SOLID STATE CHEMISTRY AND FUNCTIONAL MATERIALS
V. G. Bamburov
Institute of Solid State Chemistry, Ural Division of Russian Academy
of Sciences, Ekaterinburg, Russia
The theory and practice of modern functional materials creation
arose to date in the framework of solid state chemistry (SSC) play an
important role in the progress of chemistry and materials science.
Comparison of regular features established in condensed matter research
permits a most efficient technical application of the developed materials.
Major attention in SSC is focused on combined chemical and
physical properties of solids, which qualitatively distinguish them from
individual molecules. Peculiarities of condensed states determine the
basic trends in SSC investigations including (1) analysis of the
dependence between physicochemical properties and reactivity of solids
and their real structure; (2) research of transfer processes in solid phases
associated with diffusion or chemical transformations; (3) investigations
of phase transformations occurring during interactions in chemical
reactions.
The Institute of Solid State Chemistry of the Ural Branch of the
Russian Academy of Sciences is one of the leading research centers of the
Russian Federation in the field of solid state chemistry and materials
science involved in systematic studies of targeted synthesis of compounds
and alloys in various structural states, investigation of their physical,
chemical, and mechanical properties with the aim of development and
application of novel and promising materials, improvement and
development of advanced technologies for processing of mineral raw
materials and technogenic waste products.
Let us consider the main results of the Institute’s recent research
activities and formulate the nearest prospects for investigations using
some particular examples.
5
Much attention has been conventionally devoted to synthesis of
novel compounds and exploration of interphase interactions and
chemical transformations, which were ultimately directed at developing
advanced materials and technologies.
This can be illustrated by the investigations of complex lithium
oxides. These compounds are the basic materials for developing devices
for direct (without intermediate stages) conversion of chemical energy to
electrical energy. Noticeable progress was achieved in the synthesis of
these compounds and exploration of their electrophysical properties.
The fundamental problems concerning lithium transfer
mechanisms, the high-conductance phase generation, and the role of the
electronic structure in the formation of transport properties of complex
oxides with a spinel structure are being solved. The spinel structure has a
large capacitance with respect to metal cations giving rise to a large
number of compounds of different composition but similar structure.
The presence of vacant octahedral and tetrahedral sites is a prerequisite
for rapid transport of lithium in the spinel structure. Besides, the ability
of the spinel frame to confine cations of one element with different
degrees of oxidation fosters reversible redox reactions thus determining
the application of such oxides as electrodes in lithium batteries. This
favorably distinguishes them from familiar complex mixed conductors
with a layered LiNiO2-type structure. Vanadium can be also used as an
element with a variable valence to form mixed conductors, since in the
spinel structure it may occur in three degrees of oxidation 3+, 4+, and
5+. It was shown that new variable-composition phases of the
Li12xCo1+xVO4 type have a high portion both of ionic and electronic
conduction in a wide lithium concentration range.
The defect structure and transport properties of new oxides with a
high degree of conductivity in oxygen ions and electrons have been
studied systematically. An unusually high level of conductivity in oxygen
ions at temperatures above 650С and electrons in a wide oxygen
pressure range (Fig. 1) was observed for the first time for vacancyordered phases formed in the La-Sr-Fe-Ti-Ga-O system.
6
-1
-1
lg(s/Oм см )
SrFeOy
1
o
950 C
0
-1
o
700 C
-20
-16
-12
-8
lg(pO2/атм)
-4
0
Fig. 1. Isotherms of total electrical conduction of strontium ferrate.
This effect combined with a high thermodynamic stability
permits using those materials in ceramic membranes for developing
entirely new technologies for natural gas conversion, oxygen generation,
and direct conversion of chemical energy to electrical.
Reactions of conversion are based on a passive (i.e. without
external source of electrical energy) membrane process of hightemperature extraction of oxygen from air. Mixed conductivity
parameters obtained [1] for a number of compounds make it possible to
attain a high, attractive for practical purposes productivity of oxygen
extraction from air. The amount of oxygen produced per a square
centimeter of 1 mm thick La0.7Sr0.3Fe1-xGaxO3- membrane under usual
conversion conditions (temperature ~ 900 С, oxygen pressure gradient ~
10-17 atm/cm) is 2-3 cm3/min, which is equivalent to the productivity of
synthesis gas formation of 12-18 cm3/min. The practical aspects of the
investigations are closely related with the problems of power engineering,
organic synthesis, and environment protection.
A large body of research was devoted to phase relationships in
ternary systems of II and V subgroup oxides including
M2O3V2O5R2O5,
M2O3B2O3R2O5,
M2O3B2O3V2O5,
Y2O3Nb2O5Ta2O5, Ta2O5Nb2O5V2O5, Al2O3V2O5R2O5, where M
= Sc, Y, La, Ln; R = Ta and Nb. 43 novel compounds and solid solutions
with promising properties have been synthesized, for which we worked
7
out synthesis techniques and examined regular features of formation,
crystal chemistry, as well as spectral and luminescent characteristics. This
allowed us to discover [2] an important class of REM-tantalate-based
radiopaque substances for bronchography, which effectively absorb Xrays emitted by modern medical diagnostic equipment.
The studies into REE semiconductors have been elaborated
further. An essential increase in exchange interactions in solid solutions
Eu1-xSmxO observed earlier was the basis for developing planar
structures used to register energy variations of analytical systems, Figs.
2, 3.
In the thin-film state, the magnetic heterogeneity effect observed
for compact samples Eu1-xSmxO increases considerably. This shows
promise for applying rare-earth magnetic semiconductors in memory
elements and planar structures.
Θ
Fig. 2. Concentration dependence of lattice parameter a, ferromagnetic T k and
paramagnetic  Curie temperatures of solid solutions Eu1-xSmxO.
8
Fig. 3. Eu1-xMexO-based sensor for registering various energy fields, fitted with
a memory element.
The study of the phase diagram in the Ln2O3-WO3-SnO2 system revealed
rather an unusual structure versus concentration dependence. The
discrete character of the observed solid solutions is due to the stability of
the scheelite structure of the general formula Са4W4O16. Phases with
substitution limits in the solid solution Ln2.67+0.67xW4-xSnxO16 (Ln =
Sm….Lu) may become effective materials for luminophors with
enhanced thermal stability and color reproduction, Fig. 4.
Fig. 4. Phase diagram of the Ln2O3-WO3-SnO2 system exhibiting ternary phases
Ln2Sn2O7 (o), Ln2W3O12 (□), Ln6WO12 (), Ln2WO6 (), Ln2W2O9 () and
four-component solid solutions Ln2.67+0.67xW4-xSnxO16, where Ln = Sm  Ln,
0.90  x  0.
9
Considerable attention was focused on the effect of
nonstochiometry in condensed phases and the influence of
structural vacancies on their properties.
Continuous vacancy channels (Fig. 5) were found in a
titanium monoxide crystal with ordered metallic and non-metallic
vacancies. An experimental vacancy-visualizing image has been
obtained for the first time using a high-resolution electron
microscope (4 000 000 time magnification). The sign and value of
structural vacancy charges were established. It was found by
positron life time measurements and the method of Doppler
widening of gamma-quanta that positrons are trapped by structural
vacancies of the metallic sublattice of titanium oxide with a small
electronic density. The vacancy charge is ~ 0.3 е. It decreases as
the content of oxygen rises.
We pioneered the application of atomic vacancy ordering
[3] for producing a nanocrystalline structure in solids. A
nanostructured disperse ordered vanadium carbide was obtained by
smooth transition through the disorder-order transformation
temperature
Vanadium carbide nanocrystallites have the shape of bent
petals 400-600 nm in diameter and 15-20 nm in thickness, Fig. 6.
The surface layer contains defects of the vacancy-agglomerate
type. The microhardness of the sintered bulky samples of the
nanostructured vanadium carbide is close to that of diamond.
Phase relationships in quasi-binary systems MnO-Nb2O5 and
ZnO- Nb2O5 were studied systematically. Thermobaric synthesis was
used for the first time to obtain the standard trigonal modification of
Zn4Nb2O9, i. e. its structure is similar to that of Mn4Nb2O9, Fig. 7. For
Mn4Nb2O9, we observed a polymorphous phase transition from the
standard trigonal modification to the nonstandard rhombohedral
modification (sp. gr. R3c, Z=2), which is isostructural with LiNbO3. The
structural investigations performed allowed us to propose a
crystallochemical formula for a new polymorphous modification
Mn(Mn2/3Nb1/3)O3, which has six molecules per a unit cell.
10
[
1
1
0
]
B
1
[
1
1
1
]
B
1

2
a
/
2
B
1
[-15-2]B1

3
a
/
3
1
B
[
2
0
1
]
B
1
Fig. 5. Structural vacancy channels in titanium monoxide: model
(left), high atomic-resolution electron microscope image (right).
T
i
O
Fig. 6. Nanostructured vanadium carbide V8C7.
Essentially new oxoniobates with condensed clusters of uni- and
two-dimensional niobium monoxide were obtained in the BaO-NbONbO2 system. They arise as a result of ordering in α-phasoid, which can
be represented as a disordered intergrowth in the bulk of the matrix in the
perovskite structure.
11
Based on the studies of polymorphism and isomorphism and their
interdependence, we constructed a scheme for the formation of a
morphotropic series of bivalent metal metavanadates M(VO3)2 at various
temperatures as a function of the volume of the soft metal-oxygen
polyhedron VM-O, where M = Ni, Co, Zn, Mg, Mn, Cd, Ca, Sr, Pb. Four
isomorphous series of structural types N, BI, BII, and OR (Fig. 00) have
been distinguished and the values of VM-O determining their stability
boundaries have been established. Structural type N takes place at V M-O <
12.30; BI – at 12.3< VM-O < 15.75; BII – at 15.85 < VM-O < 17.31; and OR
– at VM-O > 17.31 Å [4].
Fig. 7. Disordered and partially ordered Mn4Nb2O9.
New composites TiO2·nH2O xС (x=0.5÷3.0) based on the
nanocrystalline titanium hydroxide and disperse carbon phase have been
obtained by the zol-gel method. The raster electron microscopy (REM)
and scanning tunneling microscopy (STM) were employed to display a
three-level hierarchic structure of titanium hydroxide particles of 100300, 30-80, and 8-30 nm dimensions. The ratio of the mean diameter of
particles from the preceding and succeeding level is constant and equals
approximately four. This suggests a unified mechanism of titanium
hydroxide nanoparticle formation during hydrolytic precipitation. It was
found that the precipitation of TiO2·nH2O on the surface of the carbon
12
phase, in contrast to the precipitate, results in a more homogeneous
texture of the titanium hydroxide phase (Fig. 8).
Спектры размеров частиц осадка TiO2 и TiO2||C.
TITO2.TXT
TIO2_CC.TXT
7
7
6
6
Par
ticl5
es,
%4
Par
5 ticl
TiO2aq||C
composite
es,
4%
3
TiO2aq
precipitate
2
1
3
2
1
0
0
200
400
0
600
Particle diameter, nm
Fig. 8. Variation in particle dimensions of titanium hydroxide on the carbon
substrate surface and of bulk precipitate.
As distinct from the precipitate, the presence of competing ions
in fresh water exerts no considerable effect on the sorption of strontium
ions by the composite [5]. This opens up wide prospects for the
application of the developed composites in radio chemistry.
The investigation of electrochemical properties of 12-row
tungsten heteropolyacids of different compositions and hydratation
degree – H3PW12O40nH2O (n = 6.5; 23), H4SiW12O40nH2O (n = 9; 18),
and H5GaW12O40nH2O (n = 10; 13) – revealed that the tungsten-silicon
acid has the maximum proton conductivity in the temperature intervals of
heteropolyanion stability. According to proton magnetic resonance
studies, the tungsten-silicon acid has the optimum ratio between the
13
strength of hydrogen bonds of acid proton with water molecules and that
of water molecule protons with oxygen from heteropolyanions. This
makes it a proton conductor superior to tungsten-phosphoricand and
tungsten-gallium acids. The results obtained allowed us to propose the
tungsten-silicon acid as the basic component for producing a composite
with titanium oxyhydrates [6].
The main regularities of the influence of synthesis conditions on
the chemistry, structure, and properties of solid-phase titanium
oxyhydrates have been established. It was shown that while hydrolytic
deposition from solutions gives rise to hydrated titanium dioxide
TiO2nH2O, heterophase ionic exchange allows synthesis of some
titanium acids. We have developed an approach to distinguish and
identify a new compound Н2TiO3, viz. a true «metatitanium acid», whose
existence was earlier in doubt. Quantum-chemical calculations of the
electronic structure of Li2-хНхTiO3 (0≤ х ≤2) compounds exhibited a
correlation between their thermal stability and changes in chemical
bonding.
Mechanical properties of cermets were improved [7-9] due to (1)
the grain dimensions of the ceramic basis (titanium carbonitride)
decreased to an ultradisperse or nanocrystalline state and (2) replacement
of the conventional nickel-molybdenum binder by intermetallics, in
particular titanium nickelide. The optimum conditions for alloy
preparation were found to be liquid-phase sintering of titanium
carbonitride and titanium nickelide powder mixture. Regions of 20-30 nm
disperse particles were established to be uniformly distributed in the bulk
of the system “ultradisperse titanium carbonitride – titanium nickelide”.
Quenching of alloys brings about self-dispersion and formation of highly
dispersed particles of size 2-5 nm.
Powders of alloys based on ultradisperse titanium carbonitrides
underwent magnetic impulse pressing. Upon sintering, this resulted in
1.5-2 times reduction in grain growth during recrystallization and
enhanced Rockwell hardness and density of the samples, see Table 1.
14
The following characteristics were achieved: hardness - 8690
HRA, ultimate lateral three-point bending strength  2000 МPа. For
comparison, ultimate strength of Т15К6 (WC 79%, TiC 15%, Co 9%)
and Т5К10 (WC 85%, TiC 6%, Co 9%) alloys having similar hardness is
respectively 1150 and 1350 МPа.
Theoretical simulation techniques based on nonempirical
quantum-chemistry calculation methods have been extensively developed
to solve modern materials science problems [10-14].
Let us illustrate their possibilities using, as an example, prediction
of promising properties of crystals (new boron-containing
superconductors), ceramic materials (the so-called sialon ceramics) and
simulation of unique symbiosis nanostructures (nanotubular composites).
A series of investigations [15-20] has been performed to model
the band structure and properties of a large number of boron-containing
compounds as potential superconductors possessing chemical and/or
structural features similar to those of the new “medium-temperature”
superconducting Mg diboride. We have considered: (1) binary phases in
the Mg-B system: MgB2, MgB4, MgB6; (2) AlB2-like phases with
graphite-like motifs of sp atoms: CaGa2, ZrBe2, HfBe2; (3) CaB2, MgB6,
CaB6 phases; (3) compounds in the Mg-B-N system: MgB2-xNy и
Mg3BN3; (4) nonstoichiometric borides (MgB2-x,Mg1-yB2) and a wide
range of possible solid solutions of the type MgB2-xХy (Х = Be, C, N, O)
or Mg1-yMyB2 (M = Li, Na, Cu, Zn, Be, Ca, Al, Sc, Y); (5) ternary
ordered borides YСrB4, Y2ReB6, MgC2B2; (6) Y, Zr dodecaborides; (6) a
new group of ternary phases with antiperovskite structure:
superconducting MgCNi3 and related compounds: MgCCu3, MgCCo3,
MgBNi3, ScCNi3, nonstoichiometric MgCNi3. Analysis of electronic
structure parameters allowed us to point out the possibilities of
discovering superconductivity in the above compounds. In particular, we
have predicted a new superconductor Be2B (Fig. 9) and a group of hole
dopants. Their introduction into magnesium diboride may favor an
increase in the critical temperature of the basis phase (see review [20]).
15
Table 1
Characteristics of cermets of the system “ultradisperse titanium
carbonitride – titanium nickelide” obtained by magnetic impulse pressing
(1.5 GPа, 300 mcm) and liquid-phase sintering at 1380 С.
No.
Alloy
composition
Pressing
density,
g/сm3 (%)
1
2
3
TiC0.35N0.35+
4.428 (86)
4.457 (86.6)
4.329 (84.2)
30 mass % TiNi
4
5
6
TiC0.35N0.35+
7
TiC0.35N0.35+
30mass % TiNi+
0,7 mass %
Al2O3
8
9
10
11
12
30 mass %
TiNi**
TiC0.35N0.35+
30 mass %
TiNi+
Alloy density
upon heat
treatment,
g/сm3 (%)
4.68
4.63
TiCN grain
dimension in
the alloy,
mcm
2.200.1
3.10.1
3.30.1
Rockwell
hadness,
HRA
4.307 (83.7)
4.316 (83.9)
4.328 (84.1)
4.59
5.06
2.370.1
3.330.1
3.350.1
78
86
87
4.461 (88.5)
4.76
2.320.1
80
4.378 (86.9)
4.80
2.790.1
88
4.360 (86.5)
4.455 (88.4)
4.413 (87.6)
4.403 (87.4)
4.43
5.16
3.550.1
2.210.1
2.820.1
3.130.1
88.4
81
88
88
80
88
87
0.7 mass %
AlMgOx
*
the samples were sintered with intermediate exposures during
10, 20, 30 min. at temperatures 600 С, 900С, 1380 С respectively
** the sample was doped with carbon to remove oxygen from
TiCN
16
Fig. 9. Energy bands of MgB2 (1), BeB2 (2), Be2B (3).
Pioneering investigations of atomic ordering processes in
complex ceramic materials, viz. the so-called 
SiAlON), have been carried out. We have found an atomic ordering effect
in the form of quasi-one-dimensional structures (aluminum oxide
“nanotubes”, Fig. 10) and elucidated their genesis [21-23]. It was
proposed [23] to use this effect for targeted modification of 
properties by intercalation of dopants inside the “tubes” thus improving
their cohesive parameters. It is suggested that here it is possible to obtain
ceramic materials with thermomechanical parameters superior to those of
the initial 
3N4 due to a peculiar “reinforcement” of the nitride’s
structure with the above “turbular” 1D-motifs of impurity atoms.
Fig. 10. Atomic ordering in sialons.
17
We were the first to analyze in detail atomic vacancy ordering
effects for another type of sialon ceramics, namely SiAlON polytypes.
The composition of those polytypes (Alx+ySi6-xOxN8-x+y, x=4, y=2n, n –
integral number) was found [21-23] to form due to the introduction of
“impurity” clusters {Si+2O+V} into AlN. The polytype structure is made
up of quasi-two-dimensional layers composed of alternating aluminum
nitride “blocks” including four adjoining monolayers of the composition
(O)-(Al0,5V 0,5)-(N)-(Si0,5Al0,5). It was speculated that in the 2D-«defect
block» the probability of formation of an “intrinsic” order in linear atomvacancy motifs is not ruled out. This can be interpreted as an appearance
of a peculiar “polytypism of polytype layers”.
The problem of encapsulation of III-VI group d-metals into
carbon nanotubes (NT) was considered. The introduction of those metal
atoms (with a high carbide-forming ability) in the “pure” state was shown
to destroy the NT. We proposed a radically new class of symbiosis
nanoturbular composites, where d-metals are incorporated inside the
tubes as ”intrinsic” stable nanostructures, namely metallocarbohedrenes
(metcars). Quasi-one dimentsional (1D) crystals, which are regular chains
of [M8C12] metcars located along the axis of monolayer nanotubes were
considered as model symbiosis structures, Fig. 11. The regularities of the
microscopic properties formation of the above nanocomposites (1DM8C12@(n,m)NТ) were examined as a function of (1) mutual chain-tube
arrangement: [M8C12]-(n,m)NТ, (2) chemical composition of
metallocarbohedrenes [M8C12], and (3) chemical composition of tubes
(n,m)NТ [24-26].
Fig. 11. Symbiosis nanostructure model: fullerene-like nanoclusters in
nanotubes.
The following examples can illustrate the development of works
for creating novel technologies and materials.
18
An important problem associated with the processing of
technogenic wastes is the utilization of ashes stored up at thermoelectric
power stations, where mazut is burnt to produce heat. One of valuable ash
components is vanadium. According to estimates, 300 thousand tons of
slime accumulated to date contain up to 5 thousand tons of vanadium.
The elaborated [27] technology of selective extraction of vanadium to an
acid solution with subsequent deposition in the form of oxides permits
obtaining a product with vanadium oxide content of up to 98 %.
A new class of periclase carbon refractories for metallurgical
units has been proposed, which possess enhanced thermal stability,
corrosion resistance and are nature friendly. The prospects of using
antioxidants and binders in carbon-containing refractories were analyzed.
A new class of boron-containing compounds was offered as antioxidants.
Comparative analysis of samples sintered at 1000 оС in air showed that
the presence of amorphous boron-95 or/and –85 in periclase-carbon
compositions increases the strength characteristics of ceramics in 1.5 – 2
times. Willow pitch (wood processing product), which contains no
carcinogenic cyclic hydrocarbons, was proposed as abinder for resincontaining refractories. The operating characteristics of refractories
retained, while the ecological conditions of their production and
application have been substantially improved.
We have elaborated a method of electrochemical cleaning and
electropolishing (in neutral electrolytes) of the surface of heat-treated
ribbon made of chrome-containing steels manufactured at the JSC UPPA.
The application of this technology sharply reduces the volume of acid
wastes and improves labor conditions.
A series of intensifying screens based on new
roentgenophosphors YTaO4 with Nb and Tm impurities was produced.
The roentgenoluminscence brightness of YNb0,05Ta0,95O4 is ~130% of that
of the standard phosphor Р -420-1 (CaWO4). The new-generation
intensifying screens have enhanced image sharpness in comparison with
industrial screens УЭ – В24.
Other Institute’s developments involve creation of (1) new
metalloceramic coatings substituting platinum in refining, (2) new
composite materials (powders and coatings) with gradient-layer structure
having enhanced mechanical and operational properties, (3) chemical and
electrochemical methods of cleaning of industrial sewage from nonferrous and heavy metals, such as arsenic, copper, lead, mercury, zinc, (4)
19
selective solid agents for extracting rare-earth metals from complex saltwater solutions. The above developments are covered by patents [28-37].
In conclusion let us outline the prospects of investigations in the
field of solid state chemistry proposed in the framework of the Institute’s
research.
Undoubtedly one of the topical problems will be synthesis of
novel compounds and materials and exploration of their properties. We
shall further investigate strongly nonstoichiometric interstitial
compounds of transition metals (carbides, nitrides, their mutual solid
solutions), which represent a unique group of compounds combining
high hardness, refractoriness, and other valuable properties also in the
nano-scale state.
Studies will be continued in the field of purpose-oriented
synthesis of novel simple and complex oxides with layer-block and lowdimensional structures, heteropolycompounds, ferrocyanides, and
intercalates including those possessing practically important electric,
magnetic, electrode, catalytic, sorption, sensor, and other properties.
Much attention will be given to the preparation of complex doped REE
oxides and fluorides, which are promising materials for electronics.
Amorphous and glassy states of REE oxochalcogenides, which serve as
ionic conductors and elements for chemical current sources, will be
intensively investigated.
More active experimental studies of the electronic structure and
physico-chemical characteristics of rare-earth metals, their compounds
and alloys in disperse, ultradisperse and nano-scale state will be
performed to work out effective energy-releasing materials and new
catalysts.
Special attention will be devoted to research and materials
science works concerning the creation of novel universal ceramic
materials based on oxides, nitrides, and complex doped oxynitrides of
p,d elements.
We plan to update and automate X-ray and electron microscopic
equipment and develop tunneling spectroscopy. Advanced methods of
attestation and analysis of properties of solid-phase compounds will be
elaborated: (1) positron annihilation method, which is a unique
technique for studying the structure of nanocrystalline substances; (2) Xray photoelectron diffraction (XPD) used for precision analysis of the
structure and properties of surfaces and interface processes; (3)
20
radiospectroscopic methods (electron and nuclear magnetic resonance)
for performing precision investigations of structural characteristics and
chemical transformations of complex polycomponent compounds and
materials.
We are going to continue investigations in the field of quantum
chemistry of solids and materials science to simulate theoretically the
conditions of materials formation and to predict their service properties.
As for applied research, we shall systematically perfect the
existing technologies and introduce novel technological processes
connected with extraction, percolation, ion exchange, adsorption, zolgel technologies for removal of toxic ions from sewage, extraction of
valuable components, complex processing of raw materials for
extracting gallium, scandium, and other elements at the plants of
Verkhnii Ufalei, Kamensk-Uralskii, Kransoturinsk and other towns of
the Ural region.
1.
2.
3.
4.
5.
6.
7.
8.
9.
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21
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28. Patents of the Russian Federation taken out for the inventions made
in the Institute of Solid State Chemistry, UB RAS:
29. RF patent No. 2171712 “Catalyst for carbon oxide oxidation “,
2001, authors V. I. Kononenko, I. A. Chupanova, V. G. Shevchenko
et al.
30. RF patent No. 2173173 “Contrasting agent for radiodiagnosis
(options) and method of its preparation“, 2001, authors M. G. Zuev,
V. V. Keshelava, L. P. Larionov et al.
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coatings“, 2001, authors N. A. Rudenskaya, V. A. Zhilyaev, V. A.
Kopysov.
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carbonitride“, 2001, authors Yu. G. Zainulin, L. Kh. Askarova, E. V.
Shchipachyov et al.
33. RF patent No. 2145313 “Charge for ceramic foam material
preparation (options)“, 2000, authors T. A. Timoshchuk, G. P.
Shveikin.
34. RF patent No. 2140998 “Method for processing red oxide of iron“,
1999, authors O. D. Linnikov, S. P. Yatsenko, N. A. Sabirzyanov.
35. RF patent No. 2149076 “Method for preparing powders of
refractory titanium-based compounds“, 20000, author G. P.
Shveikin.
36. RF patent No. 2136777 “Wear-resistant coating and method of its
preparation“, 1999, authors N. A. Rudenskaya, V. A. Zhilyaev, V. A.
Kopysov.
37. RF patent No. 2124574 “Method of preparation of scandiumaluminum master-alloy (options)“, 1999, authors A. B. Shubin, S. S.
Zobnin, S. P. Yatsenko.
38. RF patent No. 2104924 “Method of preparation of hydroxyapatite“,
1998, authors S. P. Yastenko, N. A. Sabirzyanov.
23