Temperature dependence of the elastic constants in iron single crystals: relationship

to spin order and diffusion anomalies

D.J. Dever

Citation: Journal of Applied Physics 43, 3293 (1972);

View online: https://doi.org/10.1063/1.1661710
View Table of Contents: http://aip.scitation.org/toc/jap/43/8
Published by the American Institute of Physics

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 DETERMINATION OF BURGERS VECTORS USING gb = 2 3293

been assumed in most computations, even though this
value appears to be somewhat high for the 220 reflection
in aluminum using a 25-Jl objective aperture. Even
variations down to 0.04 for ~g/~; did not alter the gene-
ral characteristics of the gb = 2 profiles, although a
given profile could be substantially altered.
The influence of several parameters can be seen quickly
with reference to Fig. 1. Figures 1(a) and 1(b) are cal-
culated dark-field profiles, for ~/~; = 0.10 and 0.05,
respectively, of a screw dislocation parallel to the foil
surface lying at half-thickness. Figure 1(c) is an experi-
mental image of a screw dislocation approximately
bisecting a wedge w ~ O. The qualitative agreement be-
tween theory and experiment is quite good for either
value of the anomalous absorption parameter. The value
of ~g/~; = 0.05 appears to be a better quantitative fit, but
since the dislocation depth is not known one cannot
accept this value as accurate.
Several other features can be seen more clearly with
reference to Figs. 2 and 3 (all for dark field). Theoret-
ical calculations predict a strictly symmetrical image
in dark field only when the screw dislocation is at mid-
depth [Fig. 2(a)1. At some arbitrary depth Fig. 2(b) is
more typical as can be seen by comparison with the ob-
served additional center fringe in Fig. 3(a). If the foil
thickness is not equal to tn~g, the profile given in Fig.
2(c) consists typically of "quadruple" fringes (light,
dark, dark, light or vice versa) as seen experimentally
in Fig. 3(c). In this case, the innermost fringes are
somewhat more difficult to resolve in thick foils. The
predicted periodic oscillations with depth [Figs. 2(d)-
2(f)] also give images with double contrast but these are
now somewhat more difficult to recognize experimen-
tally [Fig. 3(b)]. Finally, at particular combinations of
foil thickness and values of ~/~;, double contrast may
nearly disappear and a screw dislocation may be effec-
tively invisible (see Fig. 1 at t/~g=4.0, for example).
No generalization of effective invisibility could be made
however, since a large number of calculated profiles
did not reveal any regular behavior.
Although the results described here were confined main-
ly to screw dislocations, they appear to apply to edge
and mixed dislocations as well (see Fig. 3). Because of
the difficulty in checking all possible combinations g, b,
and j.J., we cannot state unequivocally that the present
results are general. It does appear that double contrast
is, if anything, somewhat easier to resolve in nonscrew
dislocations since the central background region is
wider. On the other hand, asymmetry of the image
across the core [e. g., see Fig. 3(b)] can make image
recognition somewhat more difficult, particularly for
dislocations that are nearly in the plane of the foil.
ACKNOWLEDGMENTS
The authors are indebted to Dr. P. Humble for a criti-
cal reading and several helpful comments and to NASA
and AEC for partial support of this work.
IA. Howie and M.J. Whelan, Proc. Roy Soc. (London) A267,
206 (1962).
2M.H. Loretto and L.K. France, Proc. Roy. Soc. (London)
A307, 83 (1968).
3K F. Hale and M. Henderson Brown, Proc. Roy. Soc. (Lon-
don) A310, 479 (1969).
4D. J. Dingley, Phys. Status Solidi 38, 345 (1970).
5D.E. Berry and D.M. Maher, Phil. Mag. 21,1255 (1970).
6R.C. CrawfordandD.R. Miller, Phil. Mag. 14, 1071 (1966).
7A.K. Head, M.H. Loretto, andP. Humble, Phys. status
Solidi 20, 505 (1967).
SR. Bullough and R. C. Newman, Aeron. Eng. Rev. R4551
(1964).

Temperature dependence of the elastic constants in a-iron single crystals:

relationship to spin order and diffusion anomalies*
D.J. Dever
Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439
(Received 3 February 1972)

The temperature dependence of the elastic constants of Single-crystal iron has been mea-
sured from 25 to 900 C. A nonlinearity of temperature dependence for the three measured
independent constants is associated with the degree of ferromagnetiC ordering. The c'
= (ell - CI2)/2 is nonlinear in the paramagnetic region as well. A marked difference in sen-
sitivity to spin order between the c' and C44 shear constants implies that the exchange inter-
action is, for the most part, between second, not first nearest neighbors. The nonlinearity
in temperature dependence of the elastic constants is used to account for (by means of the
Zener theory) the nonlinear Arrhenius plots for the diffusion of carbon and self-diffusion in
O!-iron.

I. INTRODUCTION the ferromagnetic region of about 1 to 3% higher than

The main objective of the present experiment was to
determine the magnetic contributions to the temperature
dependence of the elastic constants of a -iron. Earlier
investigators,l who measured the temperature depen-
dence to 500C, reported a linear temperature depen-
dence, although one might expect an increaSingly nega-
tive temperature dependence that reflects the change in
spin order with temperature. The data,l however, did
not reach temperatures near the Curie point (T c = 767
2 C where this effect becomes pronounced. Alers
et al. 2 in a similar measurement of elastic constants
through the Curie point for nickel, found increases in
the values extrapolated linearly from the paramagnetic
region.
In addition to the above-mentioned initial objective, an
application of the data has been made to explain, at
least partially, the nonlinear Arrhenius plots for the
diffusion of carbon and self-diffusion in a -iron. This
was done by comparing the temperature dependence of
both sides of the Zener equation 3
t:..S = - t:..H d(Jl IJla) (1)
a dT '
where t:..S and t:..H are activation entropy and enthalpy
for diffusion, respectively, T is temperature, and Jl is

1. Appl. Phys., Vol. 43, No.8, August 1972

3294 D.J. DEVER

TABLE 1. Elastic constants of Oi-iron at room temperature.

Value (10 12 dyn/cm2)
Mode of Elastic Present Rayne and Lord and Rotter and Leese and
measurement a constant investigation Chandrasekharb Beshersc Smithd Lord"
IOOL Cl1 2.322 2.331 f 2.28 2.314f 2.26
1l0L cl1 + c44 - C' 3.002 2.98 2.994 2.99
lOOT C44 1. 170 1.17 1.164 1. 16"
1l0T c44 1.170 1. 178 1.17
1l0T' C' 0.483 0.488 0.480 0.484

aExplanation of the notation is given in the text that "Reference 1.

accompanies Eqs. (3). fValue obtained from the combination of the 1l0L, 1l0T, and
bReference 31. 1l0T' modes, not the IOOL mode.
cReference 12. "Average of lOOT and nOT modes.
dc.A. RotterandC.S. Smith, J. Phys. Chern. Solids 27, 267
(1966) .

the "appropriate" elastic modulus that is related to the for a velocity dispersion to arise from diffraction ef-
strain energy of the lattice resulting from a diffusional fects. However, using an empirical formula,8 the effects
jump (the zero subscript denotes the value of 0 OK). The of diffraction were calculated to be inconsequential at all
term d(t:.S)/dT is determined from diffusion measure- frequencies used in this experiment compared with the
ments reported in the literature, whereas ~11/dJ"l is precision of the velocity measurement O. 01 %).
determined from the elastic constants measured in the For the propagation of stress waves along the two
present investigation. crystallographic directions [100] and [110] in a cubic
II. EXPERIMENTAL PROCEDURE structure, the following relations exist between the
velocity V of the stress waves and the three independent
A. Sample preparation elastic constants C ll , C12' and C44 :
The two single crystals of iron used in this study were
grown by a strain-anneal method from Ferrovac E %-in. PV~OOL=Cll' (3a)
bar stock. 4 One sample was prepared with opposite PV~lOL = cll + C44 - c', (3b)
(100) faces and the second with (110) faces. Orientations
were measured by means of the back-reflection Laue PV~10 = C44 ' (3c)
technique. The faces were ground and lapped through P ~10 T = C 44 [for atomic displacements along cube
3-11 diamond paste so that they were flat and parallel edge in the (110) plane], (3d)
to within 5 x 10-4 rad. The grinding and lapping technique
preserved the desired orientation to within to. 5 The and
two samples were about 3tmm thick with a cross-sec- PV~10T'=C' {for atom displacements along r110] in
tional diameter of about 7 mm. the (110) plane},
B. Density determination (3e)
The density used for the calculation of the elastic con- where P is the density and c' = t(cu - C 12 ). The numeri-
stants was 7.874 g/cm 3 , which was obtained by means of
a lattice parameter of 2.8665 A and an atomic weight of
55.847 g/mole.
C. Ultrasonic method of measurement o (IOO)CRYSTAL
The ultrasonic measurements were made by the phase- o (110) CRYSTAL
comparison methodB using a fused quartz buffer rod and
the experimental procedure described by Fisher and
Renken. 7 In the phase-comparison method, the velocity
V of the stress wave in a specimen of thickness t is
given by
V = 2ifn(n + 'Y /360)-1, (2) D

:20.96
where in is a frequency in which the "in-phase" condition ....~

exists, and n is an integer equal to the number of wave-

lengths in 2t. 'Y is a small phase angle that corrects for
the phase shift within the bonding material. The error 0.94
introduced by ignoring 'Y can be made less than the
precision of the measurement by taking measurements
at increasing frequencies In until the velocity becomes a
0
constant with frequency, and thus 'Y /360 is negligibly
0 0;;--'------;4;7.0;;:,O:---'---:6;:.;O!;;O:----'---;:;cSoo!:=---.J
0.92L-.--L---;;27::
small, as compared with n. This condition, for the
TEMPERATURE ("C)
thicknesses of the specimens used here, was usually
obtained before reaching 40 and 70 MHz for the shear FIG. 1. Temperature dependence of frequency ratio for the c44
and longitudinal modes, respectively. It is also possible modulus.

J. Appl. Phys., Vol. 43, No.8, August 1972

 ELASTIC CONSTANTS OF a-IRON 3295

TABLE II. Elastic constants of O!-iron at various temperatures cal reactions of interdiffusion of the bonding cement and
(10 12 dyn/cm2). sample are superficial, at least with respect to the ef-
c' C44 Measured Calcu- Differ- fect on the measurements. For temperatures to 650C,
(c11 + c44 lated ence a rubber paint (HT424F primer) was used, which proved
- c/l (ell + C44 to be quite satisfactory. Above 650C, a high-tempera-
-C') ture VHT lO paint has been used. Initially the VHT paint
25 2.322 0.483 1. 170 3.002 3.009 0.007 worked remarkably well with signal strengths as strong
100 2.277 0.467 1.154 2.958 2.964 0.006 or stronger than those achieved with substances suitable
200 2.215 0.441 1. 132 2.897 2.906 0.009 for use only at room temperature. This material has
250 2.181 0.426 1. 122 2.863 2.877 0.014
0.411 1. 111 2.828 2.842 0.014 worked at temperatures approaching 1200 C, 11 at which
300 2. 142
400 2.056 0.380 1.091 2.756 2.767 0.011 point the experiment was aborted for reasons other than
500 1. 968 0.344 1. 072 2.683 2.696 0.013 a failure of the bond. However, in the later stages of
600 1.867 0.301 1. 053 2.602 2.618 0.016 this work, the bond broke several times, for undeter-
650 1. 808 0.278 1.042 2.557 2.572 0.015 mined reasons.
700 1. 738 0.248 1. 031 2.505 2.521 0.016
720 1.703 0.234 1.026 2.481 2.495 0.014
740 1. 667 0.219 1.021 2.457 2.469 0.012 II\. EXPERIMENTAL RESULTS
760 1. 626 O. 199 1. 016 2.423 2.443 0.020
770 1. 598 O. 187 1. 013 2.408 2.424 0.016 A. Room-temperature moduli
780 l. 597 0.181 1. 010 2.411 2.426 0.015
800 l. 581 0.170 1. 005 2.400 2.416 0.016 Table I presents room -temperature measurements de-
820 1. 559 O. 160 1. 002 2.386 2.401 0.015 termined in this investigation along with the values
840 1. 540a 0.152 0.999 2.372 obtained by other investigators who used ultrasonic
860 1.523a O. 146 0.996 2.358 methods. The two values of C44 for the present investi-
880 1. 505 a O. 139 0.993 2. 344b
900 1. 488 a 0.133 0.990b 2. 330b gation, which were obtained from two separate speci-
mens, agree to better than 0.1%. This implies that
acalculated by Eq. (3bl, assuming a difference of 0.015 is those experimental parameters which influence the
maintained to 900C. determination of the modulus, but which are a unique
bObtained by linear extrapolation. property of the individual specimens, such as orienta-
tion, thickness, and parallelism, produce random er-
cal subscripts on V denote the propagation direction of rors less than O. 1%.
the elastic or stress wave, and the subscripts L and T
denote longitudinal and transverse (shear) waves, B. Temperature dependence of the moduli
respectively.
A typical example of the temperature -dependent data
Two samples were prepared so that five independent which were used to determine the modulus as a function
measurements could be made fo r the three independent of temperature is shown in Fig. 1. These data, which
elastic constants. This permitted internal consistency are the normalized frequency, f T/hsoc, were obtained
checks of the data because of the two redundant mea- for the C 44 modulus in two runs on separate crystals:
surements. The five measurements were made at room (100) crystal below 650C and (110) crystal above 600 C.
temperature; however, when the temperature depen- It may be seen from Fig. 1 that the data provide a
dence was measured, the C44 mode on the (110) crystal smooth curve.
was omitted below 600C, and the C 44 mode on the (100)
The variation of the measured elastic constants with
crystal was omitted above 650C.
temperature is given in Table II and in Figs. 2 and 3.
The degree of internal consistency for these measure-
D. Measurement of temperature dependence
ments may be seen from the last column of Table II
The variation of elastic constants with temperature was which is the numerical difference between the measured
calculated using the thermal-expansion data of Gold- modulus p V~lOL and the combination of the individual
schmidt. 9 The temperature was measured with an esti- measurements for Cll' C 44 ' and c/. It was impossible to
mated uncertainty of 2C by means of a chromel- measure the Cll modulus above 820C because of severe
alumel thermocouple. acoustic attenuation that was probably due to a deteriora-
tion of the bond. Therefore, the Cll values reported in
All measurements were obtained at zero magnetic field.
Table II for T> 820C were derived from the other mea-
It was assumed that magnetic domain effects are neg-
sured constants using Eq. (3b). The nonlinear tempera-
ligible at the frequencies (20-70 MHz) used in the
ture dependence of the Cll modulus found by Lord and
present experiment. This assumption seems reasonable,
Beshers 12 is more in accord with the findings of the
because the internal consistency among the redundant
present investigation than the linearity claimed by Leese
number of measurements to determine three independent
constants (see Sec. III) was quite good. and Lord. l
A notable feature of the present results is the cusps
The bonding material is the most crucial aspect of the
that exist near the Curie temperature for the two longi-
success of a high-temperature measurement. The bond-
tudinal modes of measurement (100L and 110L). This
ing agent must serve as an acoustic coupling between the
behavior is typical of longitudinal modes at Curie tem-
buffer rod and sample and simultaneously be capable of
peratures and will not be discussed further. 13
withstanding the high temperatures of the measurements,
which result in stress due to the different thermal ex- A second important aspect of the temperature depen-
pansions of the buffer and sample. The effects of chemi- dence is the marked decrease of c ' as the temperature

1. App!. Phys., Vo!' 43, No.8, August 1972

 3296 D.J.
,r---...,......-......,..--~--.,---r----,---,----r--.3.0
2.9
2.8
22 2.7
2.6
21
"'~E
11% 2.5.-E
:3 2 .0
">-'0
N
-g 1.9
<3
1.8
o LORD a BESHERS
1.7 D LEESE a LORD 2.2
1.6 2.1
1.5 2.0
FIG. 2. Temperature dependence of measured longitudinal
elastic constants of OI-iron. The experimental data points of
the present investigation are all within the drawn curves.
increases. This modulus decreases to the small value
of 0.13 x 10 12 dyn/cm 2 at 897C, which is only 28% of
its room-temperature value. The comparable values
for the other measured moduli at this temperature were
Cw 65%; P~10L' 78%; and Cw 85%. Another important
aspect is curvature. The derivative d(lnciJ)/dT becomes
more negative as the temperature increases and ap-
proaches the Curie point. As shown in Table II, this
effect is most pronounced with the c' constant, and
least pronounced with the C 44 constant. Above Tc there
is evidence of a concave upward curvature (opposite to
that below T) for the c' modulus, and to a lesser degree
for the cl l modulus. This curvature persisted to about
850C. The temperature dependence above Tc for the
other two measured moduli was linear with the limits of
experimental precision.
IV. MAGNETIC EFFECTS
A. Magnetic effects on temperature dependence
of elastic constants
The "normal" temperature dependence of the elastic
constants above the Debye temperature T 9 should be
linear, according to theory. 14 In addition, the tempera-
ture dependence of the shear constants should be much
less than that of the longitudinal constants, primarily
because of the smaller volume dependence of the shear
moduli. Many metals conform to this normal tempera-
ture dependence. However, as can be seen in Figs. 2
and 3, a -iron is an exception. Inasmuch as the anoma-
lous temperature dependence reaches a peak at the
Curie temperature T c' an obvious explanation of such an
anomaly could be the magnetiC properties of iron. A
J. Appl. Phys., Vol. 43, No.8, August 1972
DEVER
similarity of temperature dependence may be seen be-
tween
the magnetic properties (magnetization below T c
IS concave downward, and paramagnetic susceptibility
above Tc is concave upward) and the elastic constants,
especially c'. 15 The implication, of course, is not that
the moduli are directly dependent on the magnetization
and paramagnetic susceptibility, but that they are de-
pendent on the amount of spin order (alignment) related
to each. Such an effect on the modulus is possible be-
'0
cause the elastic modulus is a second derivative of the
.~
'0 total energy with respect to strain, and it is known that
the degree of spin order contributes to the total energy.
'""
.Q Because of the spontaneous magnetization that exists in
the ferromagnetic region, the spin order is long range.
In the paramagnetic region, Short-range spin order
has been proposed by WeiSS, 16 and its existence has
been confirmed with neutron diffraction studies. 17
B. Magnetic contribution to elastic constants
In the present investigation, the magnetic effects on the
elastic constants of a -iron were similar to those found
by Alers et al. 2 for nickel. They determined the mag-
netic contributions to the elastic constants by linear
extrapolation from the paramagnetic region where only
linear temperature dependence was observed. This
method will be followed here to illustrate better the
anomalies and to find the magnetic contributions at the
Debye temperature Te' The last two columns of Table
III were made with two assumptions: (i) that the anoma-
lies of temperature dependence are solely due to the
changes in spin ordering, and the temperature depen-
dence would otherwise be linear above Te; and (ii) that
the short-range spin order has reached an insignificant
0.52...--,....--,.....--,.....--.,.---,--.....--....--.....---,
1.\6
1.12
0.4
1.08 ::
o
1.04
0.40
N'
~ 0.:36 0.96
1%
10.32 %
12
1:; 0.28
D LEESE 8 LORD
024
0.20
0.16
0.120L--IJ.OO--200...I-.-..J--..J...-...L.---L--7..Joo--a-oo'----Igoo
FIG. 3. Temperature dependence of measured shear elastic
constants of CII-iron. The experimental data pOints of this
investigation are all within the drawn curves.
 ELASTIC CONSTANTS OF a -IRON
TABLE III. Slope of temperature dependence and magnetic
contributions to the elastic constants.
Modulus dlncjj (10- 4/ o C) Modulus Magnetic
dT extrapolated contribution
to Te at Te
At Te Just At
(10 12 dyn/cm 2) (10 12 dyn/cm2)
~200C below 850C
Tc
c' - 6. 8 -70 -22 0.36 + O. 08
cII -3.0 -17 - 5.66 2.08 + 0.12
C44 -1. 8 - 2.5 - 1. 50 1. 09 + O. 04
level at T> 840C, where all the moduli appeared linear
within the preCision of the measurement. Table ill shows
that substantial magnetic contributions have been made
to the c' and c l l modulus. The 22% increase at TB for c'
of iron is to be compared with the 3% increase of the c'
modulus of niCkel, which was the largest increase found
for the moduli measured by Alers et al. 2
C. Comparison of magnetic effects
on two shear constants
A large difference in magnetic effect exists between the
two shear constants c' and c44 Therefore, it is desir-
able to examine the atomic motions that correspond to
each of these constants. In Fig. 4, the atoms in a (110)
plane of a bcc structure as represented with complete
circles, and the atoms in (110) planes, which are above
and below the given plane, are represented by broken
circles. It can be seen that the (100) and (110) directions
involve first or second nearest neighbors, respectively.
In Eqs. (3), the c' constant corresponds to atomic dis-
placements of the type [110] (110), and the C 4 4 modulus
corresponds to atomic displacements of the type [001]
(110). Therefore, as seen in Fig. 4, the c' modulus is
dependent on strains that are first order with respect
to second nearest neighbors and second order with re-
spect to first nearest neighbors. The converse is, of
course, true for the C44 constant. For bcc metals, it is
known that repulsion occurs between the closed electron
shells of nearest neighbors which causes a negative
contribution to the c' modulus, and that a positive c'
probably arises from interaction with second nearest
neighbors. It must be concluded, because of the large
difference in the effect of spin order on the two shear
constants, that the exchange energy is between second
nearest neighbors and not between first nearest
neighbors.
Thus it appears that once again the simple Heisenberg
model of ferromagnetism, arising from a "direct ex-
change" between overlapping electron shells (the 3d
shells in the case of iron), does not apply. This con-
clusion is consistent with the work and conclusions of
Freeman and Watson, 18 who calculated the exchange
integral for two theoretical models of direct exchange in
transition metals and found it to be negative in each
case (a negative exchange integral explains antiferro-
magnetism, not ferromagnetic iron).
V. DIFFUSION ANOMALIES
Zener derived Eq. (1) to define the limits of Do, the
experimentally determined preexponential factor of the
3297
Arrhenius equation for the diffusion of interstitials. He
derived this equation with the following assumptions:
The energy of activation is almost entirely due to the
strain energy and the relation between stress and strain
is essentially linear, even for the large distortions
that would occur when an atom is at the saddle point.
Zener, in his application of Eq. (1), assumed that
d(JJ./JJ.o)/dT was approximately constant with tempera-
ture. This is consistent with the straight-line plots of
InD vs 1 /T, found experimentally in most cases, and
therefore a temperature-independent Do. However, for
the interstitial diffusion of carbon in a -iron, the plot
of InD vs l/T is nonlinear (a small concave upward
curvature). An anomaly, the so -called magnetic effect,
is also known to exist near T c in the Arrhenius plot for
self-diffusion in a -iron.
Numerous models l9 - 22 have been offered to explain the
anomalous diffusion of carbon in a -iron. Borg,23 how-
ever, concluded that the nonlinearity of the Arrhenius
plots for both the diffusion of carbon and the self-diffu-
sion in a -iron arise, through the Zener theory, from
an elastic anomaly. Borg used Young's modulus of
single-crystal Fe-3.1 %Si, which showed a nonlinear
temperature dependence, to arrive at this conclusion.
However, unlike the present investigation, he did not
calculate directly the AS of Eq. (1), but instead calcu-
lated a quantity that included both AS and a parameter
k, where k was a curve-fitting parameter. The elastic
anomaly model, unlike other models, does not necessi-
tate the occurrence of a new physical phenomenon to
explain the diffusion anomaly. This model merely
requires a temperature dependence of the parameter
AS heretofore expected, without theoretical justification,
to be independent of temperature.
A. Appropriate modulus
In the past, the choice of the appropriate modulus jJ. has
been inconsistent when Eq. (1) has been applied. In the
original proposal by Zener, 3 JJ. is the shear or the
tensile modulus. When applying Eq. (1) to a list of
metals, he used the poly crystalline Young's modulus.
Wert and Zener 24 used the polycrystalline shear modulus
to define the limits of Do for carbon and nitrogen dif-
fusion in a -iron. The ranges they find for AS/R are 1
[T 10J
L[OOT]
"Y /
FIG. 4. The (110) plane of the bec
Second structure. (N. N. indicates nearest
N.N. neighbors. )
/"
(
"-
\ ARr~ '\
'- .....1 VN.N, j
J. Appl. Phys., Vol. 43, No.8, August 1972
3298
16,....--,---,---,---,---~-~---r--~-~----,
-
a::
( J)
<3
ElASTIC l>S/ R
o from diffusion measurements
o o
o
o The natural logarithm of the Arrhenius equation for the
00
o~
,fjOtJj '"
100 200 300 400 500 600 700
TEMPERATURE ("e)
FIG. 5. t.S/R vs temperature for carbon and nitrogen diffusion
in OI-iron. The solid curve represents values calculated from
the Zener equation. Diffusion t.S/ R is represented by the
symbols (0) and (6) for carbon and nitrogen, respectively.
to 13 and 1 to 10 for carbon and nitrogen, respectively.
It will be seen later that the calculations of t.S/R for
the present work are, for the most part, within these
limits.
Borg 23 used the temperature dependence of both ElOO and
Em of Fe-3.1 % Si to explain the nonlinearity of the
Arrhenius plot of carbon in pure a -iron. Other investi-
gators,25-28 when applying the Zener theory to other
problems, have used a Young's modulus for a particular
crystallographic direction, a stiffness constant, or some
linear combination of stiffness constants. We believe
that Young's modulus, which allows strains in a direc-
tion normal to the applied stress, more closely fits
the concept of a barrier atom being displaced along
a line between itself and the diffusing atom at the saddle
point. The saddle point shall be defined as the point in
the path of the diffusing atom for which the strain energy
is a maximum. This will be taken as the tetrahedral
site for carbon in a -iron. Then the displacement of all
barrier atoms will be in the (210) directions. The ex-
pression for Young's modulus in any given crystallo-
graphic direction [1, m, n] 29 is
1 /E 17M = S11 - 2(l~m~ + l~n~ + m~n~)(S11 - S12 -
where 11' mu and n1 are the direction cosines and the
SIJ's are the compliance moduli. The cosines for the
(210) directions are 2/,[5", 1/,[5", and O. Therefore,
from Eq. (4) the appropriate modulus IJ. becomes
E 2lO = [Su - 8/25(Su - S12 - tSU)]-l
B. Temperature dependence of activation entropy
for carbon diffusing in a-iron
1. Details of the calculation of 6.S/R
from elastic measurements
The value of t.Ho of the Zener equation [Eq. (1)] used in
this calculation was 19.8 kcal/mole. The same value
was reported by Smith 3J for the temperature range - 50
to 150C. The measured elastic constants of the present
investigation were extrapolated from 25 to - 80C with
1. Appl. Phys., Vol. 43, No.8, August 1972
D.J. DEVER
the aid of the temperature dependencies found by Rayne
and Chandrasekhar, 31 so that the elastic t.S /R could be
extended to -80C. The ratio IJ./IJ.o was then calculated
for the modulus (IJ. = E 21o ) derived earlier from - 80 to
850C at intervals of 50C, and inserted in Eq. (1),
with the derivative of Eq. (1) replaced by t.'s. The
o
o
result is shown as a smooth curve in Fig. 5.
2. Details of the calculation of 6.S/R
diffusion coefficient D is
InD=ln(r~lI) +t.S/R -t.H/RT. (6)
800
When this equation is applied to the diffusion of inter-
stitials in a-iron, r, the geometrical factor, is kfor
the octahedral sites; la, the lattice parameter, is
2. 866X 10-8 cm;32 and II, the vibration frequency, is
approximately 1.3 x 10 13 sec-I. 24 For the purpose of
this calculation, la and II are considered to be indepen-
dent of temperature, and Eq. (6) is taken to be the
equation of a straight line between the points (Tn' Dn) and
(Tn +k , Dn +k }, where T and D with integer subscripts, are
the values reported in the literature for the diffusivities
Dn at temperatures Tn' For successive n's, it is there-
fore possible to find values of t.S/R between the points
(Tn' Dn) and (T n+k , D n+k ) from Eq. (6) and to plot these
at t(Tn + T n+ k ). The accuracy of the calculation of t.S/R
from Eq. (6) becomes better as the temperature interval
(Tn+k - Tn) increases. However, with this same increase,
a smoothing occurs that is accompanied by a loss of
definition for the desired temperature dependence of
t.S/R. Therefore, a temperature interval ranging from
a lower limit of 45C to a value compatible with the
sparsity of the reported diffusivity data was used.
The diffusion measurements which were used in Eq. (6)
for temperatures below 500C were compiled from
several sources by Lord and Beshers 33 ; for tempera-
tures above 500C, the measurements of Smith 30 were
used. The values of t.S/R obtained from Eq. (6) were
plotted at t(Tn + T n+h ) and smoothed once by taking the
median of the coordinates between successive pairs
of points. The results are plotted in Fig. 5.
tsu) (4) AH is, of course, also obtained from the solution of Eq.
(6) as a straight line. However, a plot of t.H vs T would
have the same form as the curve in Fig. 5 of t.S/R vs
T because of the thermodynamic equality
d(t.S} 1 d(t.H)
(7)
(5) ---;rr=TdT'
\
\ FIG. 6. Schematic Arrhenius
plot for diffusion of carbon in 01-
o iron. The dashed curve repre-
c sents the previously assumed
behavior. The solid curve repre-
sents the schematic behavior
determined from the results of
the present investigation.
Tc Te
I/T
 ELASTIC CONSTANTS OF a-IRON
The symbol ~ in Fig. 5 represents ~S/R for nitrogen
in a -iron, which will be discussed in Sec. V C .
3. Comparison of elastic 6S/R and diffusion 6S/R
Some of the possible reasons for the obvious lack of
quantitative agreement between elastic ~S/R and dif-
fusion ~S/R seen in Fig. 5 are discussed below.
The assumption made in using the Zener equation,
namely, that the activation energy is entirely due to
strain energy, may be wrong. If about one -half the
total activation energy were strain energy, there would
be a fit of elastic ~S/R with diffusion ~S/R in Fig. 5.
Other pertinent experimental evidence is an activation
volume of almost zero at - 23. 5 C.34 This anomalous
activation volume is also not consistent with an activa-
tion energy that arises solely from the strain of the
lattice when the diffusing atom is at the saddle point.
An additional possible reason for the poor fit, perhaps
related to the above rationale, is the fact that the strain
present at the octahedral (equilibrium) site for the car-
bon atom was ignored. This is considered to be insigni-
ficanps compared with the volume distortion necessary
in the tetrahedral site. Also, the strain of the octahe-
dral site is related to Young's modulus in the [100]
direction E 100 , which is for the most part, dependent
on the weak c' modulus. However, if the strain energy
for the carbon atom at an octahedral site is of conse-
quence, then the activation energy for the diffusional
jump will be the strain energy of the tetrahedral site
minus the strain energy of the octahedral site. But the
highly temperature -dependent c' modulus is associated
with the octahedral site and thus will reduce (because
of the minus sign for this site) ~S/R as calculated from
the Zener equation. Therefore, the modulus may more
appropriately be
(8)
where kT and flo correspond to the amount of strain in
the tetrahedral and octahedral sites, respectively.
Another possibility exists for error in the choice of the
appropriate modulus, even if the octahedral strain is
not significant. Because the temperature dependence of
c' is much greater than that of C 44 ' there is a strong
temperature dependence of the elastic anisotropy. This
means that the temperature dependence of Young's
modulus is sensitive to crystallographic direction (i. e. ,
the component of c'). The simple model used in the
present study considered the diffusing carbon atom only
when at the tetrahedral position with a displacement of
a barrier atom along a line between itself and the carbon
atom, and consequently, the "appropriate" modulus will
be E 210 However, the diffusing atom is working against
strain energy throughout the migration to the tetrahedral
position with continuously changing directions between
itself and the barrier atoms. Beshers 36 has suggested
the possibility of interstitial diffusion occurring by a
two-stage process, if the tetrahedral position is in a
metastable position for the carbon atom. If this is true,
then the saddle point (the point of maximum strain
energy) will in fact not be at the tetrahedral position,
an assumption made in the present work for the purpose
of deriving the appropriate modulus.
3299
Therefore, it seems from the above discussion that a
quantitative fit of elastic ~S/R with diffusion ~S/R
would have been merely fortuitous. Consequently,
qualitative agreement is the significant feature of Fig.
5. In Fig. 5 it appears from either diffusion or elastic
~S/R that anomalies exist in the Arrhenius plot which
are more detailed than the previously reported simple
curvature. Aside from a general increase of ~S/R with
temperature, an effect that would account for simple
curvature, a 'magnetic effect" occurs at Tc and a
noticeable change in slope occurs near Te (- 200C).
These effects on the plot of InD vs l/T, which would be
within the limits for the precision of the diffusivity, are
indicated schematically in Fig. 6.
Although the chosen appropriate modulus may not fit
reality or the strain energy may be overestimated, it
is clear that, for carbon diffusion in a -iron, the non-
linearity of the Arrhenius plot may be entirely a result
of the variation of ~S/R because of anomalies in the
temperature dependence of the elastic constants. Thus,
other models are unnecessary.
C. Activation entropy for nitrogen diffusion in a-iron
It is assumed from the evidence of Snoek peaks that
nitrogen atoms, as well as carbon atoms, can occupy
the octahedral positions in a -iron. Therefore, ~S /R
for nitrogen in a -iron, as calculated from elasticity
measurements, should be the same as ~S/R for carbon
in a -iron, except for a small decrease in ~Ho' The
activation enthalpy for the diffusivity of nitrogen in
a -iron is about 18350 cal/mole 33 vs 19800 cal/mole
for carbon.
The approximate vibration frequency II for nitrogen,
which was calculated by Wert and Zener 24 to be 1. 1
x 10 13 sec-I, and the diffusion measurements compiled
by Lord and Beshers 33 were used in the present
investigation.
The diffusion ~S/R for the case of nitrogen shows only
what might be a small increase from 0 to 800C, with
no apparent magnetic effect near T c' However, it should
be noted that above 600C, only three measurements of
diffusivity of nitrogen in a -iron were available for use
in Eq. (6), whereas for carbon there were 16 measure-
ments. In view of the large errors inherent in the pro-
cedure used for finding the temperature dependence of
the diffusion ~S/R, especially with only three measure-
ments of diffusivity, it is possible that a magnetic effect
exists near T c'
D. Magnetic effect and activation entropy for
self-diffusion in a-iron
1. Magnetic effect
A "magnetic effect", an anomaly near T c in the Arrhen-
ius plot for self-diffusion, has been found in ferromag-
netic metals and alloys. Borg,23 when applying the Zener
theory to the measured moduli of Fe -3. 1% Si, concluded
that the self -diffusion anomaly in pure iron is primarily
due to an elastic anomaly. The self -diffusion anomaly
has the same characteristic near Tc as that found in the
present work near T c for carbon diffusion in a -iron
(see Fig. 6).
1. App!. Phys., Vo!. 43, No.8, August 1972
3300 D.J. DEVER
2. Activation entropy for self-diffusion in (X-iron
Experiments on the Kirkendall effect with bcc metals
have established that the vacancy mechanism is, at
least in part, responsible for self-diffusion in these
metals. 37 In this case, Eq. (6) becomes
InD=1 ( 2 )+IlSm+IlSv_IlHm_IlHv
n YllijV R R RT RT'
where the subscripts m and v refer to the motion of the
diffusing atom and the formation of a vacancy, re-
spectively. Consequently, IlS and D.H, obtained from an
Arrhenius plot, will both have two components. It
appears that a quantitative comparison of diffusion
IlS/R with elastic IlS m/R, as calculated earlier for
interstitial diffusion, is doomed from the start because
the elastic IlS m, which is given by Eq. (1), is only a
part of the diffusion IlS. However, the formation of a
vacancy (i. e., the removal of an atom from its lattice
site) will require work against the same cohesive forces
from which the elastic constants are derived. There-
fore, an expression for IlS v can be obtained in principle,
in a manner completely analogous to the Zener deriva-
tion of IlS m Nevertheless, we are left with a much
more difficult task of finding the "appropriate" modulus.
The term J-L v is now a modulus related to the rupture and
replacement of atomic bonds so that a vacancy can be
formed. It also would be impossible with a modulus I"'v'
/I
derived from the measured elastic constants of a bulk
material, to account for a possible temperature depen-
dence of a component of IlS v that results from the defect
properties of a vacancy, such as a rearrangement of
electrons and/or increased atomic vibrations around
the vacancy.
However, the choice of appropriate moduli J-L m and J-L v
will not affect conclusions made from a qualitative
standpoint, because anomalies exist in the temperature
dependence of all three independent elastic constants c',
C 44 ' and cll" Hence the "magnetic effect" for self -dif-
fusion in a -iron is, in some part, if not entirely, due to
the effect of anomalies in the elastic constants on both
IlS v and IlS m
VI. CONCLUSIONS
(i) The spin order (alignment of spins) increases all the
elastic constants in the ferromagnetic region. This
contribution is stronger for the c' and Cll moduli and
weaker for the C44 modulus.
(ii) The temperature dependence of the c' modulus (and
to a lesser extent the Cll modulus) shows a curvature in
the paramagnetic region that reflects a contribution
from short-range spin order, albeit a much smaller
contribution than from the long-range order in the
ferromagnetic region.
(iii) The difference of magnetic effects on the two shear
constants C44 and c' indicates that the ferromagnetic
exchange interaction for a -iron is, for the most part,
between second nearest neighbors.
(iv) The nonlinearity of the Arrhenius plot for the dif-
fusivity of carbon in a -iron may be explained by anom-
alies in the temperature dependence of the elastic
constants. This nonlinearity is better defined than was
J. Appl. Phys., Vol. 43, No.8, August 1972
possible from diffusion measurements alone, with a
"magnetic effect" near Tc and a change in slope near the
Debye temperature. However, when the "appropriate"
modulus of the present work was used in the Zener
theory to find IlS m (the entropy of motion), a quantitative
fit did not result with the IlS determined from diffusion
(9) measurements.
ACKNOWLEDGMENTS
The author is appreciative of the association of E. S.
Fisher, who proposed the work. The suggestions of S. J.
Rothman were particularly helpful, and his assistance
in preparing the paper is gratefully acknowledged. The
author also thanks Professor P. Gordon and Professor
D. L. Albright of Illinois Institute of Technology for
their advice, and R. E. Black for his work in growing
and preparing the single crystals.
*Work performed under the auspices of the U. S. Atomic
Energy Commission.
IJ. Leese and A.E. Lord, Jr., J. Appl. Phys. 39, 3986
(1968) .
2G.A. Alers, J. R. Neighbors, and H. Sato, J. Phys. Chern.
Solids 13, 40 (1960).
3C. Zener, Imperfections in Nearly Perfect Crystals, edited
by W. Shockley (Wiley, New York, 1952), p. 289.
4Purchased from the Crucible Steel Co.
5E. S. Fisher (private communication).
6H.J. McSkimin, IRE Trans. Ultrasonic Engr. 25, PGUE-5
(1957) .
7E.S. FisherandC.J. Renken, Phys. Rev. 135, A482 (1964).
8H.J. McSkimin, J. Acoust. Soc. Am. 32, 1401 (1960).
9H. J. Goldschmidt, Advances in X-Ray Analysis (Plenum,
New York, 1962), Vol. 5, p. 191.
IOManufactured by the Sperex Corp.
liE. S. Fisher and D. J. Dever, The Science, Technology and
Application of Titanium, edited by R. 1. Jaffee and N. E.
Prouisel (Pergamon, New York, 1970).
12A.E. Lord, Jr. and D.N. Beshers, J. Appl. Phys. 36,
1620 (1966).
13Review articles are given by B. Liithi, T. J. Moran, and R. J.
Pollina [J. Phys. Chern. Solids 31,1741 (1970) and.by C.W.
Garland [in Physical Acoustics, edited by W. P. Mason and
R. N. Thurston (Academic, New York, 1970), Vol. 7, p. 52).
14See, for example, H. B. Huntington, in Solid State Physics,
edited by F. Seitz and D. Turnbull (Academic, New York,
1958), Vol. 7, p. 328.
15Quantitative comparisons are made by E.S. Fisher, C.N.
Reid, J. L. Routbort, and D. J. Dever [Acta Met. 19, 1307
(1971)J .
16p. R. Weiss, Phys. Rev. 74, 1493 (1948).
17See, for example, M. K. Wilkinson and C. G. Shull, Phys.
Rev. 103, 525 (1956).
18A. J. Freeman and R. E. Watson, Phys. Rev. 124, 1439
(1961) .
19C.G. Homan, Acta Met. 12,1071 (1964).
2oR.B. McLellan, M.L. Rudee, and T. Ishibachi, Trans.
AIME 233, 1938 (1965).
21M. Wuttig and J. Keiser, Phys. Rev. B 3, 815 (1971).
22M. Wuttig, Scripta Met. 5, 33 (1971).
23R. U. Borg, in Diffusion in Body-Centered Cubic Metals
(American SOCiety of Metals, Metals Park, Ohio, 1965),
p. 225.
24C. WertandC. Zener, Phys. Rev. 76, 1169 (1949).
25A. D. LeClaire, Acta Met. 1, 438 (1953).
26D. Lazarus, Phys. Rev. 93, 973 (1954).
27H.1. Aaronson and P.G. Shewmon. Acta Met. 15, 385 (1967).
28F. S. Buffington and M. Cohen, Acta Met. 2, 660 (1954).
29U. F. Nye. Physical Properties of Crystals (Oxford U. P. ,
Oxford, England, 1957), p. 145.
30R. P. Smith, Trans. AIME 224, 105 (1961).
 ELASTIC CONSTANTS OF a-IRON 3301

l1J.A. Rayne and B.S. Chandrasekhar. Phys. Rev. 122, 1714
(1961) .
32W.B. Pearson. A Handbook of Lattice Spacings and
Structures of Metals and Alloys (Pergamon, New York,
1958) .
"A.E. Lord, Jr. and D.N. Beshers, Acta Met. 14, 1659
(1966).
34J. Bass and D. Lazarus, J. Phys. Chem. Solids 23, 1820
(1962).
35S ee , for example, C. S. Barrett, and T. B. Massalski,
Structure of Metals (McGraw-Hill, New York, 1966), p. 237.
36D.N. Beshers, J. Appl. Phys. 36, 290 (1965).
37p.G. ShewmonandJ.H. Bechtold, Acta Met. 3,452 (1955).

Motion of a screw dislocation in a crystal at finite temperature*

N. Flytzanis and V. Celli

Physics Department, University of Virginia, Charlottesville, Virginia 22901
(Received 23 June 1971; in final form 16 March 1972)

In a simple model of a cubic lattice with piecewise linear nearest-neighbor interactions, a

solution is obtained for the motion of a straight screw dislocation at finite temperature T,
under the action of a constant applied stress. This external stress is balanced by the fric-
tional stress due to the scattering and emission of phonons by the core of the dislocation.
The results are compared with those obtained by the authors and others for the case of zero
temperature. It is found that the thermal agitation greatly affects the dislocation motion for
T comparable to the Debye temperature. At low T, the shape of the stress-velocity curve is
the same as at T=O, except that an additional phonon-scattering term, proportional to the
number of phonons, is present.

I. INTRODUCTION the frictional stress acting on the dislocation is calcu-

In a previous paper! (referred to hereafter as I) we
treated the problem of the motion of a straight screw
dislocation in a crystal at zero temperature. It was
found that the dislocation radiates energy when its vel-
ocity equals the phase velocity (in the direction of mo-
tion) of some lattice waves. The applied stress needed
to keep the dislocation moving at a constant velocity
shows a minimum in the physically realistic region of
the model for dislocation velocities near one-half of the
speed of sound. At small velocities the stress diverges
whenever the dislocation velocity is equal to both the
phase velocity and the group velocity of some lattice
waves, which indicates that kink-controlled motion must
occur in this region. The same conclusions have been
reached by Ishioka in a concurrent and independent
paper2 on the same problem.
In this paper we extend the treatment to finite tempera-
tures. The crystal now contains thermally excited lat-
tice waves that scatter from the dislocation. As a re-
sult the dislocation velocity fluctuates about the aver-
age. These fluctuations will be considered to be a small
effect, which is a valid approximation for high average
velocities and moderate temperatures. The main limita-
tion of the treatment is that the dislocation is still con-
sidered to be straight, and only transverse thermal
waves with displacement parallel to the dislocation are
included.
The equations of motion of a cubic crystal with nearest-
neighbor interactions containing a screw dislocation are
given and solved formally in Sec. II. The position of
the dislocation is coupled to the lattice vibrations
through the nonlinearity of the bond-snapping process.
The response of the dislocation to lattice waves is de-
termined in Sec. III. After taking the thermal average,
lated in Sec. IV by a direct method and confirmed from
energy-balance consideration. As expected, both the
emission and the scattering of lattice waves contribute
to the frictional stress. A discussion of the results is
given in Sec. V.
II. EQUATIONS OF MOTION
The simple model of dislocation motion is described in
detail in Sec. II of paper I. In what follows, we shall
assume the reader is familiar with I, to which we shall
refer frequently.
The force law between nearest neighbors is assumed to
be a piecewise linear function of the relative displace-
ment D, i. e. ,
F(D) = -A(D -vb), (2.1 )
where b is the lattice spacing in the direction parallel
to the dislocation (also the magnitude of the Burgers
vector), and v is an integer such that I D - vb I < ib.
To examine the frictional stress exerted by the scatter-
ing of phonons on a straight screw dislocation mOving
at high velocity in a crystal, at small finite tempera-
tures (T*O), we introduce a function R(m) such that
the time tm when the mth bond snaps is given by the
following relation:
m=vtm-R(m), (2.2)
where v is the average dislocation velocity, with the
lattice constant in the plane perpendicular to the dislo-
cation taken equal to unity. If R(m) is independent of m,
then the dislocation moves at a constant velocity [and in
this case it is convenient to choose R(m) =0]; otherwise,
the dislocation velocity changes from cell to cell.

1. Appl. Phys., Vol. 43, No.8, August 1972