The atomic jump processes involved in the vacancy mechanisms of selfdiffusion in metals are reviewed with particular
attention to disvacancies. The most important measurements which are helpful to separate mono and divacancy contributions  temperature, mass, and pressure dependence of the diffusion coefficient and correlation effects  are discussed. The
recent experimental progress will be considered also. The extension of direct tracer studies to much lower temperatures has
greatly increased the reliability with which monovacancy properties may be deduced. Amongst the indirect techniques like
nuclearmagneticrelaxation, Mijssbauer effect and quasielastic neutronscattering, especially nuclear magnetic relaxation
may be considered nowadays as a quantitative tool. In a discussion of individual metals the above mentioned topics will be
illustrated by examples, with emphasis on those metals where a considerable deepening of our understanding of atomic
jump processes has been achieved.
Les processus de saut atomique quimpliquent les mecanismes lacunaires dautodiffusion dans les m&aux sont pass& en
revue en portant une attention particuliere sur les bilacunes. Les mesures les plus importantes qui permettent de s&parer
les contributions des monolacunes et desbilacunes, les relations entre coefficient de diffusion et les variables tempkrature,
masse et pression et les effets de correlation sont discuties. Les progris exp&imentaux ¢s seront aussi consid&s. Lextension des Etudes directes par traceurs B des tempiratures beaucoup plus basses a augment6 considkrablement la pouibilitd
de d6duire les propri&s des monolacunes. Parmi les techniques indirectes, comme la relaxation mag&tique nucldaire,
leffet Mllssbauer et la diffusion quasihlastique des neutrons, sp&ialement la relaxation magn6tique nuclhaire, peuvent
6tre consid&es maintenant comme des outiles quantitatifs. Dans une discussion concernant certains m&aux, les methodes
mention&es cidessus seront ill&r&es par des examples en mettant laccent sur ceux des r&taux pour lesquels an approfondissement considerable de notre comprehension des processus de saut atomique a 6th obtenu.
1. Introduction
Selfdiffusion in crystals is one of the most important manifestations of point defects in thermal equilibrium. In metals it is generally agreed that selfdif38
39
have
(2.1)
where N is the number of different types of jumps.
r, (a: = 1 ) .... iV) denotes the number of jumps of type
(Ymade by an atom per unit time and Ax, the xprojection of the pertaining jump distance. For a defect
mechanism of diffusion r, is given by
>
r, =ca?,
cm
12.3)
whereas in hexagonal crystals two tensor components
parallel (II)
DT,I = f
11
@D,
and perpendicular
(2.4a)
(1)
DT,~ = f DSW
(2.4b)
to the hexagonal axis must be distinguished. The correlation factor(s) is (are) characteristic for a given diffusion mechanism and may be calculated if the jump
frequencies of the atoms involved are known. The
methods for calculating correlation factors have been
reviewed by LeClaire [9] and Mehrer [lo] and will
not be discussed here. Correlation factors have been
worked out for almost all cases of practical interest
and will be discussed in section 2.3.
2.1 .I. Monovacancy mechanism
In thermal equilibrium the concentration of monovacancies in a monoatomic crystal is given by
CIV =exp(Sj"v/k)exp(~~~/kT)y
(2.5)
40
=fiv
CIV hv a2 ,
(2.7)
where a is the cubic lattice constant andfiv the monovacancy correlation factor (fiv = 0.781 in an fee and
fiv = 0.723 in a bee structure [l 11).
In hexagonal closepacked structures two different
jump frequencies must be considered  one (v*v,A)
for jumps within and another (v~~,~) for jumps obliqu
to the basal plane. The components of the tracer selfdiffusion coefficient may be written as
DTG = 3;~ clv vlV,B
c:c
*2v12
=2c%v*v21
>
(2.8)
(2.7a)
C*
and
D;$
V2Vf2
(2.7b)
"2vrr
In
0.31
.2
.I
"2vrr
v2v12
2n
.6
.8
)
.8
.6
.4
.2
vzytl
Vzvrr
41
f)sv
22
 Ja
In
Czv(vav1t
+ v2v12)fzv
(2.9)
ln
2n
(2.10a)
=4C%2~21
and
12&2~24
(2SOb)
= GCy2v42
DTv = 2 a2%@2V21
(2.11)
+ v2V24)f2V
In
0.466
0.3
0
cl.33
.2
.I
.6
3uL
iV.?L
.6
.B
0.4
0.6
0.8
7.0
0.8
0.6
0.L
0.2
.6 .4 .Z
%w
0.2
selfdiffusion
fvzv,*a
)
VZV,dR
in a bee lattice,
Fig.
%,A.4
vrv,ns
a hcp lattice,
[ 131.
42
(2.12a)
= c2C%v~~,~Bf8v
and
(2.12b)
where the correlation factor components are multivalued functions of the atomic jump frequencies shown
in the lower part of fig. 3.
2.2. Temperature dependence of selfdiffusion
Within a limited temperature range selfdiffusion
data may often be represented with sufficient accuracy
by an Arrhenius law
(2.13)
where both the preexponentia1 factor Dzff and the
activation enthalpy QeT ;e taken as independent of
temperature (k denotes Boltzmanns constant).
By inserting eqs. (2.5) and (2.6) into eq. (2.7), we
obtain for the activation enthalpy of selfdiffusion by
monovacancies
Q1v=H,v
M
fHlV
(2.14a)
preexponential
factor
(2.14b)
of cubic crystals. The interpretation of measured values of Qeff and Dgff in terms of eq. (2.14) has sometimes been called the standard interpretation
of selfdiffusion.
However, deviations from an Arrhenius behaviour
appear to be an almost common feature of selfdif
(2.15)
H. Mehrer /Atomic
position of various Arrhenius terms with slightly different activation enthalpies and may imply a temperature dependent correlation factor [see eqs. (2.9) and
(2.1 l)]. However, since the divacancy contribution is
often only a small correction term in DT it may be
difficult to resolve the details of the divacancy mechanism from an analysis of the temperature dependence. On the other hand correlation and mass effects
discussed in section 2.3 are more sensitive to such
details.
For those fee metals where it is sufficient to consider the simple divacancy mechanism, eq. (2.15)
reduces to a superposition of two Arrhenius terms
DT=Dy
exp(g)+Di
exp(z),
(2.15a)
where the abbreviations in eq. (2.14) for the monovacancy parameters and
Q2v = Wyv  H::
D!: = 4f2va2v$
exp
+ H% ,
2sF; + A&v + s %
k
D:v +QzvD;v ,
DT
of the activation
DT
enthalpies
(2.16)
(E),=T(%lp.
(2.1 Sb)
43
(2.17)
44
DT =DTv = 07 exp[QPva(l
f ~R2)/k7],
(2.19)
(2.20)
Table 1
Correlation factors and isotope effect for selfdiffusion in metallic structures
Facecenteredcubic
Hexagonalclosepacked
Parallel caxis
Perpendicular caxis
fiv
EIV =fivAK,v
.Eiv =ftvA&v,B
fiv
flv
fh
see fig. 3
E& <g$v
see [I31
_l. ..._.
~_.
fiv=0.781
Bodycenteredcubic
[ll]
Monovacancy
EIV =fivAK,v
see 1121
simple divacancy
Divacancy
fiv
= 0.468 [ 14161
Ezv =f2vA&vWW
see fig. 2
and [17]
&
< f2v
see fii. 3
and {13]
The most important method for obtaining information on fin metals, however, is the measurement of
the isotope effect in diffusion (for a recent review see
[33]). A quantitative measure is the isotope effect
parameter defined by
Dal@
EE
(mp/m,)i2  1
(2.21)
fT =f($,
(2.22)
U(Vj>
VT.
U(Vj) +
(2.23)
=f:v
AK,v ,
(2.25)
*If P(mplm,)1/2
 1
(mplm,)'i2 1
(2.24)
45
1 + G(vT, vi)
(2.26)
46
H. Mehrer /Atomic
=gzv
AKav
(2.27)
E =fivAKlv
BTV
+g,vAKzv
&
(2.28)
Sincefiv
>gzv (see table 1) and since A&V Q AKrv
we expect E to decrease with temperature even if
AKiv are temperature independent. Due to anharmoniticy effects the AK factors may slightly decrease
with temperature. However, theoretical estimates [39]
suggest that this temperature dependence is small.
2.4. Pressure dependence of selfdiffusion
Between the Gibbs free energy G of a solid and
its volume V the following thermodynamic relationship holds :
ac/ap = V,
(2.29)
(2.30)
t correction
term
(2.31)
AVeff = Aviv
DTV
6
+ AVav 3
(2.32)
c=&t
exp4x
t
X2
(3.1)
Here C denotes the tracer concentration, X is the distance from the surface, t is the diffusion time and Co
is a constant. In the most precise diffusion studies the
tracer distribution is measured with the help of an
appropriate serial sectioning technique which permits
material removal in thin layers parallel to the initial
surface and subsequent counting of the radioactivity
in each layer. Such measurements allow one to determine the tracer selfdiffusion coefficient to a fairly
high accuracy of a few percent (see, e.g. [ 11) and
provide unambigous information on the diffusion
kinetics.
From the viewpoint of deducing reliable defect
properties from tracer experiments it is important to
base such an attempt on measurements which cover
a temperature range as wide as possible. In the high
temperature region between the melting temperature
T, and about fT,,, mechanical sectioning techniques
can be used. In this region the diffusion coefficient
varies for a typical metal between about 1O cm2 /s
(near T,,,) and about lo* cm*/s. In cases where the
halflife of the available tracer isotope limits the time
for the diffusion anneal it may even be difficult to
reach the lower limit.
Fortunately nowadays powerful microsectioning
techniques are available which permit serial sectioning
on a submicron level.
Since the pioneering work of Pawel et al. [48501
various chemical and electrochemical techniques have
been developed (for a brief survey see, e.g., section 2.2
in [Sl]). These techniques.usually
consist of a twostep polishing process where oxide or halide formation is followed by dissolution of the oxide or halide
film in an appropriate solvent.
In very recent years sputtering methods have been
adapted for serial sectioning in tracer diffusion measurements. Two variants have been developed, one by
Gupta and Tsui [52] and another by Maier and Schtile
41
10
0,)
0.01
Fig. 4. Penetration plots of nickel selfdiffusion obtained by
means of a sputtersectioning technique [57].
48
H. Mehrer /Atomic
(4.la)
is satisfied, where w,, = yH, with y denoting the gyromagnetic ratio. The corresponding relation for T,, is
7w1=1.
(4.lb)
c=Ta,dip+Tol,ey
where a! = 1, lp. The effect of atomic jump processes
on T, is mainly contained in the dipolar contributions
which under appropriate experimental conditions lead
to a minimum of Tcyas a function of temperature. A
good example is provided by the measurements of
Messer [66] onisotopically
pure 7Li shown in fig. 5
where both the T1 and the TIP minimum have been
observed.
The electronic contributions to the relaxation rates
49
= ;y+Pz(1+
x (2wo)l *
42.0
3.0
1.0
Fig. 5. Nuclearmagneticrelaxation
according to [66].
5.0
6.0
35 Mffz
is well understood.
t Jt2)(2wo)}
i4.3a)
l){J@)(2wr)
+ lOJ()(wo)
+ P)
(4.3b)
1751.
A comprehensive treatment of the influence of
correlated diffusion on nuclearmagneticrelaxation
has been given recently by Wolf 1761. He obtained
numerical results for diffusion via monovacancies in
bee and fee crystals. The divacancy mechanisms in
cubic crystals and the simultaneous action of monoand divacancies has been considered in [77] and more
rigorously in [77aj. Both Tr,din and Tr,,unshow
minima near temperatures where either wo? = 1 or
wr? % 1. The exact position, shape and width of the
minima as functions of temperature depend on the
diffusion mechanism. From a fit of the theoretical
results to the data the mean jump time ? may be
determined.
(iii) The mean jump time is related to the uncorrelated selfdiffusion coefficient by the EinsteinSmoluchowsky relationship which for cubic crystals
may be written as
DSD = b=/fi,
(4.4)
where b is the jump distance. According to eq. (2.22)
the correlated diffusion coefficient is given by
D zfz>S= .
(4.5)
50
 cr) ,
(4.7)
where CY
is a small correction term. A critical comparison between experiments and theory has been
given recently by Janot 1791. According to eq. (4.7)
the activation enthalpy of diffusion may be simply
determined from an Arrhenius plot of Ae versus
reciprocal temperature. However, whenabsolute values of the diffusion coefficients are deduced and compared with tracer measurements, most experiments
indicate that the broadening is smaller than the
value predicted by theory. This is confirmed by a
recent paper by Lindsey [80] who investigated the
selfdiffusion of Fe in airon stabilized by small
amounts of vanadium. Although various improvements of the SingeSj~lander
model have been
proposed (SlSS] the theory is still not yet completely satisfactory. It appears that the situation is
Sine
*,pQ2
=f(e)
f@12+(Ml2 .
(4.8)
Here hw and &Q denote energy and momentum transfer during the scattering event. The DebyeWaller
factor e pQ2 determines the intensity of the line. The
energywidth of the line depends on Q like f(Q). For
jump diffusion in a lattice f(Q) is a periodic function
which depends on the lattice geometry and on the
diffusion mechanism. The extrema of f(Q) are directly
related to the atomic jump vectors. For small values
of the momentum transfer (Q + 0) the halfwidth
approaches 2 h2Q2DSDwhich permits a determination of the macroscopic seifdiffusion coefficient.
Recently AitSalem [90] and Goeltz [9 1] have
shown that selfdiffusion in sodium indeed affects the
quasielastic line. AitSalem concludes that selfdif
5. Application
to specific metals
5.1.1. Silver
The analysis of selfdiffusion data has been
reported in detail elsewhere [23]. It was based on
the most reliable high temperature data [21] and on
two recent measurements of low temperature selfdiffusion 122,231 by means of chemical microsectioning. The Arrhenius plot of selfdiffusion is curved. To
reveal the curvature more clearly the deviations of the
data [21231 from a single Arrhenius term, obtained
by force fitting eq. (2.13) to the data, have been
plotted in fig. 6. The mono and divacancy contributions deduced from the analysis of the temperature
80%
700
?O 8po
600
51
500
100 
TKJ
300
+
A
+
A
40%4
20%
e0
00
20 % 
+*
09
Y
l Qeff
+
+
0+
~ A
a
= 0.235 cm24
=
1.86 eV
10% 
I
0.8
I
1
I
1.2
1.1
lo/
1.6
T TKI
)
I
1.8
Fig. 6. Deviations of silver selfdiffusion data from a single Arrhenius term [23].
SO 800 700
i
600
8
TTCJ
coo
500
I
300
Ag selfdiffusion
D Rorhmon ( Pet~son vnd Robinson
+ tom, Kbthmon, Mehrer und Nowicki
d &c&us, Bokker und Mehnr
600
fly =c1782correlation
factor
for monovacancy
t
14
to7
$
.p
.
TECl
700
sCaa
800
900
Rothmon
AgtqAgllO
fJv=
0.8
0.468
correlation
factor
0.9
1.0
et al. I19701
isotope
effect
for simple
103/T
divocanc
, mecL*m
1.1
lK*]
_)
Fig.
I@@
0.8
1.0
1.1
1.6
lO+T c
1.8
Fig. 7. Arrhenius plot of tracer selfdiffusion in silver; monoand divacancy con~ibutions according to [ 2 31.
by fig. 1. Using the mono and divacancy contributions shown in fig. 7. The adjusted parameters are the
kinetic energy factors AKrv = 0.99 and AR2v = 0.95,
which are assumed to be temperature independent.
Reasonable fits, which imply AKzv Q AK, < 1,
have been achieved only when vzvl a jumps have been
taken into account. A ratio ~~v~r/v~vr~ between 0.3
and 0.7 near the melting point is compatible with the
data.
The pressure dependence of selfdiffusion has been
studied in [93] at a temperature not far below the
melting temperature. The observed activation volume
A pff = 0.9 atomic volumes is consistent with diffusion be mono and divacancies. However, a measurement of AVeff over a wide temperature range which
appears to be possible by means of appropriate microsectioning techniques would help to establish values
for AV,v and AVav.
5.12. Copper
Selfdiffusion in copper has been measured in the
high temperature region with high accuracy by
Rothman and Peterson [94] and by Bartdorff [95].
Rothman and Peterson also measured the isotope
effect and obtained an average value of E = 0.68 + 0.02
53
TCCI
100
600
selfdiffusion
0
Rothmon
Bartdorff
M&r,
in Cu
and Peterson
1969
1970
Schdc
extrapolation
IO+4
W73
and Seeger
1969
\
5.1.3. Nickel
lo7
0.8
I
1.0
1.2
1.4
10+/z CKI
1.6
Fig. 9. Arrhenius plot of tracer selfdiffusion in copper. Extrapolation from high temperatures according to [96].
T,,,=US3
1200
1000
800
600
Bakker
Maier,
and
1968
Mehrer.
Schiile
Lenmann
(1976)
54
,o?51
2.5
3.0
3.5
;\
1.0
4.5
,a
5.0 5.5
103K
T
cording to eq. (2.20) this ratio is just the average COTrelation factor of the diffusion process. Below 40C
the data approach the value flv = 0.727 which is
characteristic for a monovacancy mechanism. The
decrease with increasing temperature is fairly direct
evidence for a strong divacancy contribution at higher
temperatures. From eqs. (2.20) and (2.13) we obtain
for the simultaneous action of mono and divacancies
D%
f=flV~+f2vgg.
(5.1)
or
$5
.9
.7+
.6 .5 .L 
.3 
:I, , , , ,
2.0
2.2
2.1
(
2.6
2.8
,
3.0
,
3.2
t
3.4
3
j0.K
T
in lithium 166 1.
H. Mehrer /Atomic
and Smith
100
0.8
75
Li
AV,,,=AV,,D:,/D+AV,,D:,/D
of self
Table 2
Effect of isotopic mass on the mean jump time of lithium
according to (661
6Li
T Fl
50
9
to identify the mechanisms
in sodium.
diffusion measurements of the temperature, pressure, and mass dependence have been performed. The
temperature dependence of the tracer diffusion coefficient was measured by Mundy [108,109]. The Arrhenius plot shown in fig. 5.8 is clearly curved upward.
The pressure dependence was investigated by Nachtrieb et al. [l lo] and Mundy [109] by means of a
radiotracer technique and by Hultsch and Barnes [ 11 l]
by means of nuclearmagneticrelaxation.
The effective activation volume deduced from these experiments shown in fig. 14 increases with increasing temperature. The isotope effect data [108,109] plotted
in fig. 15 show a gradual decrease with increasing temperature.
It is tempting to attribute these findings to the
simultaneous contributions of mono and divacancies
to selfdiffusion. A fit of the temperature dependence
LO.6
5.2.2. Sodium
In an attempt
5.5
04
8Li
:
0.937
1.088
0.926
1.068
3.0
3.5
103/T
4.0
WI

of selfdiffusion
4.5
in
H. Mehrer /Atomic
56
0.6
0.5
.
a
Mundy
Mundy,
E = AK,,I,,
*
0;
/D
AKJv gJv
0:
10
ij&+..F
0.3
0.2
?
0.1
Acknowledgements
I am grateful to Dr. R. Messer for making available
his NMR measurements on lithium prior to publication. I also benefited from discussions with Professor
Seeger and with my colleagues Dr. K. Maier, Dipl.Phys. G. Hettich and Dipl.Phys. G. Reiu.
References
Fig. 15. Isotope effect of selfdiffusion in sodium.
[II N.L. Peterson, in: Solid State Physics, Vol. 22, F. Seitz,
in terms of eq. (2.15) is shown in fig. 13 as a solid line.
The mono and divacancy contributions shown as
dashed lines are described by 0:" = 3.76 X low3
exp(0.365
eV/kT) cm2/s and Dzv = [0.292
exp(0.457
eV/kT) + 8 exp(0.575 eV/kZJ] f2v
cm2/s, withf2v given in fig. 2. The two activation
enthalpies in the divacancy contribution pertain to
the two saddle points between the various divacancy
configurations. The strong divacancy contribution is
supported by the pressure and isotope effect data.
Fits of eqs. (2.33) and (2.28) to the data are shown
in figs. 14 and 15 as solid lines. In these fits the monoand divacancy contributions deduced above have been
used. The fit to the pressure data yields A V,v =
0.32 52 and A V2v = 0.59 52 (52 = atomic volume). The
numerical values of the activation volumes also support the view that the two mechanisms are indeed
due to mono and divacancies. The kinetic energy
factors in the fit of the isotope effect data AK,v =
0.68 and AKzv = 0.55 are in reasonable agreement
with theoretical predictions for bee metals mentioned
in section 2.3.
In the immediate vicinity of the melting point the
selfdiffusion data reveal a sharp upward curvature of
the Arrhenius plot. A possible interpretation
of this
phenomenon could be secondnearestneighbour
jumps caused by divacancies as suggested by the
findings of quasielastic neutron scattering discussed
in section 4.3. Another explanation could be the
57
58
H. Mehrer /Atomic
Discussion
D. Lazarus: I should like to emphasize that the general
picture of a strong divacancy contribution at high temperatures, while resonable, should still be questioned because:
(1) there are no isotope effect measurements for
D 5 lo13 cm*/s;
(2) the Hart mechanism may contribute to D at low temperatures, causing an enhancement in the monovacancy contribution; and
(3) the AilionSlichter NMR measurements on sodium,
over an enormous range of temperatures, do not indicate any
curvature compared to hightemperature tracer data.
D. Gupta: The contribution of the Harttype dislocation
enhancement to the lattice diffusion should be kept in view
while examining the data for curvatures in the Arrhenius plot.
It has been our experience that such effects may become significant in the 10l * 10l 6 cm* diffusivity range for
annealing times of a few hours. At lower temperatures and
diffusivities, < 10l 6 cm*/s, the effect is always negligible
even for high dislocation densities of 10 lines/cm* and the
quality of the data improves.
H. Mehrer: (1) It is true that there are no isotope effect
measurements for lower temperatures and diffusivities. The
reason for this is that such measurements are difficult to perform. It appears, however, that nowadays isotope effect
experiments at lower temperatures could be done by means
of the microsectioning techniques discussed in section 3 of
my paper. Such measurements, when performed under conditions where a dislocation enhancement of the lattice diffusivity is negligible, would indeed be highly welcome. They
would provide unambiguous information about the kinetic
energy factor AK1 V of the monovacancy mechanism.
(2) I agree with the comments of Professor Lazarus and
Dr. Gupta that a possible influence of diffusion short circuits
on the observed diffusivity must be kept in mind and, if
necessary, must be eliminated to obtain reliable values of
the bulk diffusivity. This has been done in all the examples
discussed in my paper.
The influence of dislocation short circuits may be eliminated if highly single crystals and/or the microsectioning
techniques discussed in section 3 are used. Whether dislocation pipe diffusion influences the value of the diffusivity
deduced from the gaussian segment of the penetration profile
in a standard tracer experiment depends upon the conditions
under which the experiment is performed. When the mean
lattice diffusion length, a,
is large as compared to the
mean dislocation distance, 7, the observed diffusivity may
be enhanced through d,rocation pipe diffusion (Harttype
H. Mehrer /Atomic
59
enhancement). When a microsectioning technique is used diffusion may be investigated under conditions where
fi
<< a. The penetration profile then consists of a gaussian segment which is mainly due to lattice diffusion and of
a socalled tail due to dislocation pipe diffusion, thus permitting an unambigous separation of both contributions. In
 a
cases where m
 this separation may indeed be difficult
as pointed out in the comment of Dr. Gupta.
(3) According to my knowledge there are no NMR measurements on sodium by Ailion and Slichter. Presumably the
third comment of Professor Lazarus refers to measurements
on lithium [DC. Ailion and C.P. Slichter, Phys. Rev. 137
(1965) A 235; see ref. (68) of the present paper]. It is true
that these measurements cover almost the same temperature
region as the NMR data of Messer discussed in detail in section 5.2.1 of my paper. The very recent data of Messer are,
however, by far more comprehensive since both Tf, and TI
have been measured for various relaxation fields also. On
the other hand there is no discrepancy between the raw data
of both investigations for the same relaxation field. However,
since the pioneering work of Ailion and Slichter the NMR
theory of relaxation through diffusional motion in solids has
been considerably improved. In particular the effects of specific diffusion mechanisms in metals and of temporal correlation between atomic jumps have been included into the
theory asoutlined in detail in section 4.1 of the present paper.
These improvements have already been utilized in the evaluation of Messers data. The arrhenius plot of the macroscopic
selfdiffusion coefficient deduced from Messers data is shown
in fig. 11 of the paper. It clearly reveals considerable curvature.
D.N. Seidman: This comment is in response to Professor
Lazarus comment about the existence of divacancies. I would
like to point out that in the case of quenched platinum
[AS. Berger, D.N. Seidman and R.W. Balluffi, Acta Met. 21
(1973) 1231 we have observed directly by means of fieldion
microscopy, both monovacancies and first nearestneighbor
divacancies. The direct measurement of the divacancytomonovacancy concentration ratio enabled us to determine
the Gibbs free binding energy of a divacancy for a quench
temperature very close to the melting point of platinum
[A.S. Berger, D.N. Seidman and R.W. Balluffi, Acta Met. 21
(1973) 1371.
C.P. Flynn: The Gibbs functions ordinarily met in thermodynamic relationships define the enthalpies, volumes and
entropies of bodies according to:
s = (aG/aT)p:
V = @G/a&:
H = G + ST.
(1)
cp = (aHfaT), = r(as/ar),
(2)
There are also stability relations [ 1121 that constrain the possible behaviour of G for solid materials to be such that
c, > 0,
c>o,
(3)
asT+0.
(4)
60