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],
is shown in Fig. 11.

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
Supra-piezo-vitreous Si0 2
Compact vitreous Si0 2
Si0 2 —M (silica M)
- 2 7 3 to 1723 m formed by rapid cooling
of liquid Si0 2
m
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
Thermodynamic data on Si0 2 at high temperatures [41]

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
Thermodynamic data on Si0 2 at high temperatures [35]

# 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 ^iil^U^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
State Glass Research Institute,
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)

[1] BRUCKNER, R.: J. Non-Cryst. Solids, 5 (1970), 2, p. 123-175
[2] BLANKENBURG, H. J.: Quarzrohstoffe, VEB Deutscher Verlag für Grundstoffindustrie, Leipzig,
1978
[3] DINGER, K. - JEBSEN-MARDWEDEL, H.: Glastech. Ber. 30 (1957), 7, p. 320
[4] FLÖRKE, O. W.: Fortschr. Mineral., 44 (1967), 2, p. 181
[5] ROST, R. — KOCAR, M.: Atlas nerostü (Mineralogical Atlas), State Pedagogical Publishing
House, Prague, 1964
[6] GAZO, J. et al.: Vseobecnä a anorganicka chemia (General and Inorganic Chemistry), ALFA-
SNTL, Bratislava-Prague, 1974
[7] PAULING, L.: The Nature of the Chemical Bond and the Structure of Molecules and Crystals,
Cornell University Press, Ithaca-New York, 1960
[8] PRYANISHNIKOV, V.P.: Sistema kremnezema (The System of Silicon). Izdatelstvo literatury po
stroyitelstvu, Leningrad, 1971
[9] PAULING, L. - SHERMAN, J. A.: J. Am. Chem. Soc, 59 (1937), 8, p. 1450-1456
[10] BALTA, P. — BALTA, E.: Introduction to the Physical Chemistry of the Vitreous State. Editura
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
[22] BRILL, R. W. - HERMANN, G. - PETERS, C : Die Naturwissenschaften, H 40 (1939), p. 676-677
[23] BRILL, R. W.: Ceram. Age, 61 (1953), 3, p. 31-36
[24] GULUTVIN, Ju. M.: Teploty obrazovanya i tipy chimicheskoy svyazy v neorganicheskich kristallach
(Formation Temperatures and Types of Chemical Bonds in Inorganic Crystals). Izdatelstvo AN
SSSR, Moscow, 1962
[25] BRAGG, W. H. - GIBBS, R. E.: Proc. R. Soc. London, Ser. A, 109 (1925), A 751, p. 405-427
[26] WYCKOFF, R.W.G.: Analytical Expression of the Results of the Theory of Space Groups. Carnegie
Inst. Publ., 318 (1922), p. 104, 105, 144
[27] SINELNIKOV, N.N.: D.A.N. SSSR 106 (1956), 5, p. 870-872
[28] FLÖRKE, O.W.: Ber. Dtsch. Keram. Ges., 12 (1955), p. 369-381
[29] JOHNSON, W. - ANDREWS, K.W.: Trans. Br. Ceram. Soc., 55 (1956), 4, p. 227-236
[30] SINELNIKOV, N.N.: Proc. 5th Congress on Experimental and Technological Mineralogy and
Petrography, 26-31. 3. 1956. Izd. AN SSSR, Moscow, 1958, p. 371-381
[31] MOSESMAN, M.A. - PITZER, K.S.: J. Am. Ceram. Soc, 63 (1941), 9, p. 2348-2356
[32] BARTH, T.F.: Amer. Jour. Sei., 23 (1932), p. 350, Am. J. Sei., 24 (1932), p. 97-110
[33] SCHOENFLIES, A.: Theorie der Kristallstruktur, Borntraeger, Berlin, 1923
[34] International Tables for X-ray Crystallography, Vol. 1, Symmetry Groups. Kynoch Press, Bir­
mingham, 1952
[35] SHICK, H.L.A.: Chem. Rev. 60 (1960), 4, p. 331-362
[36] TOROPOV, N.A. - BARZAKOVSKII, V.P.: Vysokotemperaturnaya chimia silikatnych i drugich
okisnych sistem (High-temperature Chemistry of Silicate and other Oxidic Systems). Izdatelstvo
AN SSSR, Moscow, 1963
[37] TOROPOV, N.A. — BARZANOVSKH, V.P. — BONDAR, I.A. — UUAI ov, Ju.P.: Diagrammy sostoyania
silikatnych system (Diagrams of the Constitution of Silicate Systems). Spi-avucluiik T 2L, Nauka,
Moscow, 1970
[38[ BEZBORODOV, M.A. - PRYANISHNIKOV, V.P.: Opt.-Mekh. Prom., 36 (1934), 7, p. 3-8
[39] BREWER, L. - MASTICK, D.: J. Chem. Phys., 19 (1951), 7, p. 834-843
[40] PORTER, R.F. - CHUPKA, W.A. - INGRAM, M.C.: J. Chem. Phys., 23 (1955), 1, p. 216-217
[41] BERGMAN, G.A. - MEDVEDEV, V.A.: Tr. Gos. Inst. Prikl. Khim., 42 (1959), p. 158-172
[42] BREWER, L. - ROSENBLATT, G.: Chem. Rev., 61 (1961), 3, p. 257-263
[43] BORISOV, V.P. - YUDIN, B.F.: Ogneupory (1968), 3, p. 3 7 ^ 0
[44] FANDERLIK, L : Opticke vlastnosti skel (Optical Properties of Glasses) SNTL, Prague, 1979
[45] VOLKENSTEIN, M.V.: Struktura a fyzikalni vlastnosti molekul (The Structure and Physical Pro­
perties of Molecules) NCSAV, Prague, 1962
[46] LAKATOS, B. - BOHUS, J. - MEDGYESI, G.J.: Acta Chim. Acad. Sei. Hung., 20 (1959), 1, p. 2-52
[47] JATKAR, K. - JYENGAR, B.: Indian J. Phys., 23 (1949), 4, p. 145-152
[48] BERNAL, J.D.: Discuss. Faraday Soc. (1936), p. 27, Nature (London) 183 (1959), p. 141-147
[49] FANDERLIK, M.: Struktura skel (The Structure of Glasses) SNTL-ALFA, Prague-Bratislava, 1971
[50] RUFF, O. - KONSCHAK, M.: Elektrochem., 32 (1926), 11, p. 515-525
[51] GERCBERG, G.: Kolebatelnye i vrashchatelnye spektry mnogoatomnych molekul (Vibration and
Rotation Spectra of Multiatomic Molecules), Izdat. inostrann. liter., Moscow, 1949
[52] GELD, P.V. — ESIN, O.A.: Processy vysokotemperaturnogo vosstanovlenia (Processes of High-
Temperature Recovery). Metallurgizdat, Sverdlovsk, 1957
[53] WYCKOFF, R.W.G.: Am. J. Sei., 11, (1926), 62, p. 101-112
[54] WYCKOFF, R.W.G.: Am. J. Sei., 9 (1925), 54, p. 448-459
[55] GIBBS, R.E.: Proc. R. Soc. London, 113 (1926), 764, p. 351-368
[56] KOTSMID, F.: Suroviny (Raw Materials) SNTL, Prague, 1974
[57] GOSSINK, R.G.: Proc. Xlth International Congress on Glass, Prague 1977, I, p. 114-157

92
[58] PRYANISHNIKOV, V.P. - KOZLOVA, L.N. - GORBACHEV, V.V. - BYKOV, V.l.: Fiz. ichim. steklal
(1976), 5, p. 466-470
[59] DISLICH, H.: Glastech. Bei:, 44 (1971), 1, p. 1-8
[60] Mc CARTHY, G.J. - ROY, R. - M C K A Y , J. M.: J. Am. Ceram. Soc, 54 (1971), 12, p. 637-638
[61] HETHERINGTON, G. — BELL, L.W.: Ultrapurity, Methods and Techniques. M. Dekker Inc., New
York 1972
[62] Glass Fibre for Optical Communications — A selection of papers presented at the Society's collo­
quium on optical fibres held in Imperial College, London 1979, In: Phys. Chem. Glasses 21 (1980),
l , p . 1-66
[63] ACHENER, M. - HABERT, M.: Fibre optiques, 56 (1976), 12, p. 603-605
[64] AUDSLEY, A. - BAYLISS, R.K.: J. Appl. Chem., 19, (1969), p. 33-38
[65] GLIEMEROTH, G. - KRAUSE, P. - NEUROTH, N . : Schott Inf. (1976), 2
[66] KÜPPERS, D. - KOENINGS, J. - WILSON, H.: J. Electrochem. Soc, 123 (1976), 7, p. 1079-1083
[67] HAMILTON, D.L. - HENDERSON, C.M.B.: Mineral Mag., 36 (1968), p. 832-838
[68] FLÖRKE, O.W.: Chem. Erde, 22 (1962), p. 91-110
[69] FLÖRKE, O.W.: Ber. Dtsch. Keram. Ges. (1955a), p. 369-381
[70] TRÖGER, W.E.: Optische Bestimmung der gesteinsbildenden Minerale. Teil 2 — Textband. Nagele
und Obermiller, Stuttgart, 1969
[71] WILSON, M.J. - RÜSSEL, J.D. - TAIT, J.M.: Contrib. Mineral. Petrol., 47 (1974), p. 1-6
[72] TRKAL, V.: Stavba atomü a molekul (The Constitution of Atoms and Molecules), SNTL, Prague,
1968
[73] REMY, H.: Anorganicka chemie (Inorganic Chemistry), SNTL, Prague, 1962
[74] VERTUSHKOV, G.N. - EMLIN, E.F. - SINKEVICH, G.A. - SOKOLOV, J.A. - JAKSHIN, V.l.: Trudy
Sverdlovskogo gornogo instituta, Vol. 58, Sverdlovsk, 1969
[75] KASPAR, J. - PRISTOUPIL, V.: Nerostne suroviny (Mineral Raw Materials) SNTL, Prague, 1954
[76] ZORKOVSKY, V. et al.: Loziskä nerastnych surovin a ich vyhledävanie (Deposits of Mineral Raw
Materials and their Surveying), Alfa, Bratislava, 1972
[77] KLEISL, J. et al.: Proc. VHIth Conference on Dressing, CSVTS, Ostrava 1968
[78] POLAK, A.: Nerudne nerostne suroviny (Non-Ore Mineral Raw Materials), SNTL, Prague, 1972
[79] FRANCE, J.: Geolog, pruzkum, XIX (1977), 3, p. 65-68
[80] GRECULA, P.: Geolog, prüzkum, IX (1967), 2, p. 4 7 ^ 9
[81] GRECULA, P.: Mineral. Slovaca, I (1969), 2, p. 102-118
[82] MALIS, E. - PAVLIK, J.: Collected papers, Geological Survey, Sbornik geologickeho prüzkumu,
Ostrava (1974), 6, p. 129-138
[83] URBAN, K.: Quartz and Quartzites. In: J. Slävik et al.: Nerastne suroviny Slovenska (Mineral Raw
Materials in Slovakia). Aktuality Geologickeho prüzkumu, Bratislava, 1967 (p. 290-293)
[84] BERNARD, J.H. et al.: Mineralogie Ceskoslovenska (Mineralogy of Czechoslovakia), Academia,
Prague, 1969
[85] DRNZIKOVA, L.: Miner. Slovaca, I (1969), 2, p. 119-134
[86] MIROCHNIKOV, I.I. - KOVALENKO, V.P. - AVAKOV, K.R.: Steklo Keram., (1973), 5, p. 5-7
[87] KAC, H J . : Novye metody issledovanya mineralov v gravitacionnom pole (New Methods of
Investigating Minerals in a Gravity Field). Nauka, Moscow, 1968
[88] REVNIVCEV, V.l.: Obogashchenie polevych shpatov i kvarca (Enrichment of Feldspars and Quartz).
Nedra, Moscow, 1970
[89] PETRÄNEK, J.: Vest. (JUG, XXX (1955), 6, p. 253-271
[90 J HUML, F. - HRDINA, M.: Geol. pruzkum, IX (1967), 9, p. 312-314
[91] HUML, F. - BRANT, J. - HRDINA, M.: Sb. Geol. Ved, Technol. Geochem., (1969), 9, p. 85-104
[92] MIROCHNIKOV, I.I.: Izv. VUZ, Geol. i razvedka (1964), 10, p. 84-88
[93] SHCHEKOLDIN, A.A. - SINKEVICH, G.A. - PETROV, N.A.: Steklo Keram., 20 (1963), 11, p. 6-8

93
 [94] DANA, J.D. — DANA, E.S. — FRONDEL, C : Sistema mineralogii (The System of Mineralogy),
Vol. Ill, Silicate Minerals, Mir, Moscow, 1966
[95] JERABEK, J.: Nerostne suroviny, (1978), 3, p. 89-111
[96] VERTUSHKOV, G.N. — AVDONIN, V.N.: Kratkoe rukavodstvo i tablici dlya opredelenya mineralov
(Comprehensive Handbook and Tables for the Determination of Minerals). Sverdlov. gornyi
institut, Sverdlovsk, 1967
[97] KOSTYLEVA, E.E.: Nekotorye metody izuchenia rudonosnogo kvarca (An Investigation of Ore-
Bearing Quartz). Nauka, Moscow, 1964
[98] JERABEK, J. — HUML, F.: Moznosti upravy kfemene (Dressing of Quartz). UNS, Kutnä Hora, 1977
[99] RUMYANCEV, V.N.: Zapiski VMO, 108 (1979), p. 647-657
[100] DENNEN, W.H. - BLACKBURN, W.H. - QUESADA, A.: Contrib. Mineral. Petrol., 27 (1970), p. 53-62
[101] FANDERLIK, I.: Inform, prehled SVUS, Hradec Kralove (1975), 2
[102] PROD'HOMME, L.: Revue d'Opti., 45 (1966), 4, p. 163-176
[103] ESKIN, V.E.: Rasseyanye sveta rastvorami polimerov (Scattering of Light by Solutions of Polymers).
Nauka, Moscow, 1973
[104] DUBSKY, F.: Sklär a Keram., 26 (1976), 3, p. 68-72
[105] RAYLEIGH, J.W.: On the Electromagnetic Theory of Light. Univ. Press, Cambridge, 1899
[106] TYNDALL, J.: Philos. Mag., 37 (1869), p. 384-392
[107] Mm, G.: Ann. Phys. N.Y., 25 (1908), p. 377-381
[108] GANS, R.: Ann. Phys. N.Y., 79 (1926), p. 204-209
[109] FANDERLIK, I. - DUBSKY, F.: Sb. Geol. Ved, Technol. Geochem., 17 (1981), p. 127-138
[110] MARIAN, H.: Quarzmehl für technische Spezialgläser. Schott. Inf. 3/1976

94