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A new empirical formula for the calculation of MS temperatures in pure

iron and super-low carbon alloy steels

Article  in  Journal of Materials Processing Technology · June 2001

DOI: 10.1016/S0924-0136(01)00625-2

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 Journal of Materials Processing Technology 113 (2001) 556±562

A new empirical formula for the calculation of MS temperatures in

pure iron and super-low carbon alloy steels
Cheng Liua, Zhenbo Zhaoa, Derek O. Northwooda,*, Yunxu Liub
a
Mechanical, Automotive and Materials Engineering, University of Windsor, Windsor, Ont., Canada N9B 3P4
b
Materials Engineering, Jilin Institute of Technology, Jilin Province, Changchun 130012, PR China

Abstract

It has often been observed that when the experimentally determined MS (the upper limit of the martensite transformation, or the practical
start temperature of martensite transformation) temperatures are extrapolated to pure iron from binary Fe±C, Fe±Ni, Fe±Cr, Fe±Mn, Fe±Co
alloys, anomalous temperatures, e.g. 520, 680, 700±750, 800±9008C, or even as high as the equilibrium g ! a temperature of 9128C, are
obtained. In order to shed light on these con¯icting results, a new empirical formula

795 25;000C1 45Mn 35V…Nb ‡ Zr ‡ Ti† 30Cr 20Ni 16Mo 8W 5Si ‡ 6Co ‡ 15Al
MS … C† ˆ
525 350…C2 0:005† 45Mn 35V…Nb ‡ Zr ‡ Ti† 30Cr 20Ni 16Mo 8W 5Si ‡ 6Co ‡ 15Al; where C1 < 0:005; 0:005  C2 < 0:02

is proposed to predict the MS temperature of pure iron and super-low carbon alloy steels. The effect of steel composition on the MS
temperature is discussed. The validity of this new equation together with 11 other existing empirical formulae for the calculation of MS
temperature in pure iron and super-low carbon alloy steels is examined. For more than 80% of super-low carbon alloy steels, the MS
temperatures can be predicted by this new formula to within 258C. The new formula indicates an MS temperature of 7958C for a steel
without carbon or other alloying elements (``pure'' iron). This is a better approximation to the experimental result of 7508C than for other
formulae when the cooling rates exceed 35,0008C/s, and the carbon content is lower than 0.0017 wt.%. # 2001 Elsevier Science B.V. All
rights reserved.

Keywords: MS temperature; Pure iron; Super-low carbon alloy steels; Empirical formula

1. Introduction (carbon free) is very dif®cult, and carbon analyses at low

Due to the very low stability of super-cooled austenite in
pure iron, the MS temperature for pure iron is usually
determined only when different austenite-stabilizing ele-
ments are added, or a very fast cooling rate is applied.
However, it has often been observed that when the experi-
mentally determined MS temperatures are extrapolated to
pure iron from binary Fe±C, Fe±Ni, Fe±Cr, Fe±Mn, Fe±Co
alloys, anomalous temperatures, e.g. 5208C [1±4], 6808C
[5], 700±7508C [6±12], 800±9008C [13], or even as high as
the equilibrium g ! a temperature of 9128C [14], are
obtained. Even if a very fast cooling rate is applied, the
measured MS cannot always be considered to be a very
reliable result since obtaining an ``absolutely'' pure iron
*
Corresponding author. Present address: Faculty of Engineering and
Applied Science, Ryerson Polytechnic University, Toronto, Ont., Canada
M5B 2K3. Tel.: ‡1-416-979-5102; fax: ‡1-416-979-5308.
E-mail address: dnorthwo@acs.ryerson.ca (D.O. Northwood).
values are not always reliable [13]. In principle, the MS
temperature for pure iron can be calculated by balancing the
driving force for nucleation DGg!MFe against the available
chemical free energy change accompanying the transforma-
tion from austenite to martensite. However, calculation of
the latter quantity involves the extrapolation of the free
energy surfaces of austenite and ferrite into temperature
regimes where they are not in thermodynamic equilibrium.
Different analytical methods [15], assumptions and trans-
formation parameters have to be considered in order to meet
the different phase transformation conditions. This leads to
uncertainties in calculated quantities. It has already been
shown by Anderson and Hultgren [16] that the enthalpy data
obtained by extrapolation involve an error that is of the same
magnitude as the ®nal calculated driving force for the
austenite±martensite transformation. Yeo [17] had also sug-
gested that carbon-free alloys should be studied for a
reassessment of the theories of martensite formation. There-
fore, some questions related to MS temperatures of pure iron
and super-low carbon alloy steels have also been examined.

0924-0136/01/$ ± see front matter # 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 4 - 0 1 3 6 ( 0 1 ) 0 0 6 2 5 - 2
 C. Liu et al. / Journal of Materials Processing Technology 113 (2001) 556±562
2. Theoretical analysis and discussion
2.1. The critical points of the phase transformation for
pure iron and the disadvantages of a thermodynamic
method in calculating the MS temperature for pure iron
The critical points of the phase transformation, Ae3
(where, the chemical free energy GgFe GaFe ˆ 0) for pure
iron and T0 (where, the chemical free energy GgFe GM Fe ˆ 0)
for plain martensite transformation should be totally differ-
ent since the ®rst transformation involves the diffusion of
iron atoms, whereas the martensite transformation is diffu-
sionless, displacive or shear-like. In our opinion, Ae3 should
be larger than T0 for pure iron and Ae3 T0 ˆ 60 65 C,
even though some researchers propose Ae3 T0 ˆ 912 C.
More detailed information on this particular topic can be
found in the Ph.D. Dissertation of one of the authors [18].
It is well known that the MS temperature is closely related
to T0. MS falls 2008C below T0 in the iron±carbon system
when the carbon content changes from 0.05 to 1.3 wt.%,
namely T0 MS ˆ 200 C (corresponding to a 1214 J/mol
transformation driving force) [19]. However, for pure iron
and super-low carbon steels, due to the lower coherency
shear resistance, the driving force that is needed for the
martensite transformation becomes smaller. Therefore, the
difference between T0 and MS is reduced. No chemical
factor energy terms are involved in the martensite transfor-
mation for pure iron. The total of nonchemical terms is no
more than about 272 J/mol [19], i.e., a 458C difference in T0
and MS for pure iron.
Although the general validity of the thermodynamic
method is recognized, a new anomaly occurs (see Fig. 1
Fig. 1. Change in chemical free energy attending the austenite±martensite
reaction in iron±carbon alloys as a function of temperature and carbon
content [19].
557
[19]). The curves show the almost constancy of the free
energy difference between martensite and austenite regard-
less of carbon content, and this implies that the driving force
is always around 1214 J/mol. However, Bibby and Parr [13]
found if the MS temperature for pure iron is not 5408C, but is
in excess of 7508C, then, the driving force for the martensite
transformation in pure iron will have to be considerably
reduced. In fact, the data for 0.0 wt.% C iron was obtained
from an extrapolation calculation, and no correct or reliable
MS temperature was given in Cohen's [19] calculation (as
shown in Fig. 1), since some data were not available to
estimate the difference in the free energies of mixing
between austenite and martensite. Cohen himself acknowl-
edged that some assumptions must be introduced to make up
this inadequacy [19]. Therefore, the simple extrapolation
calculation of Bibby and Parr from Cohen's diagram is
obviously unreasonable. Further, Singh and Parr [20] have
shown that an e.m.f. is generated by a cell whose electrodes
are equiaxed ferrite and martensite iron.
This, in turn, demonstrates that the free energy of
equiaxed ferrite is not the same as that of martensitic pure
iron. Hence, an assumption that is implicit in the thermo-
dynamic method for the martensitic transformation in Fe±C
alloys [20] appears to be in error.
2.2. The effects of alloying elements on the MS temperature
As mentioned in Section 1, the MS temperature for pure
iron is often obtained by extrapolation to pure iron from
binary alloys. Izumiyama et al. [21] ®rst showed the effect of
individual alloying elements on the MS temperature for iron-
based binary alloys with up to 13 elements (see solid lines in
Fig. 2). Their results show that Al, Ti, V, Nb and Co
effectively increase the MS temperature, whereas Si, Cu,
Cr, Ni, Mn and C decrease the MS temperature. Extrapola-
tion of their resulting data into zero content of the alloying
element leads to a maximum MS temperature of about 7208C
for pure iron. However, Liu's [22] study shows that all
alloying elements (Mn, V, Ni, Cr, Mo, Cu, W, Si) except
Al and Co decrease the MS temperature (see short dotted
lines in Fig. 2). An MS temperature for pure iron of 7958C is
obtained when Liu's data are extrapolated to zero alloying
element content. The different effects of alloying elements
on the MS temperature of iron-based binary alloys as
determined by the other researchers is shown in Fig. 2 [7]
(long dotted lines) and Fig. 3 [1,5,8±10,12,23±25]. It is seen
that the effect of the same individual element on MS
temperature is different since the different processing con-
ditions (austenitizing conditions, cooling rates), impurity
contents (especially, nitrogen: it is said that nitrogen has the
similar effect on MS temperature to carbon [26]), and
different grain sizes (the critical cooling rate is very sensitive
to grain size [14]) have been used. Thus, very different
values of the MS temperature for pure iron were observed
when the different experimentally determined MS tempera-
tures are extrapolated to pure iron [1±13,21±25]. Therefore,
558 C. Liu et al. / Journal of Materials Processing Technology 113 (2001) 556±562
Fig. 2. MS temperature of iron-based binary alloys after Izumiyama et al.
[21] (solid lines) and Liu [22] (short dotted lines) and Ackert and Parr [7]
(long dotted lines).
an accurate MS temperature for pure iron cannot be obtained
only by simple extrapolation, but by a more comprehensive
analysis.
2.3. The effects of cooling rate on the martensitic
transformation and MS temperature
Another interesting phenomenon concerning the marten-
site transformation is the effects of cooling rate on the MS
temperature. The work by Ansell et al. [27] shows an
Fig. 3. MS temperature of iron-based binary alloys as determined by
various researchers [1,5,8±10,12,23±25].
increase in MS of 90±1228C in a sigmoidal fashion over a
cooling rate ranging from 2750 to 24,8008C/s. The increase
in MS was attributed to a reduced segregation of carbon to
imperfections in austenite with increased cooling rate, and
was correlated to the in¯uence of a third element on the
diffusivity of carbon in austenite. Mirzayev and co-workers
[28] further con®rmed that the continuous cooling transfor-
mation of steels is a multistage process. Several plateaus are
exhibited and each plateau (stage) corresponds to a speci®c
transformation product (microstructure), and each transfor-
mation product has its own transformation start temperature
(or upper temperature limit) as shown in Fig. 4 [28]. An MS
temperature of 400±5508C is obtained for 0.01 wt.% C iron
from Fig. 4. However, in the very low alloying element or
carbon concentration range, a relatively high MS tempera-
ture, 695±7508C, is obtained for Fe±17 ppm C and Fe±
15 ppm C alloys [7,13] (see Fig. 5).
This is not surprising since the MS temperature is very
sensitive to carbon content as discussed above. Therefore,
Bibby and Parr [13] concluded that it is safe to assume that
an MS of 5408C is associated with carbon contents between
about 0.005 and 0.01%, rather than for pure iron, no matter
what cooling rate is used. Zhao [14] provided an explanation
for the above con¯ict in terms of the tendency of the critical
cooling rate (CCR) to decrease with increasing alloying
element content. He pointed out that in very dilute alloys, the
CCR of massive ferrite is very high. The cooling rates used
by most investigators are below the CCR of massive ferrite,
so that their MS temperature is neither the true MS, nor even
the true Ma (massive transformation start temperature), but a
higher transformation start temperature for grain boundary
ferrite (see Fig. 4). However, this explanation cannot provide
Fig. 4. Continuous cooling transformation start temperature versus cooling
rate for iron containing about 0.01 wt.% C showing multistage nature of
kinetics of the cooling transformation [28].
 C. Liu et al. / Journal of Materials Processing Technology 113 (2001) 556±562
Fig. 5. The g ! a transformation in very dilute iron±carbon alloys
(cooling rate range 0±50,0008C/s for solid lines [13] and cooling rate range
100±115,0008C/s for dotted lines [7]).
a satisfactory answer for the behaviour shown in Fig. 5
[7,13] since martensite was observed at a higher cooling rate
than massive ferrite. Bibby and Parr [13] thought that the MS
temperature will be essentially independent of cooling rate,
as long as this cooling rate is suf®cient to prevent any
diffusion phenomena.
2.4. The similar transformation characteristics of
martensite, bainite and acicular ferrite (Widmanstatten
ferrite) for pure iron
Martensite, bainite and acicular ferrite in pure iron can be
considered as a same ``phase'' since they are formed by a
similar diffusionless, displacive or shear-like process, and
exhibit a coherent relationship with the parent phase. The
transformation start temperature for pure iron should be
same, namely, MS ˆ BS ˆ a-WS (the start temperature for
Widmanstatten ferrite) since there is no effect of carbon or
other chemical elements on the shear transformation pro-
cess. As shown in Fig. 6, the theoretical …DG ˆ 0† and
practical transformation start temperature can be summar-
ized as: T0 (or Zg!M, at DGg!M ˆ 0) and MS for the g ! M
martensite transformation; Zg!~a (at DGg!a ˆ 0) and a-WS
for the g ! a-W (Widmanstatten ferrite) transformation;
Ae3 (or Zg!a, at DGg!a ˆ 0); Ar3 for the g ! a diffusion-
controlled ferrite transformation. The practical transforma-
tion start temperature should be 5±108C lower than the
theoretical value for the diffusion-controlled transformation
[22]. However, for the g ! a-W (Widmanstatten ferrite)
transformation, since only carbon is involved in the diffu-
sion, rather than both carbon and iron atoms (iron atoms will
transform in a diffusionless, displacive way), the practical
559
Fig. 6. The transformation start temperatures of g ! M, g ! a-W and
g ! a in iron±carbon binary alloys.
transformation start temperature should be 458C lower than
the theoretical transformation start temperature since the
nonchemical terms total is no more than about 272 J/mol
[19]. For the g ! M martensite transformation, as discussed
in Section 2.1, MS falls 2008C below T0 in the iron±carbon
system when the carbon content changes from 0.05 to
1.3 wt.%. However, for pure iron, only a 458C decrease
can be calculated from T0 to MS, similar to the g ! a-W
transformation.
2.5. Comparison of formulae for predicting MS
temperatures
There have been several formulae which have been
attempted to relate the MS temperature with alloy composi-
tion. These formulae are given in Table 1 [14,22,29±35]
together with our new formula. The new formula indicates
an MS temperature of 7958C for a steel without carbon or
other alloying elements (``pure'' iron). This is a better
approximation to the experimental result of 7508C than
for other formulae (see Table 1, the other formulae predicted
MS from 420 to 5618C for pure iron) when the cooling rates
exceed 35,0008C/s, and the carbon content is lower than
0.0017 wt.% [13]. The temperature of 7958C is suf®ciently
close to the quoted Curie temperature for iron (7708C) to
remind one of Zener's [37] contention that f.c.c. iron should
transform to the b.c.c. structure at the Curie temperature.
However, we do not have an accurate value for the Curie
temperature of high-purity iron. That's why Bibby and Parr
[13] thought that MS temperature for pure iron would lie
between 800 and 9008C after they extrapolated their very
low carbon results to zero carbon. The validity of our new
 560
Table 1

C. Liu et al. / Journal of Materials Processing Technology 113 (2001) 556±562

Chronological tabulation of formulas for calculating MS temperatures and application to pure iron

No. Source Date, Equation Calculated MS

Reference temperature
for pure iron

1 Payson and Savage 1944, [29] MS … C† ˆ 499 308C 32:4Mn 27Cr 16:2Ni 10:8Si 10:8Mo 10:8W 499
2 Carapella 1944, [30] MS … C† ˆ 496…1 0:62C†…1 0:092Mn†…1 0:0033Si†…1 0:045Ni†…1 0:07Cr†…1 0:029Mo†…1 0:018W†…1 ‡ 0:012Co† 496
3 Rowland and Lyle 1946, [31] MS … C† ˆ 499 324C 32:4Mn 27Cr 16:2Ni 10:8Si 10:8Mo 10:8W 499
4 Grange and Stewart 1946, [32] MS … C† ˆ 538 350C 37:7Mn 37:7Cr 18:9Ni 27Mo 538
5 Nehrenberg 1946, [33] MS … C† ˆ 499 292C 32:4Mn 22Cr 16:2Ni 10:8Si 10:8Mo 499
6 Steven and Haynes 1956, [34] MS … C† ˆ 561 474C 33Mn 17Cr 17Ni 21Mo 561
7 Andrew 1965, [35] MS … C† ˆ 539 423C 30:4Mn 12:1Cr 17:7Ni 7:5Mo …linear† 539
MS … C† ˆ 512 453C 16:9Ni 9:5Mo ‡ 217…C†2 71:5…C†…Mn† ‡ 15Cr 67:6…C†…Cr† …nonlinear† 512
8 Liu 1981, [22] MS … C† ˆ 550 361C 39Mn 35V 20Cr 17Ni 10Cu 5Mo 5W ‡ 16Co ‡ 30Al 550
9 Liu 1981, [22] MS … C† ˆ 538 317C 33Mn 28Cr 17Ni 11Si 11Mo 11W 538
10 Zhao 1992, [14] MTM
S ˆ 420 208:33C 72:65N 43:36N2 16:08Ni ‡ 0:7817Ni2 0:02464Ni3 2:473Cr 33:428Mn 420
‡1:296Mn2 0:02167Mn3 ‡ 30:00Mo ‡ 12:86Co 0:2654Co2 ‡ 0:001547Co3 7:18Cu 16:28Ru ‡ 1:72Ru2 0:08117Ru3 a
11 Zhao 1992, [14] MLM
S ˆ 540 356:25C 260:64N 24:65Ni ‡ 1:36Ni2 0:0384Ni3 17:82Cr ‡ 1:42Cr2 47:59Mn ‡ 2:25Mn2 0:0415Mn3 540
‡17:50Mo ‡ 21:87Co 0:468Co2 ‡ 0:00296Co3 16:52Cu 17:66Rub
12 Liu, Zhao, 2000 MS … C† ˆ 795 25; 000C 45Mn 35V…Nb ‡ Zr ‡ Ti† 30Cr 20Ni 16Mo 8W 5Si ‡ 6Co ‡ 15Al …for C < 0:005† 795
Northwood and Liu
MS … C† ˆ 525 350…C 0:005† 45Mn 35V…Nb ‡ Zr ‡ Ti† 30Cr 20Ni 16Mo 8W 5Si ‡ 6Co ‡ 15Al
…for 0:005  C < 0:02†
a
MS temperature for twinned martensite.
b
MS temperature for lath martensite.
 C. Liu et al. / Journal of Materials Processing Technology 113 (2001) 556±562
Table 2
MS values obtained experimentally and calculated using the new formula

No. Investigation Experimental Cooling Chemical composition (wt.%) Calculated Derivation from
temperature rate (8C/s) temperature experimental
(MS, 8C) (MS, 8C) value (8C)

1 Esser et al. [4] 520 18000 C: 0.017, no record of metallic impurities 521 ‡1
2 Gilbert and Owen [1] 545 5500 C: 0.010, Si: 0.005, O2: 0.006, S: 0.004, P: 0.002 523 22
3 Duwez [6] 750 12000 C: 0.001, trace metallic impurities, each less than 0.001, O2 less than 0.02 770 ‡20
4 Srivastava and Parr [2] 519 10000 C: 0.005, Si: 0.02, Ni: 0.06 524 ‡5
5 Bibby and Parr [13] 750 >35000 C: <0.0017, metallic impurities: 0.0015 753 ‡3
6 Ackert and Parr [7] 750 >45000 C: 0.0015, trace metallic impurities 758 ‡8
7 Ackert and Parr [7] 675 ± C: 0.0049, trace metallic impurities 673 2
8 Bibby [36] 690 ± C: 0.0049 673 17
9 Ackert and Parr [7] 763a ± C: 0.0006, trace metallic impurities 780 ‡17
10 Ackert and Parr [7] 550 ± C: 0.0186, trace metallic impurities 520 30
11 Ackert and Parr [7] 590 ± C: 0.0141, trace metallic impurities 522 68
a
Average temperature between 725 and 8008C.

561
562 C. Liu et al. / Journal of Materials Processing Technology 113 (2001) 556±562

equation for the calculation of MS temperature in super-low [9] D.W. Gomersall, J.G. Parr, JISI 203 (1965) 275.
carbon alloy steels has been examined in more detail. For [10] J.G. Parr, JISI 205 (1967) 426.
[11] L. Kaufman, M. Cohen, Trans. AIME 206 (1956) 1393.
more than 80% of super-low carbon alloy steels, the MS [12] L. Kaufman, M. Cohen, Progr. Metal Phys. 7 (1958) 165.
temperatures can be predicted by this new formula to within [13] M.J. Bibby, J.G. Parr, JISI 202 (1964) 100.
258C, as shown in Table 2. [14] J. Zhao, Mater. Sci. Technol. 8 (1992) 997.
[15] H.K.D.H. Bhadeshia, Met. Sci. 15 (1981) 178.
[16] P.D. Anderson, H. Hultgren, Trans. AIME 224 (1962) 842.
[17] R.B.G. Yeo, Trans. AIME 224 (1962) 1222.
3. Conclusions [18] C. Liu, Ph.D. Dissertation, Harbin Institute of Technology, China,
1998.
A new empirical formula is proposed to predict the MS [19] M. Cohen, E.S. Machlin, V.G. Paranjpe, Thermodynamics in
temperature of the pure iron and super-low carbon alloy Physical Metallurgy, ASM, 1949, p. 242.
steels. The effects of steel composition and cooling rates on [20] K.P. Singh, J.G. Parr, Acta Metall. 9 (1961) 1073.
[21] M. Izumiyama, M. Tsuchiya, Y. Imai, J. Japan Inst. Net. 34 (1974)
the MS temperatures are discussed. The similarity of the 291.
bainite, martensite, acicular ferrite transformation is sum- [22] Y.X. Liu, Principle of Heat Treatment, China Mechanical Industry
marized. For more than 80% of super-low carbon alloy Press, Beijing, 1981.
steels, the MS temperatures can be predicted by this new [23] W.S. Owen, E.A. Wilson, Physical properties of martensite and
formula to within 258C. The new formula indicates an MS bainite, Special Report No. 93, Iron and Steel Institute, London,
1965, p.153.
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alloying elements (``pure'' iron). This is a better approx- [25] R.H. Goodenow, R.F. Hehemann, Trans. TMS Ð AIME 233 (1965)
imation to the experimental result of 7508C than for other 1777.
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2443.
[28] O.P. Morozov, D.A. Mirzayev, M.M. Shteynberg, Fiz. Met.
Metalloved. 32 (1971) 1290.
References [29] P. Payson, C.H. Savage, Trans. ASM 33 (1944) 261.
[30] L.A. Carapella, Met. Progr. 46 (1944) 108.
[1] A. Gilbert, W.S. Owen, Acta Metall. 10 (1962) 45. [31] E.S. Rowland, S.R. Lyle, Trans. ASM 37 (1946) 27.
[2] L.P. Srivastava, J.G. Parr, TMS Ð AIME 224 (1962) 1295. [32] R.A. Grange, H.M. Stewart, Trans. AIME 167 (1946) 467.
[3] A.B. Greninger, Trans. ASM 30 (1942) 100. [33] A.E. Nehrenberg, Trans. AIME 167 (1946) 494.
[4] H. Esser, et al., Arch. Eisenh. 6 (1933) 389. [34] W. Steven, A.G. Haynes, JISI 183 (1956) 349.
[5] W.D. Swanson, J.G. Parr, JISI 202 (1964) 104. [35] K.W. Andrew, JISI 203 (1965) 721.
[6] P. Duwez, Trans. AIME 191 (1951) 765. [36] M.J. Bibby, Master's Thesis, University of Alberta, 1963.
[7] R.J. Ackert, J.G. Parr, JISI 209 (1971) 912. [37] C. Zener, Elasticity and Anelasticity, University of Chicago Press,
[8] J.S. Pascover, S.V. Radcliffe, TMS Ð AIME 242 (1968) 673. 1952.

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