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in steels

H. K. D. H. Bhadeshia

Table 1

Mole fraction of

alloying element - UAF-"M.' J mol-I M s' K Ref.

Fe-O'O2C 1310 655 4

Fe-O'O6C 2240 415 3

Fe-O'O6C 1657 415 4

Fe-O'!44Ni 750 655 2

Fe-O'233Ni 1120 415 2

transformation in pure iron, as determined by

Kaufman et al.7

'\f* = the Zener ordering term, calculated as in Refs. 5

and 8

rl = activity coefficient of element i in phasej

R= gas constant

An estimate of the magnitude of the driving force MM:«' T= absolute temperature

available at the martensite-start temperature M. of steelsis x= mole fraction of carbon.

an important prerequisite for a detailed understanding of

the nucleation and growth characteristics of ferrous The third term in equation (1) can be expanded as

martensites. RT In (rc/rt) = LVlc -LVll: (5rr('\~s - ,\S~S). (2)

Early investigations of Fe-C alloysl,2 indicated that

~FM-«'is essentiallyindependentof the M. temperature (and where '\!l"c1' = partial molar heat of solution of carbon in

hence of the carbon content). However, lmai et a/.3 used ferrite and in austenite respectively and ,\~~ l' = the partial

statistical thermodynamics to demonstrate that I~FM:«'I molar non-configurational eutropy of solution of carbon in

monotonically increases with carbon content. Bell and ferrite and in austenite respectively.

Owen4 subsequently confirmed this conclusion using Bell and Owen chose ,\Hl: = 40 133 J mol-I (from the

Fisher's methodSfor extrapolating the free energy curves of work of Ellis et al.9) and in agreement with Fisher took

ferrite and austenite. Table 1, which contains some of the

LVl~= 85834Jmol-l. However, Lobo and Geiger 0

information of Refs. 3 and 4, not only illustrates the recently determined LVl~ to be 111918J mol-I at

sensitivity of ~FM-«' to the carbon content, but also shows temperatures below 1000K, and pointed out that their

that ~FM-«' for steelscan be rather high compared with, for experimental data were free from various 'intercept effects'

example,'carbon-free Fe-Ni martensites. which had dogged earlier investigations. Similarly, for

Since the above pioneering investigations, substantial T<1000K, they deduced '\~s=51.44Jmol-IK-I.

new and relatively accurate thermodynamic data have There seemto be no data on the variation of LVl~ or ,\~s as

become available; the purpose of the present work was to a function of x. However, Lobo and Geigerl found that

reassessand extend the results of the earlier investigationsin LVll: and ,\S~Sdo in fact vary with x. Furthermore, sincethe

the light of the new data. data of Ref. 11 were determined at relatively low

temperatures,the relationships the authors deducedshould

RESULTS be the most reliable for the present purposes.From Refs. 10

The M. temperatures utilized in all of the calculations and 11,

presentedbelow are due to Greninger,6

RTlnr':;= 111918-5r44TJmol-1 . . . . . (3a)

Fisher method RTln rl: = 35129- 7.639T

Fishers and Bell and Owen4 used the following expression +(169105-120.4T)x J mol-I. . (3b)

to determine the free energy change accompanying

martensite formation

~FM:«' = (l-x)~F~;« +(I-x)RTln (IF./r~.) RTln rc= 76789-43.8T

rt

+xRTln (rc/rt)+~f. . (1) -(169105-120'4T)x (3c)

176 Bhadeshia Martensitic transformation in steels

the following expressionwas derived using the exact activity

equations of Ref. 15

.:\FY-.' = 2xRTln x+xlL\H"c-l\jlt

- (.:\~s- L\S~s)T

+ 4m. - 6<1>yl

-4RT(1-x) In (1-x)+5RT(I-2x) In (1-2x)

by-1+3X

-6RTxln by+1-3x

I

I

-6RT(1-x) In 1 1-2Jy+(4Jy-1)x-~11

2Ty(2x-

+ 3RTx In (3 -4x)

+ 4RTx In ~5X

~ 1

0.+ 3 5x - I

where

= 19-6x(2/«+3)+(9+16J«)X211/2

<>«

= 11-2(1+ 2/y)x+ (I +8Jy)x211/2

<>y

J«,y= I-exp (-W«,y/RT)

Wy= 8054Jmol-1 (Ref, II)

The L\H and 68.s values were again represented by the data

of Lobo and Geiger. 10,II

The driving force curve calculated using equation (6) is

1 Variation of free energy change (accompanying also in Fig. I.

martensitic transformation at M. temperature) as

function of carbon content: curves 1 and 2 corres-

pond to present analysis. using methods indicated. Imai, Izumiyama, and Tsuchiya method

whereas other curves are due to Bell and Owen4 and This is essentially a statistical-thermodynamics method,

Imai et a/.3 and the final equation is given as3

£\£1'-0,= x(~ - Fi::)

I

+RTII xln

(- x~ /~,

1-2xJ

rc

RTln-ri=45668-15.56T. . . . . . . . . (4) + ( --:.-.

XZ ) (}.R T - P I - X /2

I-x I-x

Leaving the other terms in equation (1) unchanged,~Fk1~.'

was recalculated, and the results are presentedin Fig. 1,' +(l-x)L1F~-;. (7)

where

Lacher. Fowler. and Guggenhiem method

The thermodynamic formalisms of Lacherl2 and of Fowler

Pc-Ft = <I>~.-c-<I>~.-c-RTln I~/. . (8)

and Guggenhiem 13 were first elaborated and applied to and

steels by Aaronson et al.14 Shiflet et al.ls recently corrected

and reassessed theseresults and, following the proceduresof !l= 1/41{1-exp(~)}2 {2-exp(~)}

Ref. 14, provided explicit expressions for the calculation of

L\p-a,*. In order to cope with their finding that the average

carbon-carbon pairwise interaction energy in ferrite, i.e. Wa,

-2(~)exP(~)fz . , (9)

is negative, they representedthe activity of carbon in ferrite

where <I>~.-cand <I>~.-crepresent the iron-<:arbon pairwise

aa by the equation

interaction energiesin ferrite and austenite,J~Y represents

~-L\S"xs T the partition functions concerning the oscillation state of

Inaa=lnxa+

RT

(5) carbon in ferrite and austenite,and ifcY representsthe

partition functions concerning the electronic state of carbon

Specifically, equation (5) was used instead of equation (4) of in ferrite and austenite.Z is the coordination number of the

Ref. 15. However, this approximation is valid only for small austenitelattice. p is a constant related to the strain energy

Xa and cannot be satisfactory for martensite whenever the due to the tetragonality caused by a carbon atom in the

alloy concerned contains a substantial amount of carbon. ferrite lattice.

Bhadeshial6 recently analysed the accurate data of Lobo lmai et al. usedan expressiondue to Gilbert and Owen 17

and Geiger,IO and contrary to Ref. 15, found Wa to be to representl\F~;.. However, comparison with the data of

positive, with an averagevalue of 48570 J mol-I. Hencethe Kaufman et al.7 shows that this results in a large

overestimation of Il\P-.'I, and in addition, exaggeratesthe

sensitivity of l\FM:.' with respect to M.. For example, at

* A.F"-., refers to the free energy change accompanying the x = 0'02, Il\FM-.'1would be overestimatedby - 330 J mol-I

transformation of austenite to supersaturated ferrite and may be and at x = 0,06 the overestimation would be by

converted to A.P-.' by the inclusion of the A.f* term. 550Jmol-l.

Bhadeshia Martensitic transformation in steels 177

Furthermore, the inclusion of the term Ip(xj(l- x»21 in the L\FM-a'values calculated by the Fisher method tend to

equation (7) is not understood, since this really represents approach the magnitude of the stored energy at the higher

the change in internal energy accompanying the trans- carbon levels, sufficient driving force would not be available

formation of supersaturated ferrite to tetragonal for transformation should there exist an appreciable barrier

martensite.S,s Again, this would tend to exaggerate the to the nucleation of martensite. Although the M.

sensitivity of IAFT-i-.'I to Ms, and would substantially temperaturesfor evenhigher carbon steelsdo not seemto be

increase the magnitude of the driving force. well established, if we take the M. of 1.95 wt-%C steel

Imai et al. take (q,}.-c-q,~.-c) to be approximately to be - 35°C,20the Fisher analysiswould predict

equal to Mf:Y -., i.e. the heat absorbed when one mole of MM-a' = - 890 J mol-I while the LFG treatment gives

carbon is transferred from the austenite to the ferrite (or in MM.),a' = - 1450J mol- 1. This implies that there is a

other words, the enthalpy change, referred to as - AGj by maximum in the LFG curve 2; this maximum was estimated

Zener1s). However, they use a value of 23246 J mol-1 for to reach MM-a' ~ -1250 J mol-I, On the other hand, the

MY-., a value which does not agree with that given by Fisher curve continues to rise. It therefore seemslikely that

Zener (to whom they refer) or with a more recently derived the LFG calculations are nearer the true situation.

quantity of 39245 J mol-1 (Ref. 14, p. 756). Additionally, the LFG method is lessempirical and a more

In order to deduce the last term of equation (8), Imai systematic method of extrapolation compared with the

et al. refer to the Fe-C equilibrium phase diagram, a Fisher technique.

situation in which the following equations should apply3 In conclusion, it appears that the free energy change

accompanyingmartensite formation at the M. temperatures

~=ln l ~ l -ln l ~ I +~ . . (10) of steelsis rather lessthan was originally thought, and varies

RT I-x Y I-x . (I-x Y) between 900 and 1400J mol-I. It is possible that a better

estimate is given by the LFG extrapolation, in which case

the above range narrows to between 1100and 1400J mol-I

for x ~ 0.01-0.06. In addition, while L\FM-a'does vary with

carbon content, the variation is neither monotonic nor very

large,

ACKNOWLEDGMENTS

The author is grateful to the ScienceResearchCouncil for

the provision of a research fellowship and to Professor

R. W. K. Honeycombe for his interest in this work and for

the provision of laboratory facilities.

REFERENCES

1. L. KAUFMAN.S.V. RADCLIFFE.and M.COHEN: 'Decomposition of

austenite by diffusional processes' (ed. V. F. Zackay and

H. I. Aaronson), 313; New York, 1962, Interscience.

2. L. KAUFMAN and M. COHEN: Progr. Met. Phys., 1958,7, 165.

3. Y. IMAI, M. IZUMIYAMA, and M. TSUCHIYA: Sci. Rep. Res. Inst.

Tohoku Univ., 1965, A17, 173.

4. T. BELL and W. S. OWEN: Trans. Met. Soc. AIME, 1967, 239,

1940.

5. J. C. FISHER: Met. Trans., 1949, 185, 688.

DISCUSSION AND CONCLUSIONS 6. A. B. GRENINGER: Trans. ASM, 1942, 30, 1.

From Fig. 1 it is evident that the curvescalculated using the 7. L. KAUFMAN, E. V. CLOUGHERTY,and R. J. WEISS: Acta Metall.,

new thermodynamic data differ substantially from those of 1963,11,323.

Refs. 3 and 4. At all carbon levels, and especially at the 8. C. ZENER: Trans. Met. Soc. AIME, 1946,167,550.

higher carbon contents, the driving force for martensite 9. T. ELLIS,I. M. DAVIDSON,and C. BODSWORTH:J. Iron Steel Inst.,

formation

. is lower: L1FM~a' .

is also lesssensitiveto variations

m the carbon content. The agreement between the

1963, 201, 582.

10. J. A. LOBO and G. H. GEIGER: Metall. Trans., 1976, 7A, 1347.

II, J. A. LOBO and G. H. GEIGER: ibid., 1359.

calculations using the Fisher method and the Lacher, 12. J. R. LACHER: Proc. Cambridge Phi/os. Soc., 1937,33,518.

Fowler, and Guggenhiem (LFG) theory is reasonableand it 13. R. H. FOWLER and E. A. GUGGENHIEM: 'Statistical

is satisfying that both curves exhibit the same trends. The thermodynamics'; 1939, New York, Cambridge University

minima in these curves and the inflexion in the Bell and Press.

Owen curve are due to the increasing (with x) reduction in 14. H.I.AARONSON,H.A. DOMIAN, and G. M. POUND: Trans. Met. Soc.

the free energy of martensite relative to austenite by the AIME, 1966, 236, 753.

Zener ordering effect. 15. G. J. SHIFLET,J. R. BRADLEY,and H. I. AARONSON:Metall. Trans.,

It seemsdifficult to decide which of the two new curves 1978, 9A, 999.

16. H. K. D. H. BHADESHIA: Met. Sci., 1980, 14, 230.

better represents the true situation. For the set of M.

17. A. GILBERT and W. S.OWEN: Acta Metall., 1962, 10, 45.

temperatures used in the calculations, both the Fisher 18. C. ZENER: Trans. Met. Soc. AIME, 1946, 167, 513.

method and the LFG method are able to account for (at 19. J. W CHRISTIAN: Proc. Int. Conf. on 'Martensitic trans-

least) the stored energy of an isolated plate of martensite formations', ICOMA T 1979, Boston, USA, 220.

which amounts to - 700 J mol-1 (Ref. 19). However, since 20. G. KRAUSS

and A R MARDER:Metall. Trans., 1971,2, 2343.

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