5 Introduction to “Thermodynamics of Martensitic

Transformations”
in Acta Metallurgica (1958)

and “Thermodynamics of Martensitic

Transformations”
published in Martensite-A Tribute to Morris Cohen (1992)

I have had the pleasure of associating with Mats for over 50 years, since 1953 when we were both students of
Morris Cohen in the Department of Metallurgy at M.I.T. The subject paper was prepared by Mats and myself
for Morris Cohen’s Festschrift 80th birthday celebration. Our paper reviews the methods for employing ther-
modynamic data to describe martensitic transformations of parent phases to daughter phases of the same
compositions. In the early 1950’s this was not a very popular idea, especially at MIT where the practicing
faculty included Carl Wagner, John Chipman and John Elliot who were giants in the fields of experimental
and theoretical chemical as well as process metallurgy. By contrast, the graduate students in physical metal-
lurgy were researching athermal and isothermal martensitic transformations, spinodal decomposition, aging
reactions, tempering as well as pearlitic and bainitic reactions in steels. Mats Hillert’s arrival from Sweden
exposed this active research group to the ideas of Hultgren and Johannson and broadened the scope that
we envisioned for thermodynamics as an important tool in our research. Mats also brought a very tolerant
view toward consideration of a wide variety of ideas that others held in approaching these topics. The first
few pages (Figures 1–5) present the salient experimental and theoretical features of the classical (isother-
mal) and martensitic (constant composition) description of the thermodynamics of the iron-nickel system.
Pages 43 and 44 outline the method advanced to permit explicit numerical calculations of the equilibrium
phase diagrams and the driving force for diffusionless transformations. All these calculations were done by
hand by suffering though all of the missed minus signs! Nevertheless, the framework for the “Computational
Thermodynamics” was conceived, pioneered by the CALPHAD, Thermo-Calc and SGTE groups that Mats
and his students developed for the world in the past twenty years. Figure 6 published by Kubaschewski and
von Goldbeck (Kuba’s future wife Ortrude) in 1949 shows the same features displayed in Figure 3 for iron-
nickel alloys. However they completely ignored the composition at which the FCC and BCC phases have the
same Gibbs energy! This T0 − x0 relation, essential in the transformation behavior that we were observing
experimentally, was of no interest to the classical thermodynamicists (Kubaschewski and von Goldbeck) who
carried out the meticulous research required to generate Gibbs energy vs. Composition curves for the BCC
and FCC phases in Fe-Ni alloys at 527 ◦ C and 327 ◦ C. Figures 6–11 and Table 1 illustrate other examples of
martensitic and classical thermochemical data that are related explicitly. Included are examples of T0 − x0
curves for hydrated nitrates that were called “EGC” curves by Harry Oonk in 1968 (Figure 9). Harry Oonk
was completely unaware of the way metallurgists were looking at phase diagrams. It is interesting to note
that in 1953, when I told Carl Wagner about Zener’s Equation 2, he shook his head, cleared his throat and
informed me that in 1908 Van Laar showed that the correct description for the binary Fe(i)-Ni(j) system is
bcc
given by Equations 6 and 7, where GNi , the Gibbs free energy of BCC nickel, was an important descriptor of
the FCC and BCC phases of the Fe-Ni system, even though BCC nickel is unstable.
Equations 8–15 expand of the Gibbs energy to multicomponent systems using the Redlich-Kister model.
Mats Hillert, Bosse Sundman and their associates have developed a wide variety of models that describe
solid and liquid oxide, carbide, ionic and composite phases that have been applied to a wide variety of
multicomponent systems. Figure 12 discusses the differences between recent measurements of the variation
of the enthalpy of transformation of ferrite and martensite to austenite in Fe-Ni alloys in order to evaluate
the energy stored in the martensite by defects. Equations 16–18 reviews the description developed by Fisher
and Zener for the energy difference between ordered tetragonal martensite and ferrite.
In the following section Mats revisited the formation of martensite as an adiabatic process, with much the
same result as the one he obtained 35 years earlier (reference 30). Equations 19–28 can be used to calculate
the difference between the Ad (the lowest temperature at which austenite can form from martensite which is
being deformed) and Md (the highest temperature at which martensite can be formed from austenite which
88 T HERMODYNAMICS AND PHASE TRANSFORMATIONS

is being deformed). The Ad and Md temperatures bracket the T0 temperature. For a Fe-30Ni alloy, the value
of Ad − Md is calculated as 95C in agreement with experiment. Typically, Mats states that “one did not have
any right to expect such an agreement” and then goes on to further discuss the questions these findings raise.
In the final sections of this paper Mats discusses two additional relevant problems of current interest: the
interaction of diffusion with martensitic transformations which could develop into a bainitic transformation,
and the relation of martensitic growth conditions and Paraequilibrium in iron-base alloys.
These final sections illustrate how far the field has developed in the 1953–1992 period. Mats Hillert and
his students played key roles in these developments.

Larry K AUFMAN
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