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Powder Metallurgy and Metal Ceramics, Vol. 50, Nos. 7-8, November, 2011 (Russian Original Vol.

50, Nos. 7-8, July-August, 2011)



T. Ya. Velikanova1

12 August 2011 marked the 100th anniversary of Valentin Eremenko’s birth, an academician of the
Academy of sciences of the Ukrainian Soviet Republic, an outstanding physical chemist, a founder of
the Institute for Problems of Materials Science, National Academy of Sciences of Ukraine.
Eremenko’s papers on the physical chemistry of fine particulate systems and surface phenomena,
chemical thermodynamics of alloys and metal compounds, and physicochemical analysis of metal
and metallic systems have highly been praised by national and international scientific community.
Eremenko’s chemical concept of phenomena that occur at interfaces in heterogeneous systems has
been brilliantly proven by experiment and widely used in studies focusing on surface phenomena,
powder metallurgy processes, compatibility of materials, soldering, etc. The physicochemical
constants for simple and complex substances derived from analysis of the phase diagrams and
thermodynamic properties of metal, metallic, and semiconductor systems have been included into
handbooks and are an important, fundamental component of modern materials science. Eremenko’s
scientific ideas and scientific areas are further elaborated by his school of physical chemists.
Keywords: physical chemistry of inorganic materials, scientific school of physical chemists, phase
diagram, thermodynamics of metal systems.

12 August 2011 marked the 100th anniversary of Valentin Eremenko’s birth. He was an outstanding
scholar, whose studies in physicochemical materials science were well known and universally recognized in the
former Soviet Union and abroad. Valentin Eremenko was behind the establishment of the Institute for Problems of
Materials Science, National Academy of Sciences of Ukraine, and led one of the three major academic areas at that
The basic areas of physical chemistry that evolved under Eremenko’s supervision were a response to
challenges associated with the development of powder metallurgy, a new, very promising field of science and
technology of that time. Valentin Eremenko formulated them as follows: “The key scientific problem of
powder metallurgy is to establish conditions for the formation of a sintered body. The properties of starting
components that are then combined in highly heterogeneous systems, the nature of and interaction between the
components, and the surface energy, adsorption, and wetting at interfaces are major factors that determine the
production environment and properties of sintered bodies (and, consequently, the properties of articles made
of them).” This statement reflects the general challenges to be met in developing any new materials: select starting

1Frantsevich Institute for Problems of Materials Science, National Academy of Sciences of Ukraine, Kiev,
Ukraine; e-mail:
Translated from Poroshkovaya Metallurgiya, Vol. 50, No. 7–8 (480), pp. 1–10, 2011. Original article
submitted July 25, 2011.

1068-1302/11/0708-0377 ©2011 Springer Science+Business Media, Inc. 377

components and their composition, examine the structure and properties depending on ambient conditions, identify
and scientifically justify forming methods. The enthusiastic, tireless, and extensive efforts of Eremenko and his
research team led to the establishment of the following independent fundamental areas of physicochemical
materials science:
• physical chemistry of fine particulate systems and surface phenomena;
• compatibility of materials in solid and liquid states at high temperatures;
• chemical thermodynamics of alloys and metal compounds;
• heterogeneous equilibria in systems formed by refractory and rare elements (including those containing
They obtained new and highly accurate results, which were a powerful breakthrough in these research
efforts and owed, among other things, to the development of novel experimental methods and the improvement of
existing ones, and brought them to metrological precision to which Eremenko attached paramount importance. In
the development of the Department for Physical Chemistry of Inorganic Materials established by Valentin
Eremenko, a research methodology and strategy were formed, a research team was brought up, and scientific
traditions were established, i.e., a scientific school of physical chemists was created. The latter seems a no less
important result of Eremenko’s efforts than fundamental scientific generalizations that provided a reliable basis for
further research. A vast array of new, mainly reference, information on the fundamental physicochemical properties
of thermodynamic systems was accumulated. Details of the scientific heritage of Academician Eremenko can be
found in the book entitled V. N. Eremenko. Selected Papers. Memories (Naukova Dumka, Kiev, 2011) composed by
his students for the remarkable anniversary.
The contribution of Eremenko’s scientific school to the study of phase diagrams and thermodynamics of
metal systems and to the development of these areas during the first years after he passed away was highlighted
previously [1, 2]. The efforts started by Eremenko back in the 1950s and his scientific ideas were successfully
developed further by his disciples and followers not only at the Institute for Problems of Materials Science but also
in other scientific centers of Ukraine and now independent states of the former Soviet Union. A new, young
generation of scientists was brought up, who perceived the ideas and absorbed high moral principles of the selfless
service to science by which Eremenko was guided himself and which he inculcated in his students. Numerous
papers published in this anniversary issue and in Nos. 7–8 of Powder Metallurgy and Metal Ceramics for 1996 and
2001 are evidence of the successful development of this area.
The objective of this paper is to briefly describe the trends in the physicochemical analysis and
thermodynamics of metal systems developed by the scientific team, with a focus on recent efforts peculiar to the
The bar charts in Fig. 1 show the number of publications in the Department’s major scientific areas for six
decades of its existence. This figure testifies that Valentin Eremenko clearly preferred the study of surface
phenomena (capillary properties of metal melts, wetting and compatibility of materials) even in the early years
(1952–1961). Starting from the 1970s, the studies on phase diagrams and thermodynamics (in total) significantly
surpassed the overall contribution of other areas. This tendency increased with years and successfully overcame the
critical nineties. This owed to the sound foundation of experience and knowledge, which made it possible not only
to preserve the scientific area but also significantly intensify research. The research efforts were planned on a
systematic basis and research subjects were oriented at practically relevant problems. The systems studied after
1991 are shown in Table 1, supplementing the information on previously examined phase diagrams reported in [1,
Table 1] (almost 600 publications, including thermodynamic studies). The studies of phase diagrams primarily
focused on multicomponent systems (including ternary systems being the first level and part of multicomponent
systems) since they laid the foundation for future development of new promising materials for various applications;
the increasing use of computer methods and thermodynamic simulation of phase equilibria, without which the study
of phase diagrams of multicomponent systems had no prospects, was a significantly new area; the experimental
capabilities were enhanced through the extensive use of electron microscopy (scanning and transmission), the
introduction of modern data processing software, etc. This became possible through the fruitful collaboration with

55 Surface properties 58 Compatibility
60 of materials, physical
of metal melts

Number of publications
chemistry of interfaces
118 publications in total
215 publications in total
40 40
34 37
31 34
30 29
30 26
20 19
10 10
0 0
1952− 1962− 1972− 1982− 1992− 2002− 1952− 1962− 1972− 1982− 1992− 2002−
1961 1971 1981 1991 2001 2011 1961 1971 1981 1991 2001 2011
Thermodynamics of metal 54 54 Physicochemical analysis
alloys and semiconductors 350 of condensed systems 364
50 Phase diagrams
Number of publications

218 publications in total 300

40 37 39 1006 publications in total 257
30 200 176
20 108
100 91
10 49
4 50 24
0 0 1952−
1952− 1962− 1972− 1982− 1992− 2002− 1962− 1972− 1982− 1992− 2002−
1961 1971 1981 1991 2001 2011 1961 1971 1981 1991 2001 2011
Periods Periods
Fig. 1. The number of publications by the Department for Physical Chemistry of Inorganic Materials
in basic scientific areas (1952–2011): unhatched regions⎯critical reviews on phase diagrams in
international handbooks

TABLE 1. Subjects and Methods of Phase Diagram Studies (after 1991)

M1−M2; M1−M2−M3; Systems involving rare-earth metals and M1–M2–(B, C);

M1−M2−M3–M4 tin M1−M2−M3–(B, C, Si)

Sc–Rh, Ti–Ru(Ga), Cr−Re Si–Ho (Er, Y, La, Tb, Ce) C–Gd (Ho)
Cu−Zr; Ni−Os; Ti−Si (Sn, Dy) C–Ti (Cr)–Re
Al−Cr (Re, Ru, Rh, Pd, Ir) La−Ce−Si C–Sc–Ti (Cr)
Al–Ti–Nb(Ta, Cr, Rh, Pd, Pt) Ti–Si–Ga (Zr, V) C–B–Nb (Mo)
Al−Cr−Fe (Mn, Ni, Pd, Pt) Ti−Si−Sn B–Nb (Mo)–Si
Al−Fe−Ta (Mn) Ti−Zr (Dy, Ga)−Sn B−Mo−Fe (Ni)
Al−Co (Mn, Re)−Ni Ti−Tb (Zr, Dy, V)−Si B−Nb (Si)−Ti*
Al−Ni−Mn (Re, Ir, Pt) Al−Dy (Si)−Ti B−Si−Ti*
Al–Pd–Fe (Cr, Mn, Re, Co, Ni, Rh, Ir, Ti−Si−Zr (Sn, Nb)−Al B–Si–Ti–Al (Sn)
Ru); Al−Rh−Ru Ti−Dy−Si−Sn (Tb) B–Ti–Al–Ge (Sn, Nb)
Al−Cu−Ir (Rh), Al–Mg–Ca Ti–Al–Si–Ge; B–Ti–Ge (Al, Sn, V, Nb)
Al (B)−Ti,* Al (B)−Nb,* Al−Ta,* Si−Al−O−N−Ti (Zr) B−C−Si−Ti*
B−Nb (Si)−Ti,*Al−Ti−Nb (Ta),* B−Fe−Nd−Co
Ti–Ni–Sc (Zr, Ru, Os, Y);
Ru (Ti)–Rh–Sc; Zr−Co−Ir
Cu−Ti−Zr; Ti–Al–Ga
Ti–Si–Ga (Zr, V)

* CALPHAD approach is used

research teams within both the Institute and other scientific organizations in Ukraine and abroad. The Department’s
efforts in the field of physicochemical analysis and thermodynamics were firmly integrated into the global scientific
process. This is evidenced by our numerous publications in recognized international journals and participation in
international projects and prestigious international conferences.
Titanium alloys were traditionally studied by Eremenko since the early postwar years of this work at the
Academy of Sciences of Ukraine. In recent years, the Department paid much attention to multicomponent titanium-
and aluminum-containing systems, primarily as a basis for alloys with high specific strength (heat resistance). They
are titanium alloys with silicide, boride, metallide, and complex hardening phases and alloys based on titanium
aluminides. The research concentrated on the Ti–Si–X1–X2…, Ti–B–X1–X2…, Ti–Si–B–X–…, Ti–Al–X1–X2…,
Ti–Sn–X1–X2…, and Ti–Pn–X1–X2… systems and their constituent binary and ternary systems (where Pn is a
platinoid and Xi is a d- or f-metal or a p-element). The phase equilibria are conventionally studied in a wide range of
compositions and temperatures, including the region of equilibria involving the liquid phase. The physical and
mechanical properties are examined in collaboration with the Departments for Phase Transitions and Strength and
Plasticity Physics at the Frantsevich Institute for Problems of Materials Science.
The Ti–Si–Al system proposed by Eremenko to be examined in 1991 became the pioneer in the cycle of
studies on phase equilibria in the Ti–Si–p-element and Ti–Si–d-metal systems and their ternary combinations. The
Ti–Si–Ga, Ti–Si–Sn, Ti–Al–Ga, Ti–Si–Ge–Al, Ti–Si–Sn–Al, Ti–Si–Zr, Ti–Si–V, and Ti–Si–Zr–Al systems were
studied [3]. The composition ranges of the two-phase (βTi) + (Ti5Si3) eutectic and the solubility of doping
components in titanium silicide and (βTi) were established; the optimal combinations of doping components and
their concentration in TICAD alloys were justified. With a view of increasing the effectiveness (plasticity) of
TICAD alloys, the effect of doping with rare-earth metals was additionally considered: Ti–Dy–Si–Sn alloys (and
Ti–Dy–Si and Ti–Dy–Sn components) were studied [4]. It was shown that the mechanical properties of Ti–Dy–Al
alloys in the composition ranges of question were inferior to those of Ti–Dy–Sn alloys, and the mechanical
properties of Ti–Al alloys to those of Ti–Sn alloys. Following successful mechanical testing of alloys with tin, a
series of studies on the phase diagrams and properties of Ti–Sn and Ti–Sn–Al (Zr, V, Dy) alloys was undertaken. It
was found out that the optimum combination of strength and plasticity was observed near the phase boundary
(Ti) / (Ti) + (Ti3Sn), and Ti3Sn compound had high plasticity unusual for metallides, exhibited abnormally low
Young’s modulus at room temperature, and underwent a first-order diffusionless transition close to 75°C.
The phase equilibria and mechanical properties of multicomponent Ti−B−X1−X2... and Ti−Si−B−X−…
alloys, such as Ti−B−Al−Ge (Sn, Zr, V, Nb), Ti−Si−B−Al (Sn), and Ti−Si−B−Al−Sn−Zr, and their constituent
binary and ternary systems, such as Ti−Al (B), Nb−B, and Ti−B−Al (Si, Ge, Sn, V, Nb, Mo), were examined. The
composition ranges of the two-phase (β-Ti) + (TiB) eutectic, distribution of doping p- and d-elements between the
matrix and hardening phase, and their effect on heat resistance were established. Ternary Ti6Si2B compound (with a
hexagonal structure of Fe2P type (Ni6Si2B)) and the three-phase ternary (Ti) + Ti6Si2B + (Ti5Si3) eutectic involving
this compound were found, which was an interesting result of the cycle of studies on Ti–Si–B–X… systems. The
eutectic is highly fine (submicron hardening phases) and homogeneous, has a nearly optimum content of hardening
phases (~30%), and contains less brittle silicide–boride versus silicide and a low amount of silicon in the titanium
matrix (1.0–1.5 at.%) [5]. The composition ranges of the fine eutectic structure in the Ti–Si–B and Ti–Si–B–X
systems (where X is Al, Sn, or a combination of Al, Sn, and Zr) and melting points were determined. In terms of
physical and mechanical properties, the alloys hold much promise for aerospace and automotive applications as
structural materials with high specific strength and heat resistance, in particular, for parts of adiabatic engines that
perform in a heated state and, perhaps, are subjected to abrasive wear.
The Department’s new studies in the development of the titanium-related area focused on alloys based on
titanium aluminides doped with group V metals (Nb and Ta) and boron. Quaternary Ti–Nb(Ta)–Al–B and Ti–Nb–
Ta–Al systems and their constituent binary and ternary Ti–Al, Nb(Ta)–Al, Nb–B, Ti–(Nb, Ta)–Al, Ti–Al–B, Ti–
Nb–B, and Nb–Al–B systems [6, 7] were examined in cooperation with the Research Center ACCESS e.V.
(Aachen, Germany). The doping of titanium aluminide was intended to increase the fracture toughness and

plasticity of alloys through finer particle size of the two-phase α2 + γ structure and change in the shape of α2 and γ
plates. Alloys containing Ta (which belong to the fourth generation of titanium aluminide alloys) are particularly
interesting since they can undergo massive transformation to form metastable supersaturated γm solid solutions that
disintegrate when heated to produce a specific convoluted α2 + γ microstructure. It is shown that doping with boron
or borides additionally refines the structure. The alloys are considered to be promising as structural heat-resistant
materials for components and mechanisms of vehicles operating at temperatures above 600°C (to 800°C).
The advantages of combined experiments and thermodynamic modeling implemented in the CALPHAD
approach for studying the thermodynamic properties of alloys and phase equilibria are well known. Examples can
be found in papers published on this subject. The CALPHAD approach permits a proper description (and
representation in phase diagrams, as shown in Fig. 2 [8]) of not only phase transitions, which obey the Gibbs phase
rule, but also second-order transitions, whose experimental study is quite complicated. The need to involve second-
order (and higher) transitions into the Shiloh reaction scheme for a complete description of phase transitions in
systems where they occur has been long evident. Nevertheless, this aspect was addressed in detail only in a very
recent paper by a combined team from the Department for Physical Chemistry of Inorganic Materials and the
Research Center ACCESS e. V. A method is proposed to represent second-order transitions in the Shiloh reaction
scheme used in our own studies [8].
The phase diagrams of systems containing platinum group metals are traditionally studied by the
Department previously led by Valentin Eremenko. As a progress to these efforts, ternary systems based on the
binary Ti–Al system containing platinoids have been actively studied in the last decade. Like d-metals of groups V–
VI (Nb, Ta, Cr, W), platinoids are regarded as effective doping additions in titanium aluminide alloys since they
can improve both mechanical properties and corrosion behavior. The Department examined the phase equilibria and

Fig. 2. Portion of the vertical section of the Al−Fe−Ta system at 2 at.% Ta isopleth: dashed-and-dotted
and dotted lines show second-order transitions (magnetic and chemical ordering, respectively) [8]

a b
Fig. 3. Ranges of thermodynamically stable quasicrystalline phases in the ternary Al–dM1–dM2
systems with icosahedral (a) and decagonal (b) structures (dM2 is a d-metal with a more filled d-shell):
the figure is taken from [10] supplemented with data (italics) reported in [11–14]

constructed the phase diagrams of the Al–Ti–Rh (Pd, Pt) systems over the entire composition range (with Rh) or at
platinoid content lower than 50 at.% (with Pd and Pt). The phase diagrams are very complex and characterized by
the formation of numerous ternary compounds (for example, they reach ten in the Al–Ti–Pt system, many of them
have been first found [10]), extensive regions of ordered solid solutions based on βTi, and solid-state structural
transformations. The solubility of the third component in α2- and γ-phases involved in three-phase equilibria with
ternary metallides or a solid solution of CsCl structure is low in all systems.
New research efforts for the last 20 years have concentrated on aluminum-based quasicrystal forming
systems. The research findings on the Al–dM1–dM2 systems, where dM2 is Pd, Ni, or Cu⎯Al–Pd–Cr (Mn, Fe, Co,
Ni, Re, Ru, Rh, Ir), Al–Ni–Cr (Mn, Fe, Re, Rh, Ir, Pt), and Al–Cu (Rh, Ir)⎯are summarized in [10]. Stable
decagonal quasicrystals have been recently revealed in the ternary Al–Cr(Mn)–Fe [11, 12] and Al–Ir–Os [13]
systems. These findings contradict earlier conclusions on the decisive role of elements at the end of long periods
(Cu, Ni, Pd) in the formation of stable quasiperiodic structures and open up new prospects in the search for
aluminum-containing quasicrystals in systems formed by quite common and cheap (compared to platinoids) 3d-
metals (starting from vanadium) that may be of interest for practice. Figure 3 shows the composition ranges of
stable ternary quasicrystalline phases with icosahedral (Fig. 3a) and decagonal (Fig. 3b) structures. The efforts are
underway in close collaboration with the Institute for Microstructure Research (Jülich, Germany).
After 1990, the Department’s studies on the compatibility of materials concentrated on solid-phase
chemical kinetics and reaction diffusion. Reaction pairs such as Ni–Bi, Ni–Zn, Co–Zn, Ni–Sn (Fe, Cr)–B, and
chromium steel (13% Cr)–B and wear resistance of boride coatings on iron–chromium alloys and chromium steels
were examined. The kinetics of dissolution of iron–nickel and iron–chromium alloys in liquid aluminum, of nickel
in liquid bismuth and its alloys, and of nickel and cobalt in lead-free tin-based solders was studied. The proposed
kinetic theory [15] was used in discussing experimental data on the kinetics of formation of intermetallic layers at
the interfaces between condensed phases.
Eremenko’s studies on the thermodynamic properties of alloys were continued. The method of
electromotive forces was used to examine systems formed by rare-earth metals with Si, Ge, Bi, Cu, and metals of
group VIII (Fe, Ir). The thermal characteristics of rare-earth-metal silicides and germanides in a wide temperature
range from 50 K to temperatures above the melting point of compounds were studied jointly with the Department
for High-Temperature Chemistry and Thermodynamics of Refractory Compounds. Calorimetric measurements of
melt mixing enthalpies were substantially extended. Data for the majority of systems were obtained for the first

time in world practice. Melts of lanthanides with 3d metals (Mn, Fe, Co, Ni, Cu), noble metals (Ag, Au, Pd, Рt), and
nontransition metals (Al, Sn, Sb, etc.) being of great practical importance and Ag–Ca, Ag–Eu, Ag–Yb, Cu–Eu, Cu–
Yb, La–Pd, Ce–Pd, La–Pt, Ce–Pt, Eu–Pd, Eu–Pt, Yb–Pd, Yb–Pt, Al–Eu, Al–Yb, Eu–Sn, Ce–Sb, Co–Sb, Fe–Sb,
and other melts were examined; thermodynamic studies of ternary systems (Ce–Co–Sb, Ce–Fe–Sb, Al–Fe–Nb)
were started. Methodological improvements allowed successful examination of melts based on liquid Sm, Eu, Yb,
and Lu, which are the most challenging for experimental studies among lanthanides. Data on the thermodynamic
properties of phases in solid and liquid states in binary systems of rare-earth metals with gallium, carbon, silicon,
germanium, tin, and lead in the above-mentioned semiconductor systems, as well as available data on phase
diagrams, have been systemized in a series of reviews published in preprints and collected papers of the Frantsevich
Institute for Problems of Materials Science. The results of the thermodynamic studies were included in national and
foreign handbooks on the thermodynamic properties of substances.
The continuation and development of the research efforts pioneered by Valentin Eremenko are living
memories of the remarkable scholar. The grateful memory of the fascinating individual willing to communicate
with, carefully and kindly listen to, and support everyone who needed it, both in matters of work and life, will
remain forever in the hearts of all people who were lucky enough to meet him in living human communication at
different life stages—students, post graduates, doctoral candidates, and colleagues.

Photo 1 of 1978:
left to right⎯V. E. Listovnichii (in 1987–1990, Head of
Department for Physical Chemistry of Inorganic
Materials, Doctor of Chemical Sciences), N. D. Lesnik
(PhD in Chemical Sciences), and T. Ya. Velikanova
(since 1990, Head of Department for Physical
Chemistry of Inorganic Materials, Doctor of Chemical

Photo 2 of 1986:
right to left⎯G. M. Lukashenko (in 1977–1990,
Head of Laboratory for Thermodynamics of Metal
Alloys, Department for Physical Chemistry of
Inorganic Materials, Doctor of Chemical Sciences)
and V. R. Sidorko (since 1990, Head of
Laboratory for Thermodynamics of Metal Alloys,
PhD in Chemical Sciences)
Valentin Eremenko and his followers

The author is very grateful to K. E. Kornienko for the assistance in preparing the paper and to
A. A. Bondar, M. V. Bulanova, V. R. Sidorko, and V. G. Khoruzha for the material provided for discussion.

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of Ti–Dy–Si–Sn alloys,” Intermetallics, 14, 435–443 (2006).
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Silicide or Boride–Germanide Phase, STCU Project 3382, Final Report (2006–2009).
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Alloys Compd., 493, 99-104 (2010).
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Materivaloved. NAN Ukrainy, Kiev (2002), p. 315.