen in a molten metal or alloy [22]
Metallurgical production is at present undergoing far-reaching fundamental

changes [22]. New progressive elements of measuring technology are increasingly
used to control the manufacturing process precisely.
As the sole manufacturer in Czechoslovakia in 1967, the Poldi Steelworks intro
duced the manufacture of thermal probes. More than 6 million of these probes are
now manufactured annually (Fig. 197).
These probes are used to measure the temperature of molten metals, e.g. in open-
hearth furnaces, electric arc furnaces, converters, casting ladles, etc. The main com
ponent of the thermal probe (Fig. 198) is a thermocouple placed in a protective tube
of clear silica glass.
The Poldi TSO-3 Universal probe serves to determine the content of free oxygen
while simultaneously measuring the temperature of metals or alloys.
292
5.8 ELECTRICAL ENGINEERING, ELECTRONICS
AND COMMUNICATION TECHNOLOGY
The present electronics and electrical engineering technology demands

high-quality electrically insulating materials [14] with superior electrical, thermal,
mechanical, optical and other properties. Most electrically insulating materials meet
only some of these requirements, while silica glass is one of the few materials satisfying
most of them. It has high dielectric strength, low electrical conductance even at
elevated temperatures, minimum dielectric losses, a comparatively high softening
point, high resistance to thermal shock and very satisfactory chemical durability
(cf. Chapter 4). For these reasons, opaque silica glass is used to manufacture electrical
insulators for Lodge-Contrellove, Luigi and other electrostatic separators [14]
which find application in the chemical and metallurgical industries. These insulators
operate under extremely difficult conditions (working voltage up to 70 000 V, tem
perature 500-600 °C, in a medium of chemically corrosive gases, vapours and dust
particles).
High-voltage insulators of silica glass are currently used in the manufacture of
various fuses, lightning arresters, switches, distributors, etc. Silica glass is further
used as the material for various bushings, particularly high-voltage, bushings for the
Fig. 199 — Optical waveguides can

be used for a large number of
simultaneous phone calls; the
Siemens cable with eight waveguides
can simultaneously transmit up to
30 000 phone calls
293
frames of self-induction coils, sockets and panels for cathode ray tubes, insulating
elements for precise measuring instruments, in the design of special electron valves,
in vacuum technology, in the construction of gas lasers, etc.
Silica glass constitutes the material of various structural elements for high-fre
quency transmitting electron tubes, such as tubular pieces for insulating flexibly
mounted cathodes and holders for fitting the cathodic spring and anodic grid.
Current products of vacuum electronics and low-pressure and high-pressure mercury
and halogen discharge lamps, have already been described in Section 5.2.
Fig. 200 — Optical waveguide connectors by Socapex, a branch of Thomson-CSF
Clear silica glass is also used in the manufacture of bulbs for high-pressure xenon
discharge lamps with an output of up to 6500 W [14] and a life of up to 1200 hours.
Tungsten lamps with windows of clear silica glass (the window sealing carried out
by means of intermediate glasses) [10, 24] find application as photometric standards
or as comparison lamps for spectroscopy, photometry, polarimetry, pyrometry, etc.
Atomic absorption spectrophotometry makes use of lamps with a hollow cathode
and a window of clear silica glass.
294
Electronics has been called the nervous system of modern society [26]. It transmits
news, enriches the cultural life, is a source of progress in computer and automation
technology, and an effective tool in the development of all fields of science. A con
tinuous and intensive flow of new findings in microelectronics, optoelectronics and
quantum electronics are the decisive factors ensuring penetration of electronics into
all spheres of human life.
Rapid development in one of the fields of telecommunication technology has been
made possible by technological advances in the manufacture of clear silica glass
fibres for the transmission of optical signals. The future in this field belongs to optical
systems with light conducting cables. High-purity silica glass plays the main role
in the manufacture of these cables [25].
Some examples of optical conductors are shown in Figs 199 and 200.
5.9 ASTRONOMY AND SPACE RESEARCH
Because of its very low thermal expansion, silica glass is used in the con
struction of large astronomical telescopes (Fig. 201).
Such telescopes will also be placed in space.
Both clear and opaque silica glasses are used in the construction of spaceships
and satellites. Optical silica glass has been used in the construction of the so-called
reflector placed on the surface of the Moon within the framework of the Apollo
program (Fig. 202).
Fig. 201 - NASA telescope 2.4 m in diameter (to be placed in cosmos).

It is made of clear silica glass with an addition of Ti. Product of Corning Glass Works.
295
A high-output ruby laser placed on Earth irradiated a circular area of the Moon
about 12 km in diameter. Although only 0.2 of the 1019 photon pulses transmitted
from the Earth was received back, the distance between the Earth and the Moon
was measured with an accuracy of ± 15 cm.
Fig. 202 — Laser reflector containing

100 corner reflectors of Suprasil W glass [3]
A similar laser reflector was used within the framework of cooperation between
Soviet and French scientists, as well as in the Lunokhod I and Lunokhod II projects
(cf. Fig. 167).
Silica glass has become a significant structural material in the construction of
spaceships [30]. The Corning Glass Works has developed eleven various sizes and
shapes of windows for manned spaceships (Fig. 203).
296
In the case of the space shuttle, visibility is ensured by six frontal windows, two
ceiling windows and two windows into the payload space. Each of the six frontal
windows consists of three separate plates (panes) of glass (Fig. 204). The outer and
inner plates are made of clear silica glass, the middle plate of aluminosilicate glass.
Fig. 203 — Special windows

of clear silica glass in the
Columbia space shuttle made
by Corning Glass Works [31]
W ' Wi0**,
Fig. 204 - Schematic diagram of the triple glazing of the

Columbia space shuttle [30]: 1 — outer pane; 2 — middle
pane; 3 — inner pane; 4 — outer jacket of the shuttle;
5 — the crew module
Fig. 205 - Shaped insulating tiles protecting the outer shuttle skin
297
The outer plates are designed to resist the high temperatures during re-entry into
the Earth's atmosphere. Their diagonal dimension is 106.7 cm and their thickness
1.5 cm. The middle plate (the so-called high-pressure plate) is made of toughened
glass 3.3 cm in thickness. Its outer surface is provided with a coating reflecting
infrared radiation, but it transmits radiation in the visible part of the spectrum. To
improve visibility, the internal surface is provided with an antireflective layer.
Fig. 206 — The Soyuz 3 spaceship on the Baykonur cosmodrome [33]
298
More than 70% of the surface of the Columbia space shuttle [203] is covered by
about 34 000 insulating lining tiles of silica glass (Fig. 205). These plates are further
provided with a lining of special silica glass. The insulating tiles, made by sintering
silica glass fibres, should resist temperatures of up to 1260 °C during 100 flights,
and are the key material for successful application of the space shuttle. The surface
glaze, 0.38 mm in thickness, improves the thermal properties of the insulating plates
which are otherwise porous. Each plate is shaped so as to fit the curved surface of
the shuttle.
Up to 1988, the USSR had launched more than 2000 space objects, instruments
and ships, in which silica glass found a wide field of successful applications (special
windows, optical systems, cover sheets on solar cells, in electronic systems, etc.).
Figure 206 shows the pre-launch preparations of a spaceship at Baykonur [33].
REFERENCES
[1] MISKARIK, S.: Modern! zdroje svetla (Modern Sources of Light). SNTL, Prague, 1979
[2] ANON.: About Vitreosil Pure Fused Quartz and Silica. The Thermal Syndicate Ltd., Great Britain,
June, 1958
[3] ANON.: Quarzglas für die Optik. Heraeus Quarzschmelze GmbH, Prospectus No. Q —B 1/112,
Hanau, 1979
[4] PEROV, V.D. — STACHEYEV, Yu.L: Kosmicheskie apparaty issleduyut Lunu (Cosmic Apparatus
Investigates the Moon). Znaniye, Moscow, 1979
[5] ANON. : Vysokotlake rtutove vybojky (High-Pressure Mercury Discharge Lamps Tesla). Prospectus,
Kovo, Prague, 1969
[6] ANON.: High-Pressure Discharge Lamps, Halogen Light Bulbs. Prospectus, Kovo, Prague, 1979
[7] ANON. : Quarzglas für die Halbleitertechnik. Heraeus Quarzschmelze. Prospectus QB 3/113. Hanau,
1979
[8] ANON.: Undurchsichtiges Quarzgut Rotosil. Heraeus Quarzschmelze GmbH, Prospectus No.
Q - C l / 1 1 2 , Hanau, 1974
[9] MOHN, H.: Quarzglas und Quarzgut im Laboratorium und in der Technik. 25 Jahre Hochvakuum
technik. W.C. Heraeus GmbH, Hanau, 1961
[10] CECH, B. - BROUKAL, J. - HOVORKA, O. - MALINSKY, I.: Vysokoteplotni materialy (High-Tem-
perature Materials). SNTL, Prague, 1966
[11] ANON.: 60 Jahre Quarzglas. 25 Jahre Hochvakuumtechnik. W.C. Heraeus GmbH, Hanau, 1961
[12] FRG Patent No. 1696061
[13] ANON.: Blocs refractaires en silice pure fondue opaque. No. 82-3 A. Quartz et Silice, Paris, 1967
[14] BOREC, T.: Tavene horniny — taveny kremen (Fused Rocks — Fused Quartz). Alfa, Bratislava,
1970
[15] ANON.: Verrerie de laboratoire en silice pure fondue. Catalogue Quartz et Silice, Paris, 1955
[16] ANON.: Vitreous Silica. Catalogue of Thermal Syndicate Ltd., Wallsend, Northumberland, 1980
[17] ANON.: Quarzglasrohre. Prospectus Q —B2/112 by Heraeus, Hanau, 1979
[18] ANON.: Prospectus of VEB Quarzglasgeräte. Quarzschmelze Staaken, Berlin, GDR, 1957
[19] ANON.: Vitreosil, Pure Vitreous Silica. Laboratory Ware. Catalogue of Thermal Syndicate Ltd.,
Wallsend, 1967
[20] ANON. : Ressorts en silice pure fondue transparente. Prospectus SI-IB of Quartz et Silice, Paris, 1967
[21] ANON.: Properties of Glasses and Glass-Ceramics. Corning Glass Works, Corning, N.Y., 1973
299
[22] ANON.: Poldi Thermoprobes. Catalogue of Poldi-Steelworks, National Corporation, Kladno, 1977
[23] ANON.: Hanauer Quarzglasoptik auf dem Mond. Prospectus of Heraeus, Hanau, 1969
[24] BROUKAL, J.: Informativni pfehled SVUS, Hradec Krälove, X (1967) 3
[25] BEALES, K.J. - DAY, C.R.: Phys. Chem. Glasses, 21 (1980), 1, p. 5-20
[26] ZiMA, V.: Slahoproudy Obz., 39 (1978), 11
[27] ANON. : Composants pour liasons par fibres optiques. Prospectus of Socapex, Suresnes-Cedex,
Paris, 1979
[28] ANON.: Corguide Optical Fibres. Prospectus Telecommunication, Products Dep. Corning G.W.,
New York, 1977
[29] ANON.: Coming Products News (1979) 2
[30] ANON. : Glass 54 (1977) 9, p. 372
[31] ANON.: Prospectus of Corning Glass Works, Corning, N.Y., 1978
[32] ANON.: Am. Glass Rev. (1976) 5, p. 12
[33] CHERNYSHOV, M.: Orbitami Gagarina (On Gagarin's Orbits). Press Agency Novosti, Moscow, 1981
APPENDIX TO REFERENCES
[1] ZLJTHER, G.: Phys. Status Solidi, 59 (1980), 1, p. K 109-113
[2] THOMSON, E.R. — BACON, J.F.: Aluminium-oxidfaserneerverstärktes Kieselslas als möslicher Werk
stoff für Radarnasen. Symp. Electromagnetic Windows, 14th, Atlanta, Ga., VI. 21-23, 1978
[3] PAPANIKOLAU, E.: J. Non-Cryst. Solids, 38-39 (1980), p. 563-568
[4] BiHUNiAK, P.P.: Dis. trav. Alfred Univ., New York, 1979, n. 7926489, p. 156
[5] BREBEC, G.'.Acta Metall., 28 (1980), 3, p. 327-333
[6] NUCHO, R.N. - MADHLJKAP, A.: Phys. Rev. B, 21 (1980), 4, p. 1576-1588
[7] LDCOVSKY, G.: Phil. Mas. B., 41 (1980), 4, p. 457-467
[8] LUCOVSKY, G.: J. Non-Cryst. Solids, 35-36 (1980), II, p. 825-830
[9 I EicKEMEiER, J.: Silikatieclmik, 32 (1981), 7, p. 221
[ 10] BODEN, G.: XHIth Conf. on Silicate Industry and Silicate Science, Budapest, 1-5 June 1981, Sect. 1,
p. 22-25
[11] ENGELKE, R.: Phys. Solid A, 65 (1981), 1, p. 271-280
[12] DAYSH, F.: Br. Soc. Scient. Glasshl. J., 20 (1982), 2, p. 27-29
[13] BODEN, G. - RICHTER, E.: Silikattechnik, 33 (1982), 11, p. 346-349
[14] SHYB, E.I.: Soviet J. Glass Phys. Chem., 8 (1982), 4, p. 335-340
[15] CHOTIMTCHENKO, V.S. - VASILOI, JU.V.: Stek/o Keram., (1983), 6, p. 13-14
[16] WRIGHT, F.E.: Fusion, 30 (1983), 1, p. 6
[17] MACK, G.X. - ANDERSON, A.C.: Phys. Rev. £, Condensed Mat., 31 (1985), 2, p. 1102-1106
[18] PARICKII, V. Ν.: Stek/o Keram., (1986), 4, p. 8
[19] PAVLAS, P.: Silikaty, 30 (1986), 2, p. 169-188
[20] RUTHERIORD, J.: Br. Scient. Glasshl. J., 24 (1986), 3, p. 67-75
[21] SILINJ, H.R.: XVth Intern. Congress on Glass, Leningrad, 1989, vol. la, p. 234-239
[22] COCITO, G.: CSELJ leclm. Rep., 14, 2, p. 99-101
[23] CASTANO, V.M. - TAKAMORI, J..J. Am. Ceram. Soc, 70 (1987), 4, p. 77-78
[24] DAY, Gu.Zh.: A Study on strengthened quartz in glass. XVth Intern. Congress on Glass, Leningrad
1989, vol. 2a, p. 281-286
[25] BIHUNIAK, P.P. — JAIN, V.: Steady state ionic conduction in doped fused silica. XVth Intern. Con
gress on Glass, Leningrad 1989, vol. 2a, p. 249-252
[26] KINSER, D.L. - QUARLES, R.A.: Radiation induced charge storage in Si0 2 . XVth Intern. Congress
on Glass, Leningrad 1989, vol. la, p. 233.
300
SUBJECT INDEX
Absorption of radiation, 249 Chlorite, 138, 140

Absorption spectrometry, 70 Chromite, 55
Actinolite, 137, 140 Coesite, 17
Albite, 55, 79 Condensed phase, 17
Alkalis, liberation of, 136, 137 Constant,
Alamandine, 55 equilibrium, 41
Amphibol, 55 Madelung's, 21
Analysis, photoelasticity, 266
acoustic, 116, 135 Coordination number, 22, 23
chemical, 6 9 - 7 8 Corundum, 55
mineralogical, 79 Covalence radii, 24
sieve, 80 oc-Cristobalite, high temperature, 17, 33
Ankerite, 137, 140 ß-Cristobalite, low temperature, 17, 33
Anorthite, 55 Crucibles, 279
Apatite, 55, 137, 140 Crushing the quartz, 154
Apparatus, Crystallization, 232
chemical, 273
water distilling, 281 Decomposition vessel, 70
Apparent density, 64, 66 Decrepitation, 116, 136
Atmosphere, furnace, 141 Delay lines, 273
Atom, Density characteristics, 63
oxygen, 19 Deposits,
silicon, 20 quartz sand, 55
vein quartz, 47
Baryte, 55 Dewatering, 154
Biotite, 55, 138, 140 Diaspor, 55
Bond, Differential thermal anlysis, 90
covalent, 20, 24 Dispersion,
ionic, 20, 21 anomalous, 246
siloxan, 29 mean, 248
Brown coal, 55 partial, 248
radiation, 245
Calcination, 156 Disthene, 55
Calcite, 138, 140 Distribution of impurities, 80
Capilaries, 286 Drying, 154
Centrifuging methods, 50 Durability,
Chemical analysis, 69 to acids, 201
Chemical apparatus, 273 to alkalies, 202
Chemical properties, 195 to other agents, 203
Electrical disruptive strength, 239 Kaolinite, 55
Electrical properties, 236 Keatite, 17
Electrical resistivity, 237
Electron affinity, 21 Laboratory melts, 91
Electron density, 151 Laboratory ware, 278, 289
Electron envelopes, 22, 23 Laser, 290
Emission spectrometry, 70 Laser reflector, 296
Energy, Leaching of quartz, 157
free, changes in, 41, 43 Lechatelierite, 19
ionic bond, 21 Leucoxene, 138
ionization, 21 Light,
potential, 21 absorption of, 242, 249
Epidote, 55, 138 dispersion of, 245
Evolution of refining methods, reflection of, 242, 243
163 refraction of, 242, 245
scattering of, 242, 261
Fasriges, 19 transmission of, 83, 242
Feldspar, 55, 140 Limonite, 50, 130
Free energy, changes in, 41, 43 Loss factor, 241
Luminescence, 262
Garnet, 138 Lunar vehicle, 274
Glass fibres, 290
Glassmaking pots, 283 Magnetite, 55
Goethite, 140 Mechanical properties, 206
Grain size distribution, 61 Melanophlogopite, 17
Gravimetric thermal analysis, 90 Melting,
Grinding the quartz, 154 atmospheric, 171
electric, 170
Halloysite, 55 gas, 169
Halogenide discharge lamps, 272 plasma, 171
Hardness, 211 vacuum, 171
Heat exchanger, 287 Melting furnace,
Hematite, 138, 140 Fortey, 166
Hybrid orbit, 25 Hänlein, 175
Hybridization, 25-30 Quartz et Silice, 178
Hydrated oxides, 59 Thermal Syndicate, 177
Hydrolysis, Melting process, Bottomley, 166
in aqueous medium, 183, 186 Mercury discharge lamp, 271
in flame, 183, 185 Metastable equilibrium, 86
Method,
Ignition loss, 90 centrifuging, 90
Ilmenite, 55, 138 DTA, 90
Inclusions, flame hydrolysis, 185
gas-liquid, 116 IVPO, 183
liquid, 116 OVPO, 183
Isomorphism, sol gel, 187
heterovalent, 81 thermal oxidation, 184
isovalent, 81 VAD, 183
302
Method VTA, 90 Pyrop, 55
Mineralogical analysis, 79 Pyroxene, 55
Minerals,
accompanying, 137 Quartz,
heavy, 82, 139 a-, 17, 33, 36
hydropergenous, 79 ß-, 17, 33, 36
Model of [SiOJ 4, 17 crystalline modification of, 31
covalent, 24 deposits of, 48
ionic, 21 formation of, 44
Modifications of SiO , 17, 31, 36 phase transformation of, 31
Modulus of elasticity, 206 Quartz raw materials, 44 — 60
Monosilane, 60
Montmorrillonite, 55
Radiators, I. R., 277
Muscovite, 55, 79, 138, 140
Refining, 154
evaluation of, 163
Nepheline, 55 zonal, 281
Reflection of radiation, 243
OH groups, 253 Refraction,
Olivine, 55 of radiation, 245
Opal, 19 optical, 245
Optical emission spectrometry, 70 Relaxation time, 96
Optical properties, 242 Resistance,
Optical waveguides, 293, 294 to aqueous solutions of salts, 199
Overlap degree, 25 to radiation, 264
Overlap integral, 25 to thermal shock, 217
to water, 199
Parameters, structural, 149 Ripidolite, 79
Permeability to gases, 230 Rock crystal, 160
Permittivity, 240 Rods, 286
Phase, Rutile, 55, 138, 140
amorphous, 97—102
condensed, 17 Sand,
transient, 99 clayey, 56
Phase conversion, 145 ferric, 56
Phase transformation, 95 limy, 56
Photoelasticity constant, 266 quartz, 56
Photogoniodiffusiometer, 85 Scattering indicatrix, 84 — 89
Photometry, 70, 73 Scattering of radiation, 261
Pilot plant melting, 91 Semiconductor technology, 278
Poisson's ratio, 206 Seriate, 79
Polarization, Siderite, 138
horizontal, 83, 84 Sieve analysis, 80
of light flux, 83, 84 Silica glass,
vertical, 83, 84 composition of, 196 — 199
Polarizing effect of ions, 21 Corning 7940, 16, 194
Porosity, 67 Corning 7943, 16, 194
Prismatic reflector, 282 Fondal, 196
Pyrite, 55, 138 G. E. 104, 15, 194
Germisil, 16, 194 Space shuttle Columbia, 297
Herasil, 15, 194 Spaceship, 298
Homosil, 15, 194 Specific heat, 224
I. R. Vitreosil, 16, 194 Spectra, EPR, 153
Infralux, 15, 194 Spinel, 55
Infrasil, 15, 194 Spiral coil, 290
KU-1, KU-2, KV, KV-R, 16, 194 Staurolite, 55
M62, M84, 16, 194 Structural parameters, 149
O. G. Vitreosil, 16, 194 Surface tension, 232
O. H. Vitreosil, 16, 194 Suspension plates, 284
OHF, 16, 194
opaque, 166 Telescope, 295
optical, 181 Thermal conductivity, 228
Optosil, 15, 194 Thermal expansion, 37
Pursil 453, 16, 194 Thermal expansivity, 213
Pursil Optique, 15, 194 Thermal properties, 213
Pursil Ultra, 15, 194 Thermoprobes, 292
Ql, 02, Q3, Q4, 16, 194 Topaz, 55
Rotosil, 196 Transformation point, 145
Silquartz, 15, 194 oc-Tridymite, 17
Spectrosil, 16, 194 ß-Tridymite, 17
Suprasil, 16, 194 γ-Tridymite, 17
synthetic, 182 Tubes, 286
Translucent Vitreosil, 196 Turmaline, 55
Trasil, 15, 194
Ultrasil, 16, 194 Vacuum drying chamber, 279
Vycor, 190 Vacuum furnace, 291
Zerosil, 16, 194, Vein quartz, 162
151, 16, 194 Viscosity, 218
Silicic chloride, 59
Silicic fluoride, 59 Zircon, 55
Silicic oxide, 17, 145 Zoisite, 55
304

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GLASS SCIENCE AND TECHNOLOGY

Volume 1. J. Stanek, Electric Melting of Glass

for all remaining areas

Library of Congress Cataloging-in-Publication Data

ISBN 0-444-98755-X (vol. 11)

© SNTL - Publishers of Technical Literature, Prague, 1991

In terms of chemical composition, silica glass is the simplest amorphous substance

Ing. Josef Broukal, CSc,

a activity (fugacity of gases)

a0 lattice constant (nm, μιη)

Silica glass is finding ever-broader fields of application in various branches

2.2 NATURAL RAW MATERIALS

quartz high tempera-| tridymite silica

crystalline fine crystalline amorphous

higMempera- cristobalite tridymite

Group Type Number of shared oxygen atoms

t Fig. 1 — States of electrons in the oxygen atom

Fig. 4 — Energy of the crystalline structure,

where b and q are constants.

s= 1 _ e -' / 4 <* A -* B ) 2 , (5)

where the electronegativities of atoms A and B, respectively.

Fig. 6 — Electron configuration

where iPhybrid is the hybridization wave function,

The sp2 hybridization:

The sp3 hybridization:

A linear combination of one s orbit and three p orbits is capable of creating

Modification Si—O distance Si—O—Si bond angle

Low-temperature 0.1603 + 0.0003 147

High-temperature 0.162 146

Low-temperature 0.162 147

High-temperature 0.154 180

Amorphous Si0 2 0.162 180

Fig. 7 — Schematic diagram of the covalent model of the

2.2.1.3 Characteristics of the Si—O bond

Fig. 8 — Electron density

These values can be calculated from the equation

*AB = rA + rB - βΔχ Α _ Β (8)

where rAB is the interatomic distance between atoms A and B,

Figure 9 shows a phase diagram of the stable modifications of quartz under

Low-temperature ß-quartz and high-temperature en-quartz

The structure of low-temperature /?-quartz, according to Bragg and Gibbs [25],

Fig. II - The structure of high-temperature α-quartz Fig. 12 - The structure of low-temperature

In high-temperature α-quartz, the Si and O atoms are arranged in spatial groups,

Low-temperature ß-cristobalite and high-temperature a-cristobalite

The structural transformation of j8-cristobalite into α-cristobalite and vice-versa

In contrast to this, Barth [32] considers the spatial group T 4 ; P 2 a 3.

Low-temperature y-tridymite, medium-temperature ß-tridymite and high-temperature

The elementary modification of tridymite is the stable form of high-temperature

high-temperature α-tridymite „ medium-temperature

Modification Temperature Form Notes

Crystalline modifications of Si0 2

Low-temperature quartz - 2 7 3 to +573 s atm. pressure

Tridymite S-I - 2 7 3 to +64 m atm. pressure

Tridymite M-I - 2 7 3 to +117 m atm. pressure

Low-temperature cristobalite - 2 7 3 to +272 m atm. pressure

High-temperature cristobalite 1470 to 1723 s atm. pressure

Si0 2 —W (silica W| Monotropic form, chain structure at

Amorphous modifications of Si0 2