2656

TECHNICAL NOTES Vol. 32, pp. 2656-2659.

J. Phys. Chem. Solids

A diffraction study of diffusion in the Mo-Cr system

(Received 29 December 1970)

A DIFFRACTION method for studying interdiffusion in powder compacts was first proposed by D u w e z and Jordon[l], and later put on a quantitative basis by Rudman[2] and applied to the C u - N i system by Fisher and Rudman[3] and also be Heckel[4]. Diffraction method has also been applied to analyze diffusion under one dimensional conditions [5, 6]. The present work is concerned with an application of the R u d m a n - D u w e z method to a b.c.c, system. Specifically, M o - C r system was chosen for this purpose as information relating to interdiffusion in this system is rather scanty and also somewhat conflicting: Pines and Smushkov[5] and Gruzin et al. [7] have reported parameters characterizing the diffusion of Cr in Mo (see Table 1; a summary of their original Russian paper appears in the Chemical Abstracts [6]). Proloshkin and Sidunova[8] and Arzhanyi and Volkova[9] from experiments with diffusion

Table 1. Average diffusion parameters for b.c.c, binary systems

System Mo-Cr Mo-Cr Mo-Cr Mo-Ti Mo-Cb Cb-V Do (cm2/sec) 2.9 2-7 7.5 l'0 x I-0 5.0 x 10-a 10-a 10-~ 10-a 10+a 10-2 Q (k cal./mole) 61.4 58.0 84.0 66-0 137 68"0 Ref. This work 7 5 12 12 12

couples, on the other hand, have concluded that Mo and Cr do not form a continuous series of solid solutions and postulated the existence of an intermediate phase contrary to other works on this system[10]. The diffraction method for studying interdiffusion is suited to systems with complete range of solid solubility and our preliminary measurements were concerned with this question. We how-

ever failed to detect any intermediate phase or any other deviations from complete solid solubility in Mo-50%Cr powder compacts following successive diffusion anneals at 1050 or 1200~ F o r the diffusion runs, samples were prepared by mixing thoroughly high purity + 325 mesh size Mo and Cr powders in equiatomic proportions. The mixture was compressed into 1 in. dia. billet forms under 35,000 psi pressure and given diffusion anneals at 1050 and 1200~ for times ranging from 50 to 1600 min under continuous flow of argon. Following each annealing treatment the sample surface was gound on 400 and 600 grit papers to remove any oxidized surface layer. The small degree of cold work introduced in this process was relieved by a short anneal (15 min) at a lower temperature (800~ (In a separate run it was established that no measureable diffusion occurred at this temperature even after annealing for 1600 min. Following the strain anneal the sample was lightly ground and etched before making the diffraction runs. These consisted of recording the (200) diffraction profiles of Cr and Mo in a single continuous run following each diffusion anneal. Filtered Mo K a radiation was used and the peaks were scanned at 0.2~ counter velocity in a 0 -- 20 scanning diffractometer equipped with a scintillation counter. Following Rudman[2], each measured profile was corrected for instrumental broadening and the remainder of the broadening attributed to composition fluctuation in the sample. The corrected profile f(20) may then be shown to be related to N(c), the number of unit cells of composition c in the sample by the equation [2]

N ( c ) = Q(c)f(20)
where

(1)

Q (c) = [kA-'vd' (c)dK~t (c)] X[cfMo+(1--c)fc~ -2,

TECHNICAL NOTES

2657

20 is the scattering angle, c is the atom frac1.0 tion Mo in the sample, dakt(c) is the (hkl) _.......~_...~ interplanar spacing which is a function of c, d ' ( c ) = d ( d h k z ) / d c , v is the volume of the 0.8 unit cell, A is the absorption factor, the f ' s ...... represent the atomic scattering factors for Cr and Mo corrected for anomalous dispersion 0.6 and k is a constant. The lattice parameters for / t ~ . ~ i _ _ - ~. . . . . . . . . . . . . . . . . . . the M o - C r system, was taken from the work ~ I,, ---of Goldschmidt and Brand[1 1] which gives a o.4 ~ ~ i , - - - ~ 6 0 0 linear variation between 3.145 ,~, for Mo to ~ ~---t=so 2.880 ,~, for Cr from which d' (c) was com. --t=120 puted. In order to obtain the concentration0.2 penetration profile, Rudman[2] defines a o parameter x, equivalent to the penetration ;, parameter used in conventional diffusion o.o '0'.4 '' 016'' '0~' ' '1.0 studies, in terms of N ( c ) 0.2 X"~Fig. 1. Fraction Mo (c) as a function of the penetration parameter (x) for M o - C r powder samples interdiffused at 1200~ for the indicted times (t) in minutes.

Using equations (1) and (2), the measured (200) M o - C r diffraction profile after each diffusion anneal was reduced to a c - x profile. The results for the 1200~ diffusion runs are shown in Fig. 1. Similar curves were obtained for the 1050~ anneals. The concentration penetration curves (Fig. 1) have the expected shapes except near the regions x ~ 0, 1 where there is a tendency for the curves to round off. Straight line extrapolations shown by the dashed lines in Fig. 1, however, appear more reasonable as it is unlikely to have a few isolated regions of pure metals in the sample nor instantaneous contamination of all metals at the earliest possible annealing time, as the rounding-off of the c - x curves would seem to indicate. Similar behavior has also been reported for the C u - N i system by Fisher and Rudman[3] who considered it as an artifact arising from the approximate nature of the instrumental broadening correction. It is possible to derive from these curves the time v a r i a t i o n o f the degree of interdiffusion which is defined by the ratio (mt/m| where mt is the net mass transfer across the interface between the components at time t and

moo is the same quantity at infinite time [2, 3]. mt is given by an integration over the c - x profile:
mt = ~ct~.,=o~ x' dc
JO

(3)

where x ' = 0 defines the original interface between the components. The variation of (mt/m=) with time is shown in Fig. 2 for the two interdiffusion temperatures used in this study. Assuming an Arrhenius type temperature dependence for m t, a n average activation energy Q for interdiffusion in the M o - C r system may be derived from this data; the result is listed in Table 1. In addition to Q, it is also possible to derive information about the average D and hence Do from the c - x profiles (Fig. 1) by postulating a specific model for diffusion. From the w o r k s on the C u - N i system it appears that the concentric sphere model [3, 4] is perhaps the most appropriate one for describing interdiffusion in powder compacts. The validity of this model in the present work was determined by metallographic examina-

2658 0.7 ....-~.0.6

E

TECHNICAL NOTES

E "-40.5
Z

2o0"c

0.4 _z 0.3 = 0.2 0.1

I I I

10

20 t I/2 (min.)

30

40

Fig. 2. Degree of interdiffusion as a function of (time)89 during annealing of M o - C r powder compacts at 1050 and 1200~ respectively.

tions which revealed, quite early in the process, roughly spherical Cr rich regions in the sample surrounded by Mo rich material; this pattern continued until the entire Cr-rich core had been consumed. (A micrograph of the sample after 75 min at 1050~ is shown in Fig. 3.) Adopting this model and with appropriate boundary conditions[3], the diffusion equation may be solved for c(x) for different values of D and t. By comparing these curves with the experimental c(x) curves a value of D is found which gives the best fit between the two sets for a given temperature. The results obtained in this manner are listed in Table 1 along with the Do and Q values for several other b.c.c, systems taken from the literature [12]. It is seen that the Q value for the M o Cr system follows the same, generally higher trend found for other b.c.c, systems while the Do values do not seem to show much correlation; the X-ray values and that of Gruzin et al.[7], however, are in good agreement. The X-ray analysis yields only the average diffusion parameters, corresponding to diffu-

sion in a concentrated solution. It is possible, however, to draw some qualitative conclusions regarding the relative diffusivities of the two components. F o r example, the c - x profiles (Fig. 1) show that after 50min at 1200~ no pure Mo is left in the sample while considerable Cr remains. This faster contamination of Mo by Cr may be indicative of a higher intrinsic diffiusivity for Cr compared to Mo, a result which is expected to hold especially in concentrated solutions. Second, we note that despite the high interdiffusion temperatures used and the high Q value found in the present work indicating the dominance of volume diffusion, it is unlikely that some surface diffusion is not involved in the sintering of the powder compacts. In fact, the quick encircling of one metal by the other mentioned above does indicate the importance of surface diffusion during the early stages of annealing. However, the overall rate controlling process in achieving homogenization is volume diffusion and this is what the composition profiles and the Do and Q values derived from the diffraction data represent.

Fig. 3. Photomicrograph of M o - C r powder compact after interdiffusion at 1050~ for 75 min. Cr rich and Mo rich regions are in light and dark contrasts respectively. Mag. approx. 170x.

[Facing page 2658]

TECHNICAL

NOTES

2659

School of Engineering Science, Florida State University, Tallahassee, Florida

P. H. H O L L O W A Y * G. P. M O H A N T Y

REFERENCES 1. D U W E Z P. and J O R D A N C. B., Trans. Am. Soc. Metals 41, 194 (1949). 2. R U D M A N P. S.,Acta crystallogr. 13,905 (1960). 3. F I S H E R B. and R U D M A N P. S., J. appl. Phys. 32, 1604 (1961). 4. H E C K E L R. W., Trans. Am. Soc. Metals 57, 443 (1964).

5. P I N E S B. Ia, and S M U S H K O V I. V., Soviet Phys. Tech. Phys. 28, 626 (1958). 6. T E N N E Y D. R., C A R P E N T E R J . A. and H O U S K A C. R.,J.Appl. Phys. 41, 69 (1970). 7. G R U Z I N P. L., Z E M S K I I S. V. and R O D I N A I. B., Met. 1. Metalloved. Chistykh Metal., Sb. Nauchn. Rabot. 4, 243 (1963); Summary in Chem. Abst., 60.2602 g. 8. P R O K O S H K I N D. A. and S I D U N O V A O. I., izv. vyssh, ucheb. Zaved., Mashinostr. 5, 101 (1960). 9. A R Z H A N Y I P. M. and V O L K O V A R. M., Russ. J. inorg. Chem. 3, 354 (1963). 10. H A N S O N M., Constitution of Binary Alloys, p. 537, McGraw-Hill (1958). 11. G O L D S C H M I D T H. J. and B R A N D J. A., J. less-common Metals 3, 44 ( 1961 ). 12. H A R T L E Y C. S., S T E E D L Y J. E. and P A R S O N S

*Now at the Rensselear Polytechnic Institute, Troy, N.Y.,U.S.A.

L. D., Diffusion in Body Centered Cubic Metals, p. 51,J. Am. Soc. Metals (1965).