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The application of supercritical drying in the synthesis of silica-based

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Article in Russian Journal of Physical Chemistry B · December 2015

DOI: 10.1134/S1990793114070112

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ISSN 19907931, Russian Journal of Physical Chemistry B, 2014, Vol. 8, No. 7, pp. 44–52. © Pleiades Publishing, Ltd., 2014
Original Russian Text © A.I. Puzynin, 2014, published in Sverkhkriticheskie Flyuidy: Teoriya i Praktika, 2014, Vol. 8, No. 3, pp. 25–36.

The Application of Supercritical Drying in the Synthesis

of SilicaBased Materials
A. I. Puzynin
Joint Institute for Nuclear Research, Dubna, Russia
email: apuzynin@jinr.ru
Received August 20, 2012

Abstract—The supercritical drying technology applied in the synthesis of materials based on pure silica, such
as aerogel, mesoporous silica glass, optical quartz glass, and noble opal is described. The parameters of super
critical drying for the case of silica material synthesis in ethanol and methanol are optimized.

Keywords: supercritical drying, autoclave, aerogel, mesoporous silica glass, optical quartz glass, synthetic opal
DOI: 10.1134/S1990793114070112

INTRODUCTION opal material (depending on the size of the spherical

particles forming the given material and the type of
The materials based on pure silica continue to find their densest packing). During the drying of these
new fields of application both in science and industry. materials, the capillary pressure of liquid P appears in
The aerogels based on silica are used in highenergy their pores under standard conditions, which is
physics as the radiators of Cherenkov charged particle described by Laplacian equation:
detectors. Mesoporous silica glass can be used for the
production of membranes, in chromatography, and for 2σ
P =  cos θ, (1)
the production of object glasses in UV microscopy. r
The optical quartz glass is widely used in various
instruments (cells, lenses in UV spectrometry, defense where r is the capillary (pore) radius, σ is the interface
coatings of intense light sources, astronomical optics, tension, and θ is the contact angle.
and others). Synthetic noble opal represents a valuable In Table 1, the capillary pressures that were esti
raw material for jewelry. mated by Eq. (1), which appear in silica pores with the
During the production of silicabased porous average effective diameter of ~45 nm [1] at their drying
materials, various methods for molding the final arti under standard conditions, are given as an example for
cles can be used. Aerogels and mesoporous silica glass water, methanol, and ethanol.
are obtained with the use of solgel synthesis. In this Because the porosities of the described silicabased
case, the aggregation of silica sol particles is per materials are large (80–95% for alcogels and ~30% for
formed, which are preliminarily molded to the forms precipitated opal material), during their drying under
of the required size; as a result, the spatial structures standard conditions, the internal stresses caused by
which comprise the bonded SiO2 particles are formed high capillary pressure in pores are inevitably realized
in them. The pores of these structures are filled by liq as a crack network. The lower the pores and higher the
uid, water (in hydrogels) or alcohol (in alcogels); at the
synthesis of alcogels, lower alcohols are used most
often, namely, methanol and ethanol. Contact angles of quartz glass θ, surface tension at the air
boundary σ, and capillary pressure P appearing in silica gel
During the synthesis of optical quartz glass from pores with the mean effective diameter ~45 nm for water,
silica sol particles, centrifugation is used to mold arti methanol, and ethanol
cles; in the production of noble opal, spontaneous
sedimentation of sols under the action of gravity force Liquid θ, deg* σ, mN/m [2] P, MPa
is used.
Water 47 71.7 ~4.3
The general necessary subsequent step for all these
processes of synthesis is the removal of the liquid from Methanol 24 22 ~1.8
the pores of molded materials, that is, their drying. 22.1
Ethanol 28 ~1.7
The principal difficulty of this step is that intrinsic
pore sizes of dried materials are relatively small, 10– * The data were obtained on the EasyDrop instrument that mea
100 nm in silica gels and 150–250 nm in precipitated sures contact angle (Kruss manufacturer).

44
 THE APPLICATION OF SUPERCRITICAL DRYING IN THE SYNTHESIS
porosity of the material the denser the cracks appear
ing in it; this process will develop up to the complete
destruction of the sample. The cracks also appear
along entire porous materials when drying is per
formed for a long time, limiting the surface area of
vaporization of the liquid.
With the aim to eliminate the appearance of cracks
during the drying of alcogels based on silica, S. Kistler
developed and used for the first time the method of
supercritical drying in the 1930s [3]. The alcogel sam
ples were placed in an autoclave, where supercritical
temperature and pressure were achieved for the alco
hol gels in the pores by heating, and, then, the liquid
vapors were removed from the autoclave. As a result,
alcohol in alcogel vapors was replaced by air and alco
gels converted to aerogels. During supercritical dry
ing, no internal stresses caused by the capillary pres
sure of the liquid in the pores appeared in the alcogels
and, consequently, the cracks did not appear in the
samples. This method of drying of alcogels with vari
ous modifications is recently used in the production of
aerogels.
The author of article optimized the mode of super
critical drying, which is used for the synthesis of aero
gels based on silica and mesoporous silica glass, and
also used this method for the first time in the devel
oped laboratory method of the production of optical
quartz glass and the synthesis of noble opal. In this
paper, the physicotechnical aspects of the use of this
method and principles of its optimization, which were
not given in previous publications, are described in
detail.
SETUP FOR SUPERCRITICAL DRYING
Supercritical drying was conducted in two high
pressure autoclaves. The optimization of technology
and the production of the samples of small
microporous materials were conducted in a 1L auto
clave with an inner diameter of 105 mm. The large
samples were dried in a 37L autoclave with the inner
diameter of 300 mm. Autoclaves represent thickwall
(the wall thickness is 75 mm) stainless vessels, which
are packed by aluminum spacers. The maximum
working pressure in autoclaves is 12 MPa (calculated
maximum pressure is 24 MPa) and working tempera
ture is 280°C. Autoclaves are set in an individual place
with induced ventilation. During supercritical drying,
operators stay in the neighboring room, where the
control panel is held, which allows controlling the
technological process.
In Fig. 1, the flow scheme of the experimental
setup for supercritical drying is given. The forms,
where there are raw microporous materials, are placed
in an autoclave which is preliminarily twothirds filled
by ethanol or methanol. Previously, on the production
of aerogels based on silica, methanol was used; how
ever, recently, the technology has been developed,
where both synthesis and supercritical drying of all
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
45
M2
7 8
6
M1 9 11
B1 B2
5 10
1
4
3
2
Ar
12
Fig. 1. Scheme of the setup of supercritical drying: (1)
autoclave with cap, (2) input for thermocouple (one
chromel–alumel thermocouple in a 1L autoclave and
three thermocouples in 37L autoclave at various heights),
(3) heating elements (five elements of 250 W in a 1L auto
clave and three groups by 10 kW in a 37L autoclave), M1
is highpressure manometer, M2 is highpressure sample
manometer, (4) balloon with inert gas (argon), (5) gear
box, B1 and B2 are fine adjustment valves, (6) MT100R
pressure sensor, (7) block of signal transduction BPS90P,
(8) spring emergency valve, (9) membrane emergency
device, (10) condensation container with water cooling,
(11) flow gage of gas flow, and (12) Miniterm400 temper
ature controller.
microporous materials are performed only with the
use of ethanol, which is preferable due to the high tox
icity of methanol. Autoclave is sealed and its prelimi
nary blowing is performed with the aim to replace air
in the autoclave by inert argon. The argon flow passes
through the autoclave, a sealed condensation con
tainer, and then emerges in the atmosphere. On blow
ing, the flow rate is controlled by a fine adjustment
valve B1 at the open valve B2 and it is measured with
the use of flow gage 11. The flow rate is usually set at
around 1 and 10 L/min for the autoclaves with the
capacity of 1 and 37 L, respectively; the time of purg
ing is 10 min.
After that, valve B2 is closed and the argon is deliv
ered to the autoclave until the pressure inside the auto
clave reaches 0.5 MPa. This measure prevents the eth
anol from possible effervescence upon heating when
the autoclave is packed insufficiently and there is an
insubstantial leak through its spacer. Then, valve B1 is
also closed and the autoclave is gradually heated. The
heating parameters (heating rate and points, where it
changes) are set by a Miniterm400 electron tempera
ture controller. The temperature in the autoclave is
controlled with the use of a thermocouple. The mea
surement of pressure in the autoclave is duplicated; it
Vol. 8 No. 7 2014
46
25
20
σ, mN/m
15
10
5 The polymerization proceeds from 7 to 10 days and
0 result, the silicabased alcogel is formed, which repre
250 300 350 400 450 500 550
T, K
Fig. 2. Dependence of interface tension of ethanol vs. tem
perature.
is measured by a sample manometer and an MT100R
pressure sensor combined with a BPS90P signal
transducer block.
With the transition through the critical point (for
ethanol, 516 K, 6.4 MPa), the surface tension at the
interface of the ethanol and its saturated vapor (Fig. 2)
and, accordingly, the capillary pressure of the ethanol
in the alcogel pores become zero. All the liquid in the
autoclave, including that in the pores becomes a
supercritical fluid without boiling. In practice, the
heating of the autoclave without a pressure loss is con
ducted up to ~550 K. It is necessary to overcome the
critical point with some reserve to prevent condensa
tion of ethanol vapors in the autoclave at a possible
slight cooling upon subsequent pressure loss, which
would result in the appearance of flaws in the porous
samples. After that, valve B2 is opened and the vapors
from the autoclave are gradually removed; the temper
ature in the autoclave is maintained constant. The
vapor enters the condensation container with water
cooling. Because there are barely any losses of ethanol
during supercritical drying, this reagent can be used
many times. After the pressure loss in the autoclave to
atmospheric pressure, the final purging of the internal
volume of the autoclave by argon is performed with the
aim to remove residual ethanol vapors in order to pre
vent their condensation on the cooling of the auto
clave. After that, the heating of the autoclave is shut
off.
OPTIMIZATION OF PARAMETERS
OF SUPERCRITICAL DRYING
AT THE SYNTHESIS
OF SILICABASED AEROGELS
Recently [4], during the synthesis of silicabased
aerogels, reagents such as methanol and tetramethox
ysilane Si(OCH3)4 were used. The preparation of
aerogel starts from the synthesis of silicabased alcogel
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
PUZYNIN
from the hydrolysis of tetramethoxysilane in metha
nol:
Si ( OCH 3 ) 4 + H 2 O → Si ( OH ) 4 + CH 3 OH.
Orthosilicic acid Si(OH)4 easily polymerizes and
condensates into silica:
nSi ( OH ) 4 → ( SiO 2 ) n + 2nH 2 O.
is conducted in the forms from stainless steel. As a
sents a threedimensional spatial structure that is
composed of the chains of spherical silica particles
with the diameter ~4 nm linked to each other by silox
ane bonds. The pores of this alcogel with sizes ranging
from 10 to 150 nm are filled by methanol.
The subsequent step of the synthesis of aerogel is
supercritical drying. The forms with silica alcogels are
placed in the autoclave. After that, the autoclave is
sealed and heated. After the achievement of the super
critical parameters in the autoclave (temperature and
pressure) for methanol, the pressure is dropped, upon
which the methanol vapors are removed from the alco
gel pores. Initially, after supercritical drying, intrinsic
flaws were often detected in the prepared aerogel sam
ples. The appearance of these flaws is caused by the
overly rapid heating of the autoclave, during which the
expanding methanol affected the unstable three
dimensional structure of the alcogel pushing apart its
samples from inside, as a result of which there were
large cross and longitudinal cracks after drying even in
relatively small aerogel samples dried in a 1L auto
clave (Fig. 3). In order to avoid the appearance of
these flaws and transfer to the synthesis of large aerogel
samples in the 37L autoclave, the author improved
the process parameters of supercritical drying.
In accordance with Stokes’s equation, the friction
force Ffr acts on the spherical particle with the radius r
moving in liquid with the dynamic viscosity of μ at
rate u:
F fr = 6πμru.
When the liquid that expands at heating in the
autoclave leaves the alcogel pores, its flow rate uliq rel
ative to the spherical silica particles forming the gel
structure is proportional to the change of the density of
liquid ρliq with the change of its temperature:
dρ lig ( T )
u lig ( T ) ∼ .
dT
In order to minimize the action of the friction force
from the expanding liquid both on individual spherical
silica particles and the entire spatial framework of the
alcogel, it is suggested to maintain the heating rate of
the autoclave Wh.auto at each time moment reversely
proportional to this friction force; i.e.,
dT auto 1 1
 ∼ 
W h.auto =   ∼ 
.
dt μ ( T )u lig ( T ) dρ lig ( T )
μ ( T ) 
dT
Vol. 8 No. 7 2014
 THE APPLICATION OF SUPERCRITICAL DRYING IN THE SYNTHESIS 47

Fig. 3. Intrinsic flaw in aerogel sample based on silica (diameter of sample 60 mm, height 25 mm) formed after rapid heating of
autoclave at supercritical drying.

0.9 0.9
0.8 0.8
2
0.7 0.7
0.6 0.6
μ, Pa · s · 103

ρ, g/cm3
0.5 0.5
0.4 0.4
0.3 0.3
1
0.2 0.2
0.1 0.1
0 0
250 300 350 400 450 500 550
T, K

Fig. 4. Dependence of dynamic viscosity and density of methanol vs. temperature: (1) dynamic viscosity and (2) density.

Thus, the heating rate of the autoclave at the cur
rent time moment should be reversely proportional to
the product of the dynamic viscosity of the liquid and
the temperature derivative of the density function of
the liquid at the same moment. The dependence plots
of the dynamic viscosity and density of methanol vs.
temperature are given in Fig. 4.
After the required calculations (differentiation of
density of methanol on temperature and integration of
the function of the temperature change in the auto
clave over time), the graph of the heating rate of auto
clave was plotted. The time scales of the process (inte
gration coefficients) were experimentally determined
for various sizes of dried alcogel samples. In Fig. 5, the
simplified (linear) view of the drying condition is
given for the synthesis of large samples (170 mm ×
170 mm × 50 mm) of alcogel based on silica in the
autoclave with a volume of 37 L. The points of the
change of the heating rate were added to the Mini
term400 temperature controller.
In order to dry small samples (diameter 60 mm,
height 25–30 mm) of alcogels in the autoclave with a
volume of 1 L, this graph was contracted on the

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 8 No. 7 2014

48
300
250
200
T, °C
150
100
C
50
AB
0 10
Fig. 5. Change of the parameters with time at optimized mode of supercritical drying of silica alcogels (removal of methanol) in
a 37L autoclave: (1) change of temperature in autoclave and (2) change of pressure in autoclave.
abscissa axis by a factor of over three; the period of this
process of supercritical drying in this case is ~12 h.
At the initial step (AB section), the autoclave is
heated relatively slowly, because the dynamic viscosity
and density of methanol are high at low temperatures;
then, the heating rate gradually increases, in the BC
and CD sections. In the DE section, the heating rate
decreases again, because with the transition through
the critical point, it is necessary that the liquid trans
fers to vapor simultaneously in the entire volume of the
autoclave, including the gel pores. The heating rate in
this section will provide the necessary homogeneity of
the temperature distribution in the autoclave. In the
DE section, the pressure loss is initiated. It is per
formed in such a way that the pressure in the autoclave
does not grow above 110 atm with the increase in tem
perature, the maximum working value for the given
autoclave set, which is set from the safety requirements
during its use. In the EF section, the pressure loss from
the autoclave is realized at constant temperature; in
the FG section, the purging of the autoclave with
argon is carried out with the aim to remove the residual
methanol vapors; and the GH section corresponds to
the drop of the temperature after the end of heating.
The mode of the pressure loss of the methanol
vapor from the autoclave also required optimization.
Even in the critical state, the fluid densities are suffi
ciently high (for methanol, ρcr = 0.272 g/cm3). If the
pressure loss is carried out too fast, the dense fluid
leaving the aerogel pores would also destroy its struc
ture. During optimization, the rate of the pressure loss
at the current time moment was set reversely propor
tional to the absolute value of the pressure at that
moment; i.e., the pressure loss P from the autoclave
was achieved in accordance with the following equa
tion:
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
PUZYNIN
14
E F G
12
H 10
D
P, MPa
8
1
6
2 4
2
0
20 30 40
Time, h
dP
 ∼ – 1.
dt P
The time scales of the pressure loss were also exper
imentally determined. The optimized mode of the
pressure loss is given in Fig. 5. The use of optimized
modes of the temperature rise and pressure loss
enabled us to avoid the appearance of intrinsic flaws in
the alcogel samples upon their supercritical drying.
THE USE OF SUPERCRITICAL DRYING
DURING THE SYNTHESIS OF NOBLE OPAL
AND OPTICAL QUARTZ GLASS
The synthesis of noble opal and the method of syn
thesis of optical quartz glass from silica sols can be
divided by four stages.
1. Synthesis of alcohol sols of monodisperse silica
particles.
2. Formation of raw opal material via spontaneous
sol sedimentation under the action of gravity force
during the synthesis of opal and centrifugation during
the synthesis of quartz glass.
3. Removal of liquid from the pores of raw opal
material, that is, its drying.
4. Filling the pores of dried opal material by plastics
or secondgeneration silica at the synthesis of opal or
caking this porous material in s muffle furnace during
the synthesis of quartz glass.
If we perform the drying step of the opal material
under standard conditions even for a long time, multi
ple internal stresses appear in the material, which turn
into cracks (Fig. 6).
The use of supercritical drying upon the synthesis
of opal or optical quartz glass initially looked problem
atical. The pore sizes in the densely packed structure
of opal material are by far greater than the pore sizes in
Vol. 8 No. 7 2014
 THE APPLICATION OF SUPERCRITICAL DRYING IN THE SYNTHESIS
Fig. 6. Cracking of opal material after its long (above 2 months) drying under normal conditions.
aerogels. This should ease the exit of the expanding
liquid from the pores on heating the autoclave. How
ever, spherical monodisperse silica particles, which
compose the opal material, are synthesized in aan lkali
medium (pH 8–9) in contrast to aerogels, during the
synthesis of which the aggregation of silica sols to alco
gels is conducted in acidic media. The particles are
synthesized via hydrolysis of tetraethoxysilane with
ammonia and subsequent polymerization of ortho
silicic acid:
Si ( OC 2 H 5 ) 4 + 4H 2 O → Si ( OH ) 4 + 4C 2 H 5 OH,
nSi ( OH ) 4 → ( SiO 2 ) n + 2nH 2 O.
The surfaces of these silica particles carry similar
charges due to hydroxyl ions OH– adsorbed from the
liquid phase. The repulsion forces between similar
charges prevent the coagulation of the silica particles,
due to which stable sols are formed. These repulsion
forces also lead to the fact that opal material sedi
mented or centrifuged from these sols represents a very
unstable structure, which resembles viscous “por
ridge” in terms of its physical consistence. The heating
of this opal material composed of chemically
unbonded silica particles in the autoclave may lead to
its redispersion to a sol under the heat motion of liq
uid. For this reason, the problem of optimization of
the supercritical drying conditions was realized
assuming the dependence of the dynamic viscosity and
density of ethanol vs. temperature. The optimization
of the temperature rise and pressure loss at supercriti
cal drying in ethanol was performed according to the
algorithms which are analogous to those described for
methanol.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
49
The practice showed that, during supercritical dry
ing, substantial strengthening of the opal material
samples proceeds in autoclave, because siloxane bonds
form between neighboring silica particles at high tem
peratures:
≡Si–OH + OH–Si≡ → ≡Si–OH⋅⋅⋅OH–Si≡
→ ≡Si–O–Si≡ + H2O.
Thus, as a result of the application of supercritical
drying, flawless strengthened samples of porous opal
material were obtained.
ECONOMICAL ASPECTS OF THE USE
OF SUPERCRITICAL DRYING DURING
THE SYNTHESIS
OF SILICABASED MATERIALS
It should be noted that supercritical drying is highly
consumptive. This is related to the high cost of used
equipment, the energy capacity of the process,
demand for the continuous checking of the highpres
sure autoclaves from the operators. The volume of
used autoclaves limits the output of ready production.
Therefore, it is necessary to consider the economical
feasability of the use of supercritical drying in the pro
duction of these silicabased materials.
Aerogels based on silica. In the Laboratory of
Nuclear Problems of JINR, aerogels, both conven
tional refraction indices (n = 1.005–1.06) and
extremely high parameters (n = 1.08–1.23) were syn
thesized [4]. During the synthesis of aerogels, the use
of supercritical drying is necessary, because it is impos
sible to obtain flawless aerogel samples in another way.
Due to their high cost, including the cost of the used
Vol. 8 No. 7 2014
50 PUZYNIN

Fig. 7. The materials based on silica obtained with the use of supercritical drying: (1) silica based aerogels, (2) mesoporous silica
glass, (3) optical quartz glass, and (4) synthetic noble opal.

supercritical drying i, these aerogel samples can be ments (Stardust project, NASA [6]). The use of flaw
useful only in various statefound fields of science, for less aerogel samples as heat isolation material is com
example, as radiators of Cherenkov radiation, which mercially ineffective.
are used in highenergy physics [5] or space experi

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 8 No. 7 2014

 THE APPLICATION OF SUPERCRITICAL DRYING IN THE SYNTHESIS 51

Fig. 7. Contd.

Mesoporous silica glass. Initially, supercritical dry
ing was also a necessary step for the synthesis of meso
porous silica glass in analogy with the synthesis of
aerogels. However, later, the authors of the patent from
[7] designed the technology giving the opportunity of
preliminarily strengthening alcogels based on silica
produced prior to drying. This strengthening led to the
decrease in the porosity of the final material compared
to the aerogels synthesized in JINR (from 80–95% to
60–80%); however, it decreased substantially its cost,
giving the opportunity to dry alcogels under standard
conditions.
Optical quartz glass. Due to the relatively low cost
of optical quartz glass, the method of its synthesis with
the use of supercritical drying is of interest only from
the scientific viewpoint. In industry, the use of this

RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B Vol. 8 No. 7 2014

52 PUZYNIN
method would not be profitable. Nevertheless, the
method of supercritical drying allows one to produce
samples of optical quartz glass under laboratory condi
tions [8].
Synthetic noble opal. The flawless porous opal
material without any internal stresses, which is real
ized as cracks during its subsequent multiple soakings
by concentrated secondgeneration silica sols, was
obtained with the use of supercritical drying. As a
result, the opal was synthesized, which is identical to
the natural noble opal by all its physical and chemical
properties, as well as the absence of any intrinsic
microflaws [9].
This identity features the given synthetic stone
from many other counterparts, for example, synthetic
Gilson opals [10], which are recently widely repre
sented on the global jewelry market. In Gilson opals,
the “lizard skin” intrinsic microflaw is easily detected
under a microscope, which represents the network of
microflaws in the entire volume of the material, which
resembles a lizard’s skin on the polished surface of
products made from it. This flaw is not intrinsic for
natural opals; therefore, its presence readily reveals
the artificial identity of Gilson opals. This flaw pre
sumably appears upon the drying of raw opal material
under standard conditions.
The closer the synthetic material in terms of all
properties to natural mineral, the higher its market
cost. Assuming a sufficiently high cost of natural noble
opals on the global jewelry market, the synthesis of
these stones using supercritical drying, which provides
the complete identity of the properties of synthetic
opal with natural mineral, is economically profitable.
CONCLUSIONS
The optimized method of supercritical drying was
successfully used in the synthesis of porous materials
SPELL: 1. Federalnoe, 2. Gosudarstvennoe
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY B
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from silica and the final products based on it such as
aerogel, mesoporous silica glass, noble opal, and opti
cal quartz glass (Fig. 7). The use of supercritical drying
is necessary in the synthesis of aerogels and economi
cally profitable in the synthesis of noble opals.
ACKNOWLEDGMENTS
The author is grateful to his colleagues at Federal 1
noe Gosudarstvennoe Unitarnoe Predpriyatie 2
NauchnoIssledovatelskiy Institut Prikladnoy Akus
tiki (FGUP NIIPA) M.V. Dmitrovskaya and R.V.
Novichkov for their work on the measurement of con
tact angles and discussion of the obtained results.
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Translated by A. Muravev
Vol. 8 No. 7 2014