PHASE

TRANSFORMATIONS

IN IRON-RUTHENIUM HIGH PRESSURE?
LARRY KAUFMAN3

ALLOYS

UNDER

L.

D. BLACKBURNS,

and MORRIS

COHEN1

At atmospheric pressure, iron-~thenium alloys containing less than 12 atom percent ruthenium exhibit a diffusionless a(b.c.c.) s y(f.e.0,) transformation on heating and cooling, while alloys containing 12-36 atom percent ruthenium exhibit a diffusionless e(h.c.p.) s y(f.c.0.) transformation. High pressure displaces the a + y reaction to lower temperatures, but shifts the E z y reaction to higher temperatures. These effects appear to be governed by the pressure dependence of the thermodynamic properties. The application of pressure also produces a new transformation, cc* E, at room temperature in alloys which contain the a-phase at atmospheric pressure. Pressure-temperature diagrams at constant eomposition thus contain triple points involving a(b.c.c.f, y(f.c.c.) and e(h.c.p.). As the ruthenium content is increased, the t,riplo-point pressure decreases si~ificantly. Comparison of the alloy pressur~~mperature diagrams with the high-pressure behavior of iron demonstrates that the pure metal also exhibits a triple point, at which the high-pressure, low-temperafor ture phase is E. A thermodynamic analysis has yielded values of AF a+~[ 211 pure iron, thus establishing the relative stability of the e-phase in iron. TRANSFORMATION DE PHASE SOUS PRESSION ELEVEE DANS LES ALLIAGES Fe-Ru

Lors d’un chauffage ou dun refroidissement B la pression atmospherique, les alliages Fe-Ru eontenant moins de 15% at. Ru, poss&lent une transformation sans diffusion a(c.c.) + y(c.f.0.); dams les memes conditions, les alliages contenant 12 a 36 % at. Ru possedent une transformation sans diffusion e(h,c.) + cc(o.f.e). Sous pression &e&e, la reaction x - y se deplace vers des tempkratures plus basses elors que la transformation E -+ y se deplace vers des temperatures plus &levees. Ces effets semblent 6tre en relation avec l’influence de la pression sur les proprietes thermodynamiques. L’application d’une pression produit Bgalement une nouvelle transformation, a + E, qui apparait it la temperature ambiante dans les alliages contenant la phase a 8. la pression atmospherique. Les diagrammes pression-temperature, a composition con&ante, contiennent des points triples pour lesquels existent siInultan~ment les trois phases a(c.c.), y(c.f.c) et l (h.c.p.). Lorsque la teneur en Ru s’accroit, on observe une diminution signifieative de la pression au point triple. La comparaison entre les diagrammes pression-temperature et le eomportement sous haute pression du fer PUP, montre que le metal pur possede aussi un point triple pour lequel la phase l existe, sous haute pression et basse temperature. Une analyse thermodynamique a fourni des valeurs de A&-e [T] pour le fer pur. Ceci prouve la stabiliti! relative de la phase E dans le Fe. PHASEN~TMWA~DL~GE~ UNTER IN EISE~-RUTHE~~U~~-LEGIERUNGE~ HOHEM DRUCK

Eisen-Ruthenium-Legierungen mit weniger als 12 At. - % Ruthenium zeigen eine diffusionslose Unwandlung a(k.r.z.) $ y(k.f.2.) beim Hochheizen und Abkiihlen unter hohem Druck. Legierungen mit 12-36 At. - ‘4 Ruthenium zeigen eine diffusionslose e(hexagona1 dichtest gepackt) ;=t y(k.f.z.)Umwandlung. Hoher Druck versohiebt die a + y-Reaktion zu niedrigeren Temperaturen, jedoch die E - y-Reaktion zu hoheren Temperaturen. _ Diese Effekte soheinen duroh die Druckabhiingigkeit der thermodynamisohen Eigenschaften kontrolliert zu werden. In Legierungen, welche die a-Phase bei atmosph~risch0m Druck enthalten, fiihrt die Einwirkung eines Druckes ebenfalla zu einer neuen DL e-Umwandlung bei Raumtem~rat~. + Druck-Tem~raturDiagramme enthalten folglich bei konstanter Legierungszusammensetzung einen Tripelpunkt zwischen den Phasen a(k.r.z.), y(k.f.2.) und e(hexagona1 dichtest gepackt). Mit zunchmendem Rutheniumgehalt nimmt der Druck am Tripelpunkt marklich ab. Ein Vergleich der Druck-Temperatur-Diagramme der Legierungen mit dem Verhalten von Eisen bei hohem Druck zeigt, daB beim reinen Metal1 ebenfalls ein Tripelpunkt auftritt, an dem E die Phase bei hohem Druck und niedriger Temperatur ist. Eine thermodynamische Analyst? hat Werte fiir AFa-e [T] in reinem Eisen ergeben und somit die relative Stabilit&t der e-Phase in Eisen sichergestellt.

1. INTRODUCTION

The application of high pressure may have important effects on phase relationships in metals and alloys. t Received May 6,1964. This research was sponsored by the Metallur~ Branch, Office of Naval Research, W~hing~n, D.C. under Contracts Nom 2600(00)-NR 031-627 with ManLabs Inc., and Nonr-1841-35 with the Massachusetts Institute of Technology, and is based on a doctoral thesis submitted to the Department of Metallurgy, M.I.T. in May 1963 by L. D. Blackburn. $ Formerly Department of Metallurgy, M.I.T., presently Lieutenant USAF, Air Force Materials Laboratory, WrightPatterson Air Force Base, Ohio. 5 ManLabs, Inc.. Cambridge, Mass. ff Department of Metallurgy, Massachusetts Institute of Technology, Cambridge, Mass.
ACTA METALLURGICA, VOL. 13, MAY 1965

For example, polymorphism becomes more common when both temperature and pressure are variables, rather than temperature alone. Pressure also changes the temperatures of melting and polymorphic transformations, and may thus permit a direct study of solid phases at temperatures beyond their normal range of stability at atmospheric pressure. Detailed studies of such effects may well provide new insight to the understanding of lattice stability of metals, and it is in this context that the present investigation on the iron-~thenium system was conducted. The iron-ruthenium phase diagram exhibits only

533

4 Vu. has been tentatively experiments cubic(3p6T7) hexagonal close-packed. Transformation temperatures for the diffusionless reactions were determined from electrical resistancetemperature curves.29 -0. these increments effects. A high-pressure study of the iron-ruthenium offers an intriguing possibility relationships at room duced in pure iron.f. and eventually pressure. y’ ruthenium an a 2 y transf or m a t ion. by two diffusionless Alloys containing less than 12 at.7 7. being varied from one specipossible thermal history men to the next to avoid produce a stable h. lographic observation of contamination pressure cell. while alloys con12 to 36 at.22 -0. and on the pressure dependence in pure iron. alloying with ruof the of pressure on the e.p. above 133 kb.~?ry reaction.m.) parameters Comparison of the of these alloys with the data of product as the These phases interact via a eutectoid Raub and Plate(l) shows that the metastable u and E. Atmospheric pressure experiand in a ments were conducted the high-pressure in an argon atmosphere.3 a/o Ru) 2 at approximately it is replaced tions. EXPERIMENTAL MATERIALS PROCEDURE AND for the b. mation : y(f. a(b.p.44 +0. Compositions. transformation pure iron. structures and volume relationare y ships of the four alloys used in this investigation listed in Table 1. therefore. this diagram suggests that additions of ruthenium to iron may progressively the transformation at atmospheric high-pressure pressure reaction. were conducted temperatures reaction. y. with as many as 17 cycles being obtained on a single specimen over a range of pressures. cm3/mol AV rz~(25”C) cma/mol AVe-~(25”c) oma/mol ___-0. both transformations are diffusionless. Temperatures were measured with chrouncorrected h.p.p. thus facilitating ture in question.c. the iron-ruthenium ruthenium.) and an extensive r(h.8 a/o Ru) + ~(23. VOL.(l’Vl) high-pressure Pressure calibration was based on the transitions in bismuth at 25. 2. Metallographic observations have indicated that the u z The molar volume from extrapolation y reaction is martensitic..7 kb.5 a/o Ru) 500”C. + h. Isobaric resistance-temperature cycles on a given specimen were recorded at ascending pressure increments. An entire heating and cooling cycle (25°C -+ 900°C 25°C) for each resistance-temperature in approximately 7-9 min.(9) volume. thenium may. B and C undergo an a + transformation varying the heating and cooling rates within the limits of the equipment. mel-alumel thermocouples of the cce y transformation for the effect.).534 ACTA METALLURGICA.5 to 100 at. “/o ruthenium undergo an E2 y It is the pressure dependence of these difsystem that are derived from the measured lattice parameters Plate(l) and Abrahamson.37 +0. solid solution extending with the hypothesis iron is h.‘2) fusionless reactions which is of interest here. Coupled assembly described elsewhere.16 -0. have the same composition y(9. relationships of the X-ray shown in Table 1 and data of Raub and gish.36 +0.c. y0 that pure lower Now.(1) This reaction is very slugphase transforma- parent phase.c.c.15 Alloy Composition. therefore.c.7 8.16 -0.6 kb and in thallium at 36.c. while alloy D TABLE 1. t AVa-y E VY - .8 15. 1965 three tion.19 -0.c. solid phases at temperatures below 1400°C: solid solutransfor- undergoes lattice phases.c. the X-ray of the strucof the Compositional extrapolation Several heating and cooling cycles were run at Metalof specimens showed no evidence materials used in the high- each pressure. accomplished from pressures might then verify that the reaction in the alloys is the same as that occurring in The compositions. however.c. curve was However.(3y4y5) low-temperature as either identified The structure polymorph face-centered of this high-pressure. an E* y reaction.20 -0. a/o A : D 5.(5*s) or phase diagram contains an from 23.35 to. temperature for clarifying the phase a pressure-in- CL y reaction but should raise the temperatures & It is well established iron undergoes transformation at a pressure of 133 kb.c.c. on heating and cooling. phase Judicious allow the production identification form of iron at pressures below 133 kb. exhibit taining x(4. had no effect on the measured transformation temperatures.15 -0. the data in Table Based on the generaliza1 indicate that pressure for the for tion that pressure stabilizes the phase of smaller molar should lower the transformation the E. and even with slow heating and cooling.p. Alloys A. structure and volume relationships of iron-ruthenium alloys Ru Structure at 25°C tc G( A Va-~t(25”C). 13.

p.) for this reaction.) was used to evaluate T. for the a s y reaction at higher pressures. 26I ATMOSPHERE 3 zoo 500 TE&K=ERAT”RE. Comparison of these figures illustrates quite clearly that at pressures above 42 kb. = 4(&f. the resistance-temperature curves revealed the Curie temperatures Ti. 2 and 3. the relation T. EXPERIMENTAL RESULTS lowers both Ma+“” and A.(1~12~13) A recent application of the regular solution model of Kaufman and Cohen(14)to the iron-ruthenium system has yielded values of APa+’ for the diffusionless tr~nsform~tiou as a function of temperature and cornposition.Y-” and Mr”) under atmospheric pressure are shown as a. function of composition in Fig. E replaces ct as the low-temperature phase. it was also assumed that T. pressure induces an E + Etr&nsformation. + A. 2. 1. the application of pressure FIG. + A. which is defined as the temperature at which AY”’ = 0 for a given composition. E. This G behavior is illustrated by the resistance-temperature curves shown in Figs. a new reaction replaces the CL y transf ormation in these alloys.. alloys A. He found that on applying it pressure of approximately 90 kb at room temperature.). This conclusion was verified by high-pressure X-ray diffraction experiments performed by Professor John Jamieson of the Department of Geology. Transformations at atmospheric pressure The transformation-start temperatures on heating (AZ+’ and AZ+‘) and on cooling (M. B and C contained both b. with the experimental values of 4(M. as the pressure is increased..c. I . Figure 2 presents the curves for all four alloys at atmospheric pressure and reveals the difference in hysteresis loops between the a ri: ^Jand E~ti:y transformations. 3.nd h. Figure 1 shows a comparison of these calculated values of T.c. In view of the excellent agreement shown in Fig. In addition to the transformation temperatures.BLACKRURN et ul. B and C. it is possible to calculate T&a s r). Both the resistance-temperature work and the X-ray diffraction experiments demonstrated that Eis not retained when 1. that is. the CI y s reaction vanishes and the E$sy reaction appears.c. 3. . Trans~o~~t~o~ at high pressures In alloys A. However. 1. of the u-phase. From this.: PHASE TRANSFORMBTIONS UNDER PRESSURE 535 MO- I 5 .“+‘. = g(M. 2. The present results are in good agreement with those of earlier investigat1ions. these findings are included in Fig. + A. Transformation temperatures and Curie temperatures of Fe-Ru alloys. i. u a. 1. Resistanee-temperature curves of alloy B at higher pressures are shown in Fig. university of Chicago.e. which is expected since y has the smaller molar volume (see Table 1).-C FJ 903 1 Resistance-temperature curves for Fe-Ru ELIIOJTJ at atmospheric pressure.. \ I I i is RUT(IENIUM 0 10 ATOM PERCENT 20 FIG. 1. Although a lack of thermodynamic data precludes a calculation of T&E + y).

Unfortunately E -+ a. E transformahad insufficient pressure capa- It is felt that one or both of the following explain this inability tion : (1) the equipment (2) the transformation gradual to be detected. 7. . this demonstrated. pressure for 7. OO 10 I I I 1 I 20 PRESSURE so . 13. Resistance-temperature curves for alloy at high pressures. MO 500 700 903 I in alloys A. utilizing isothermal resistancepressures for the u z E reac- tion occurs at lower pressures. but rather it reverts to u via the reverse reaction. Several experiments ure the transformation tion. However. 5.536 ACTA METALLURGICA. pressure cycles were performed in an attempt to measthese efforts were unsuccessful..7 at. In these experiments it is likely that E formed from y rather than cr.7% Ru show the variation of the transformation temperatures and T. factors may to detect the dc--. ‘A Ru alloy. and thus the resistance The first of these factors is not necessarily tent with the results of resistance-temperature where E definitely was produced. temperature accurately. In addition to the entree of the Es y reaction at high pressures. pressure range. B and C are presented in Figs. 40 so since the “settling” of the high-pressure cell on the first heating cycle always produced an irregular resistance- KILOBAf?S FIG. 4. pressure for 5. bility to produce appreciable transformation . which TEMPERAT”RE. the the pressure is released. these plots reveal that as the ruthenium content is increased. or occurs gradually over a broad change is too inconsiscycling. 4-6. VOL. subsequent cycles then showing only E = not be conclusively 1’. that is. the first cycle reactions possibility could may be u % y 2 E. in alloy C. 1965 FIG.7 at.~C 3. % Ru alloy. this reacThus. with pressure. Quantitative curve which was difficult to interpret behavior results of the transformation v: I0 Co FIG. Transformation temperatures vs. Transformation temperatures vs.

where AZ-Y dewith tem- The only exceptions in alloys creases as the pressure is raised. the agreement ured in alloy B.(16) of Ml’“. supporting No new transformations the conclusion alloys is E. pressure for 8. and calculated The l for this reaction the approximations dependence using the same pressure dependence behavior of alloy pressure. 2.(a 2 y) was carried out. occur with pressure is the C. transformation D at high the is inI that the pressure is governed by changes pressures $ A:‘Y I 900 t is shown in Fig. for the ironFIG. DISCUSSION 1. prohibits a similar calculathat E has the y reaction and M:+. I the variation to this generresult in the thermodynamic controlling alization factor. TO(u e to give a triple point.BLACKBURN et al. and A. are diffusionless. Transformation temperetures vs. In alloys A. Pressure dependence of a 22 y and E212y reactions The pressure transformation qualitative thus Mi+. This calculation is identical to thst used by Kaufman et al. The calculated considering required in the calculations. behavior or transformation This anomalous changes in Al++” or to changes mechanism in nucleation under pressure. of the pressure-temperasystems. dependence in these with of the diffusionless alloys the generalization phase is in that iron-ruthenium agreement pressure stabilizes the phase of smaller molar volume. cc& y reaction nickel system. pressure. % Ru alloy. Composition dependence qf the high-pressure transformati0n. as functions imate calculation and the driving forces at and pressure. 2 indicates y reaction values of AZ+7 are evidenced of in the data for of this M. temperatures at 16 kb. may be due to unknown perature and pressure..: PHASE TRANSFORMATIONS UNDER PRESSURE 537 creased. of the pressure transformations and At+?’ decrease with increasing prediction while MT’E and AfY A quantitative knowledge ence of those diffusionless of A Vu+y. 7. the ture diagrams 200’ FIG.8 at. reaction smaller is consistent molar volume. dependrequires a increase. the behavior with the fact suggesting properties B and that and T&E e I y) are raised as the pressure ! I I the E & y transformation tion for this reaction. of temperature Using the only available data for AFa+Y.(15) an approxof the pressure dependence A:?’ and T. The were meas- pressures for alloy A. I I I 0 10 20 30 40 PRESS"RE. A F+’ M.s An important the appearance transformations treated I 50 feature of the present of E as the high-pressure. . properties under pressure.u7) experimental somewhat in Table the u e Table 2 compares the calculated temperatures and transformation low. curves in these graphs are the boundaries between the single phase fields in this type of pressure-temperature diagram. 7) end There T&E JFs y) intersect. Thus. A. 7. 6. alloys. analogues for one-component investigation low-tempera- is ture phase in iron-ruthenium as binary Since the phase 4-7 may be Figs. phase that the high-pressure in the lower ruthenium 4. occur in this alloy. but at several has already disappeared T. Transformation temperatures vs.KILOBARS T.4 at. at atmospheric This alloy exhibits thermodynamic Unfortunately. pressure for 15. B and C.. % Ru alloy. the lack of thermodynamic In general.

kb 0 569 10 20 30 40 461 382 332 278 722 697 672 643 613 646 579 527 488 446 480 421 353 289 661 604 553 507 655 5s5 519 463 413 should.) with temperature formation of approximately 450°C. C. 13. These data demonstrate that the transformation pressure does not rise sharply with decreasing ruthenium conbent but varies smoothly to a value quite close to Fro. in The establishment immediately doubt. workos) by J. E. of course. 4-6. P. but to a lower pressure charof the triple point. the actual CI--+ E transformation Table 3 summarizes 90 kb and 130 kb.( tcG e). and T. pressure (P*) with t These alloys were kindly supplied by Dr. data do not extrapolate acteristic to a pressure of 133 kb at room However. 8 shows the compressure at a of the triple-point FIG. where of triple points nium alloys.c. Jamieson on ten alloys containing O-6 a/o ruthenium? itative information perature. (T. of the alloy data to pure iron is with the triple-point param1 2 ATOM I 4 PERCENT I 6 R”THENl”M I B P. the alloy pressure at 25°C. Variation of triple-point temperature composition. it is the experimental transformation of the direct u -+ E Therefore. reflections at a given pressure indicontents. The pressure points and temperature parameters Figs.p. additional temperature in pure iron. reflections which were observed in these alloys under pressures of approximately The increase in the pressure is deleading to number of h.(s) It should be emphasized positional variation that Fig. and T. I 0 0 JOHNSON PRESENT ET AL 124) INVESTIGATION shows that it exists. 8 and 9. for iron-rutheof the triple content) are *x5 --__ --_ ----_ 0 l l concluded the the diffusionless transformations (which vary with the ruthenium denoted as P. not the transAccordingly. Although the latter curve could not be quantitatively demonstration measured. suggests a comparison of these alloys with are still in pure iron.c. in which all the phase have been identified. Variation of triple-point composition. be a third branch intersecting at the triple point corresponding to T. . cates that the u ---f E transformation creasing with higher ruthenium the formation of more E at the test pressure. VOL. 1965 for 5. Stein and Davis. has yielded qualdependence of on the composition pressure at room temthe h. The extrapolation in very good agreement eters for iron proposed by Johnson.538 TABLE 2. S. 8.7 a/o Ru alloy at of experimental and calculated transformation high pressures temperatures P. McCallum and J. Comparison ACTA METALLURGICA.p. Abrahemson of the Watertown Amenal during the final stages of this investigation. in ironruthenium alloys do exhibit triple point behavior. 9. where the phase relationships This comparison is made in Figs. are plotted as functions of composi- tion.

Thermodynamics The transformation of h.216$ 6. perature.. This result also provides strong support for the validity From of the extrapolation these considerations of the triple-point pressures in Fig.c.3) This relation can then be integrated to yield an ex- pression for the free energy of E-iron: FyT] = Hoc + Fe + FE’[Tl - iyeT (2) where HOCis the enthalpy 133 kb. correspond state. (ll. S.55 2.O). Mossbauer effect in iron at and Jurat2*J and by Pipkorn is not ferromagnetic.c.c. that dT&P high-pressure have yielded no information However. by employing F”[T]. (lO.1).65 heat capacity of e-iron is considered in terms of lattice.02 2. However. 21) PYP[ T] (ref.p.96 4. trace of (11.p. An ya = yy. been verified ature form of iron is hexagonal conclusion has recently diffraction pressure X-ray close-packed.520 x lo-8T2) cma/mol $ The two values of B[T = O”K] given for f.\(Ref. 7. 8. (lO.695 $ 1150 6. E-iron is more stable than y-iron.O). McCallum and J. Previous iron.P reflections observed P es 130kb t. This is an imet aZ.c.e.0) and (10. (lO.061 8°K 432 432 cal ?’ mol . Thermodynamic cal H. moi 0 1303 Phase ?‘[ T = O”K] z.l).(1g~20) able value for the melting temperature known function point and Debye to the Lindermann 3. (lO.O).E@ is the magnetic capacity. (ll.O).c.O). These curves indicate that at T = As the temperbecause E has a AF”’ decreases and the known triple-point O”K. C. and (3) that the melting of h.O).3”C/kb.e. iron data on these iron-ruthenium in develproperties of the h.O).00 1.. 21) 0 Y E (31) 7.(“K)2 12 x 10-a 12 x 10-a cal pr mol 3wc( T] (ref.57 3. These parameters are then fixed by requiring: temperature perature of y 2 (1) that AFa+<[T] yield reasonable agreement with the calculated E at one atmosphere AFx’E[T] intersects at which equilibrium (i. by very high- function A F”“[ the temperature T]) . electronic and magnetic contributions : P m QOkb H. at O”K.(21) AFZ+E(=FE F”) terms of the parameters 8’ and Ho’. (ll..l).43 3.00 0. (ll. (a) to a high moment-high volume and a low moment-low volume . intersects the and that the high-pressure. of the iron-ruthenium low-temperThis data.“@’ indicate that h. form studies of the pure metal y reaction in this value of .p. (2) that A Fa+E[ T] yield a reasonat which AF”‘L[T]) AFa-<[T] experiments.@l) the in pure iron at atmospheric y has a still larger to be approximately the treatment portant piece of information Following in t!ie following of Kaufman t Recent measurements of the 25°C and high pressures by Nicol et al.3) (10. 5) GDQ[T] = C. Jamiesono*‘) Alloy composition. y and E iron. (10. (lO.(21) alloys can now be used to further advantage oping the thermodynamic of iron. Then.p. of AF”“. High-pressure X-ray diffraction results on the c( + e transformation at 25°C (after J.3) I::.C. ‘A Ru 0. it is found pressure and tempressure is analye&.O). (lO.BLACKBURN et al.c. (10. where [I f (1 + 10-4T) + yET + CDEw[T] (1) of e-iron coefficient to the heat none none none none n0IIe none none none none 8’ is the Debye temperature y’ is the electronic C.50 5.O). at..12 5. (ll. ature is increased.53 1.731 V]T] = V[T = 0](1 + 2.: PHASE TRANSFORMATIONS UNDER PRESSURE 539 TABLE 3. TABLE 4. iron earlier study’z1j yielded the result properties of a. AF”‘Y and AF”‘L functions Figure 10 shows the variation at one atmosphere the calculated with temperature. (lO. based on Ho” G 0..3) (10. (lO. (10. cZT~“~)/~P = 3. the temthe known of E-iron (i. the known values of can be formulated in It is now assumed that yE = ycl = y’ and also that FCp = 07.:\ (lo:o).l).3) (10.3) (ll. iron conform Table 4 summarizes temperature relation. larger entropy in the alloys studied here.3) (10.O). (lO. on the Ez Using the parameters for c-iron which result from these calculations and compares them with the corresponding parameters for u and y iron. than CI.l). it is evident that pure iron does indeed contain a triple-point.l). the temperature in equilibrium estimated at which y and E would be 400’K. specific-heat contribution (lO:l).043 x lo-“T 12 x IO-4 375 + 1.

1965 Frc. 13. P] is the fraction of high magnetic moments in f.t2n the a/e boundary is defined by Ai\Fa+[T.c. 21) is the location of the triple-point. the y/c boundary is defined by AFY-E[T.y(f. P] = AFY-“[T. the thermodynamic analysis yields values of AFa+<[T] which are consistent with the observed behavior of pure iron.c. Johnson.c. . and Vro is the molar volume of the low magnetic moment form in f. 10.c.c. and h.It should be noted that this calculation also yields values of AFC+‘[TJ. can now be applied to calculations of the phase boundaries in the pressure-temperature diagram. Figure 11 shows the calculated pressure-temperature diagram of iron. so y becomes more stable than E at temperatures above 39O’K. 1 of Ref. P]) V”[T]) (5) (4) The u/y boundary is defined by? RT In (1 AF[T. producing a minimum in AP”+.. is consistent with the very steep slope of the u e Eboundary in the pressure-temperature diagram (i. forms of iron at 0°K and one atmosphere is 150 cal/mol. Free ener~-~rnper~tu~ rel&ions a(b. entropy.c.c. indicating a small value of AL?‘~.9P(VC([T] - t Equation (5) corrects a typographical error in equation (39) of Ref.). 11. FIG.p. ironcal’ Finally. since at the boundaries (3) On the basis of the foregoing and t. Calculated pressure-temperature relations in Fe.540 ACTA METALLURGICA. This minimum.he earlier results.).)andliquidformsofFeat for the 1 atm. 10. the stacking fault energy of y iron would be estimated at about 30 ergs/cm2 or three times that of cobalt. Thus. + APa-‘[T.9PAV’a-E[T] + Pup[T] y[T. P] = 0 where y[T. which is simply the difference between AP”E and APa++’ in Fig.e. This difference is about three times the corresponding freeenergy difference in cobalt. 21 in which the P in the last term was omitted. At higher temperatures. 11) and the observed version (Fig.c. coupled with the known volume relationships (see Table 4).(a*Ftt)/d P = AVaJC/ASCL’E). P] PJ = 0 (6) + 23. P] = 0 = AFa+[T] AF’-“[T. d T. Equation (6) is solved numerically by adding equation (4) to equation (5). It is interesting to note that the computed freeenergy difference between the f.c.c.t-(h.c. the magnetic contribution to the entropy of a-iron becomes important.c. P] = 0 = -1303 + 23. VOL. These results are in good agreement with experimental observations of the phase relationships. iron at a given temperature and pressure. The free energy functions AFa+E.p.Ali’“Y and AIW”‘. The principal difference between the computed P-T diagram (Fig. On this basis.

for Metals.c. z h.c. G. Min.p. p. 3. the current differences between the computed and observed triple-points arise from uncertainties will require in both the calculations and the measurements. DE PASQUALI. f. LESLIE. 13. BANCROFT.. JAMIESON and A. shock- wave measurements of the u e y branch.) Engrs. 6.c. 152.12. 323 (1963). LEYENNAR and J. MARSHALL. Butterworths. PETERSON and S. 6. between the b. WEISS. AppZ. CLOUURERTY and L.T. C. C. 14. the experimental Jamieson and Dr. H. CLOUGHERTY and R. The application more detailed REFERENCES 1.c. W. L. D. (1961). July 1961.c. Rev.483 (1964). (1963). Solids Under Pressure. J. Inst. 206.B. Ann. 308. H. P. J. FRAUENFELDER. Science 145. Fixed-composition grams for the binary triple-point pressure pressure-temperature iron-ruthenium to the diffusionless b.) is gratefully tion of these differences studies along both lines. JURA.I. Strengthening Mechanisms in Solids. 557 (1962). STEIN and R..c. 557 (1956). S. and for the purpose of eliminating Secondly. M. Iron 8. J. PLATE. exhibit pressure overperformed shooting of the order of 10 to 20 kb between 850 and 1150°K.c. J. W. Ann. 477 (1960). while the triple-point constant. DE BRUNNER. HORNBOGEN and G.. 1962. 291 (1938). 19. Appl. 9. z pri- mation temperatures reaction. Thus. at M.p. 51. L. SUMMARY of pressure lowers the transforof the diffusionless alloys. Amer. A comparison pressure behavior of these diagrams of pure iron demonstrates pure metal also exhibits a triple-point. MARTELLY. 32. A. KAUFMAN.c. calculations simplifications at about 800°K values T. V. 2. are based 6. NICOL and G. Rev. and h. 11. Instrum. the triple-point decreases temperature remains essentially 4. Inst. 27. p. reaction in iron-ruthenium dependence The pressure proper- is controlled St. Resolu- and to Mr.p. RAUB and W. Hiah Preseure Measurement.c. New York (1961). C. nishing some of the iron-ruthenium financial support for one of the authors (L. L. Progress in very high pressure research. u-phase alloys exhibit alloys show a between the b. 35. C. Sot.p. 10. . 18. G. E. KAUFMAN and M. L.c. 11. E. DRICKAMER and H. P. Phys. Metals Park. 21.c.: PHASE TRANSFORMATIONS UNDER PRESSURE 541 Stein and Davis@) put the triple-point and 110 kb as opposed 750°K and P. L. JAMIESON. KAUFMAN. the high-pressure X-ray pertinent to this investigation. Abrahamson The General provided Electric of Watertown Fellowship acknowledged. KAUFMAN. York. P. 1393 (1956). PIPKORN. OBROWSKI. ACKNOWLEDGMENTS authors are indebted to Professor John C. MetaUk.c. C. This overshooting can be readily seen in Fig. DIETER. phases in pure iron which observed are consistent with the to the computed = experimentally behavior. markedly. LAWSON. E. 33. ABRAHAMSON. Phys. New 16. T. 776 (1962). D. 21. 17.(*) which were “isothermally”. 9.C. Washington.c. but raises that of the diffusionless of these transformations h. 11. A. AppZ. = 92 kb in Fig. G. ManLabs. K. J. which to thank Arsenal for furThey known parameters. 46. 622 (1962). 20. 4.BLACKBURN et al. J. private communication. A. D.c. DIETER. S. unpublished research. Progress Report No. 10. 279. marily by the variation in the thermodynamic ties with pressure. J. Research and Development on High-Pressure High-Temperature Metallurgy. TAKAHASHI and W. Ohio (1962). 90.c. Inc. DRICKAMER and A. analysis has yielded values for Acta Met. 2 f. 5. 135. Phys. E. S. 7. I. 3.c. E. N. BASSETT. McGraw-Hill. Dept. E. J. John Wiley and Sons. DAVIS. low-temperature 5. 318 (1938). p. transformations reaction at room dia- observed on heating and cooling. E. pressure. f. G. 1035 (1963). 1 of Ref. 2. B. In addition a pressure-induced temperature. (Metall.c. D. COHEN. JOHNSON. b. Phys. MCCALLUM and J. of Chicago. phases. (Private communication) to be published. L. E. Phyls. and h. KAUFMAN. Sci.c. M. E. of Geophysics. Phys. W. HARVEY. kF33(616)-6g-37. A1604 (1964). P. 200. 2. There are at least First. D. 624 (1959).c. for assistance in the also wish alloys. 22. Trans. Stewart McCallum of the University of Chicago for performing diffraction experiments program. with the highthat the with the high- As the ruthenium content is increased. A thermodynamic the free-energy differences structure being h. Naturwise. U. Amer. 15. V. Elling of ManLabs experimental Dr.p. FALLOT. Science 141. 5. the present required for unon idealizations The two reasons for these discrepancies. BLACKBURN. 1. BALCRAN. J. EDGE.