J. Phys. Chem. Solids Pergamon Press 1971. Vol. 32, pp. 939-949. Printed in Great Britain.

A MODEL FOR THE INVAR ALLOYS AND THE

Fe-Ni SYSTEM

W. F. "SCItLOSSER
Department of Physics, University of Toronto, Toronto 5, Ontario, Canada

(Received I 1 June 1970; in revised form 14 August 1970)

A b s t r a c t - A model is proposed to account for the metallurgical and physical properties of f.c.c.
F e - N i alloys, including the lnvar anomalies around 34 at.% Ni. Microscopic inhomogeneity due to
short range atomic ordering on the basis of the FeNia compound is assumed to be a dominant feature
of the alloy system. Regions of both f.c.c. Fe and FeNi3 are present in alloys in the invar region. The
electronic state of only the Fe atoms, and hence their volume, magnetic moment, and sensitivity to
external variables, is further assumed to be a function of the number of Ni nearest neighbours, which
in turn depends on such variables as cold work. With these assumptions, the properties of the annealed
alloys above the Curie point are developed, the phase diagram and metastability of the alloys is
explained and the lnvar anomalies below the Curie point are accounted for. Furthermore, the model
explains the unusual low temperature properties of these alloys as due to exchange coupling between
ferromagnetic FeNia regions and antiferromagnetic Fe regions. An extension of the model is made to
other binary alloy systems that exhibit Invar-type anomalies:

1. INTRODUCTION small and negative only above 70% Ni.

THE F.C.C. iron-nickel alloys in the Invar
concentration range, ~ 35 at.% Ni, are ano-
malous in many respects; in particular, the
fall of the T --- 0 magnetization with increased
concentration of Fe [1,2], the departure from
Vegard's Law[3] and the associated large
spontaneous volume magnetostriction[4] and
low thermal expansion[5] below the Curie
temperature, may be cited. The preceding
paper[6] has described measurements of the
large forced magnetostriction below room
temperature in invar. There is also an ano-
malously large paraprocess susceptibility [7,8]
and large temperature variation of the mag-
netization [ 1,7,8].
A feature of these anomalies is their per-
sistence to quite high Ni concentrations in
somewhat attenuated form. Deviations in the
concentration dependence of the lattice
parameter are evident at -- 57 at.% Ni[3], and
in the magnetic moment at - 5 8 at.% Ni[1].
The positive volume anomaly [5] that occurs
below the Curie temperature of the invar
alloys, although largest at - 3 4 a t . % Ni, is
still quite prominent at 60% Ni and becomes
939
Similarly, a negative term proportional to the
temperature is still present[9] in the experi-
mental fit to the thermal expansion near T ----0
for a 50 at.% Ni alloy.
Attempts to explain these anomalous prop-
erties have often involved the assumption of
a random distribution of Fe and Ni atoms
[10-17], with some further assumptions about
differences in the interatomic interactions for
the different possible pairings[16, 17]. These
models do not seem able to account for the
persistence of the anomalies to very high Ni
concentrations.
In this paper we propose a new model
applicable not only to the invar alloys, but to
the whole F e - N i system. The invar anomalies
then are seen to be a consequence of the
factors that determine the behaviour of this
system.
The existence of microscopic inhomogeneity
in the alloy is regarded as a premise. Given
this, the model rests on two main assumptions:
first (a) that the atomic ordering of F e - N i
alloys is not random, but is characterized by
extremely marked short range atomic order
940 W.F. SCHLOSSER
on the basis of the FeNi3 compound with the
tic.c. L 1~(CuAua) structure [ 18], and secondly
(b) that the number of Ni nearest neighbours
determines the electronic state of a Fe atom
while the Ni atoms are not sensitive to the
local atomic environment.
These assumptions are expanded on and
justified in Section 2. The model is developed
from them in Section 3, and applied to dis-
tinguish between the behaviour of well an-
nealed and cold worked alloys.
The model is applied to the explanation of
the invar properties in Section 4, with
particular emphasis on the results of the pre-
ceding paper. Section 5 generalizes the model
to other invar-type alloy systems.
2. ASSUMPTIONS
In the models of several authors[10-15]
inhomogeneity has been arbitrarily assumed
to avoid a singularity in the alloy properties at
30 at.% Ni. While the introduction of a fine
scale inhomogeneity certainly has important
consequences for such models, it has been
given no experimental or theoretical justifi-
cation. The model of Shiga and Nakamura
[19,20] also assumes a random distribution of
Fe and Ni atoms[21], but with a variable
electronic state for the Fe atoms. This
random distribution is insufficient to explain
the properties of F e - N i alloys over a wide
range of compositions and temperatures.
Neutron scattering data[22-24] and elec-
trical resistance studies [25,26] on the F e - N i
system indicate that extensive short range
atomic order is present over wide composition
and temperature ranges in supposedly dis-
ordered alloys. This ordering is based on the
FeNi3 compound. This compound is ferro-
magnetic[18] with a Curie temperature
between 863 and 980 K, probably closer to
863 K. There is considerable uncertainty in
this temperature as the compound disorders
at a lower temperature, 780 K. The Curie
temperature of the disordered alloy with
75 at.% Ni is -- 873 K. The importance of the
short range atomic ordering based on the FeNi3
compound is stressed in this paper. To illus-
trate this, in Fig. 1 we have plotted the liquidus
for the F e - N i alloy system, the heat of for-
mation of these alloys, the coefficient of the
linear term in the low temperature specific
heat, and the D e b y e 0. Again we wish to
point out that it is not the peculiar behaviour
of these alloys around 35 at.% Ni that is
significant, but the observation that this
peculiar behaviour begins near 75 at.% Ni.
This first assumption will allow us to make
semi-quantitative statements about the local
environments of particular atoms.
Collins et al.[22] proposed a structure in
which the cube corner sites of the f.c.c, cells
are occupied mainly by Fe atoms and the
face-centre sites are randomly occupied by the
remaining Fe atoms and the Ni atoms. The
structure maximizes the number of F e - N i
nearest neighbour pairs. The present assump-
tion differs from theirs in stressing the impor-
tance of the contribution to the stability of the
system of the FeNi3 structure as a whole. It
is probably not possible to decide between
these models on grounds of their relative
stability by a fundamental calculation; the
analogy with the f.c.c. C u - M n alloys, which
are known to evolve by segregation of Mn
atoms [27], would seem to offer some support
for the present model. In any case, the main
practical difference between these models
lies in the existence of a more well defined
interface between Fe-rich and Ni-rich regions
under our assumption. The properties of the
system are then conveniently discussed in
terms of the positions of atoms with respect to
the interface, or transition region, without
reference to the details of the background
statistical inhomogeneity which is the impor-
tant feature of the alternative assumption [22].
Our second assumption relates the atomic
behaviour to particular environments. It
follows more nearly the idea of Shiga than the
'two states of iron' idea of Weiss [33], in that
we suppose that the electronic configuration
of a particular Fe atom, which determines its
interaction with nearby atoms and hence the
 A MODEL FOR THE INVAR ALLOYS 941

oF- (

~ 150(? -
I.u
n--

i 147~

~ 1425~

-~~176
I
4Bob- I 9
9 - ,zz

/?
~- ~/ l-I ~~

'~176 7 /-q~

3ao - ~ ~ -~4.o
/
T c rrex ~ 1 1 1 3 . 6
30(
20 30 40 50 60 70 80 90 I00
COMPOSITION ( ATOMIC% Ni )
Fig. l. The liquidus[28], the heat of formation[29, 30] and
the low temperature specific heat 3,[31] and 0[31,32] for the
Fe-Ni alloy system.
942 W.F. SCHLOSSER
nearest neighbour distances and the ordered
state magnetic moment on the atom, can vary
between two limits depending primarily on
local atomic environment, and on external
variables such as temperature and magnetic
field. This assumption has theoretical support
in the work of Goodenough[34] and Bailyn
[35]. The main experimental justification for
this assumption is the observation that the
lattice parameter of 3' Fe in its region of
stability (1183 to I662 K) linearly extrapol-
ates to a 300 K lattice parameter o f - 3.574A
[36,37]. The 300 K lattice parameters[18] of
F e - C , F e - N , and F e - M n alloys against
concentration extrapolate also to - 3.57 A for
pure Fe. However, Fe atoms enter into solu-
tion in F e - N i , F e - P d and F e - P t alloys, for
not too large Fe concentrations, causing a
change in lattice parameter[38] which extra-
polates to a 300 K lattice parameter of - 3.64
A in each case. The small parameter state of
Fe appears to be antiferromagnetic at low
temperatures with a magnetic moment of
1 /x/~ or less [39-42]. The large parameter
state of Fe contributes a large moment (~ 2.8
/zB) per atom when alloyed with Nil1], Pd
[43-46] or Pt[47] at sufficiently high concen-
trations (7 - 10 at.%). An Fe atom with all Fe
nearest neighbours will then have a low
'volume', (the volume of an atom being
defined in terms of the nearest neighbour
distances), and have a small magnetic moment
oppositely oriented to the moment on the
atoms around it at low temperatures. Above
some minimum effective number of Ni
neighbours, an F e atom has essentially its
maximum moment and volume. Between
these extremes the moment and volume of the
Fe atom in question are strongly dependent on
the number of Ni nearest neighbours, as well
as on external variables. The increase in
volume with magnetic moment is a result of a
change of bonding electrons with no moment,
into non-bonding electrons with magnetic
moment[19,48]. This lower number of bond-
ing electrons results in a reduction of the
cohesive force, an increase in nearest neigh-
bour distances, and an expansion of the whole
alloy relative to a linear interpolation
(Vegard's Law) of the lattice parameters of the
two components of the alloy, f.c.c. Ni and
f.c.c. Fe. Thus, this assumption alone explains
why the presence of Ni nearest neighbours
produces an increase in volume and a large
positive departure from Vegard's Law above
Tc. Another related effect appears for those F e
atoms with insufficient Ni neighbours to have
the maximum atomic volume at To. As the
alloy is cooled below its Curie temperature
these atoms will increase their moment due to
a net increase in the magnetization with
decreasing temperature. The conversion of
non-magnetic, bonding, 3d electrons to
magnetic, non-bonding electrons in the polar-
ization process reduces the bonding of this
atom to its neighbours, resulting in a large
positive spontaneous magnetostriction below
the Curie temperature and a corresponding
large decrease in the thermal expansion
coefficient. Furthermore, an applied magnetic
field, by increasing the magnetization also
converts Fe atoms to high moment states,
producing a large high field susceptibility and
forced volume magnetostriction. The essential
feature of this paper is the application of these
ideas to the particular constraints imposed on
a model in which most of the Ni atoms are
in the FeNiz compound.
3. THE MODEL
1. lnhomogeneity and the alloy structure
We consider first a well annealed alloy. By
this we mean an alloy annealed at low tem-
peratures sufficiently to allow the diameters of
the ordered regions to exceed several lattice
parameters. These regions are single phase
ordered domains and are generally of irre-
gular size and shape. An alloy contains three
regions of interest due to the existence of
ordering. These are illustrated in Fig. 2. Type
1 regions consist of FeNi3 of assumed perfect
order. In this core, each Fe atom has ideally
12 Ni nearest neighbours and exhibits its
maximum moment and nearest neighbour
 A MODEL FOR THE INVAR ALLOYS
I I
7.'
I I
FeNi 3
I I
I t
5 TYPE 3 I TYPE 2 TYPE I
'/I
i I
,,=, I I
i I
8 i. J total alloy volume in type 2 regions increases.
E, Fe i I
DISTANCE ALONG SECTION INDICATED IN UPPER DIAGRAM
Fig. 2, The three types of regions defined in our model of
the F e - N i alloys. The upper diagram illustrates the
regions for a low nickel concentration alloy. The lower
diagram illustrates the variation of the nickel concentra-
tion in the various regions.
distance. Type 2 regions form shells around
the regions of perfect order and are the
regions of decreasing Ni concentration and
decreasing order that separate the perfectly
ordered type 1 regions from regions designated
type 3 which are the f:c.c, iron excluded from
regions 1 and 2 due to the existence of FeNi3
order in Fe rich alloys. Type 3 regions contain
no nickel, but consist of the segregated f.c.c.
Fe atoms with small nearest neighbour dis-
tance ( - 1 . 2 6 A ) and with low moment
(~ I/zB or less).
The boundary of a type 1 region is drawn
along iron atoms with sufficient Ni nearest
neighbours that they exhibit practically their
full volume and moment at high temperatures
(above ~ 9 0 0 K ) . The material in type 2
regions is that which can exhibit large changes
in volume or moment in response to changes
in external variables. Thus an important para-
943
meter is the volume of the type 2 regions in an
alloy. For well annealed alloys, it may be
assumed that the thickness of type 2 regions
is approximately constant and independent of
the size of type 1 regions.
The general effects of decreasing the nickel
concentration in an alloy from the 75 at.% Ni
ordered compound are then as follows. D o w n
to 65-70 at.% Ni no change in the alloy proper-
ties are apparent. The minimum number of Ni
nearest neighbours has not fallen below the
defining value f o r type 1 regions. At concen-
trations below 65 at.% Ni, added Fe atoms
can no longer be accommodated in ordered
FeNi3 regions, and begin to appear as isolated
type 2 regions, still containing some nickel
which will influence the state of the Fe atoms.
As additional iron is added to the alloy, the
The presence of ordering in the alloy, obtained
through atomic diffusion, dictates that the
type 2 regions take the form of thin layers
tending to surround and isolate the ordered
type 1 regions. A maximum volume of type 2
material occurs when the ordered regions are
just separated from each other by type 2
material. The composition at which this
occurs may be estimated by considering the
type 1 material to be in spheres. The maximum
surface area of the spheres (and therefore
maximum type 2 volume for a well annealed
alloy) will occur ,when the spheres come into
contact. If the spheres are in a cubic array,
this will be when half the total volume is
inside the spheres.
If the material outside the spheres is pure
Fe and that inside is FeNi~, the maximum
occurs at - 37.5 at.% Ni. This figure is in good
agreement with the Ni concentration of the
alloy exhibiting the largest invar anomalies
(~ 35 at.% Ni) and with the Ni concentration
of the alloy exhibiting the maximum deviation
from Vegard's Law . ( - 43 at.% Ni). The
difference in these concentrations can be
understood when the finite thickness of the
type 2 regions is considered. The maximum
high temperature deviation_from Vegard's
944 w. F. SCHLOSSER

Law is expecte.d to occur at a higher Ni
concentration than that corresponding to the
maximum in the invar anomalies, because the
former is determined by the amount of type 1
material only (by the expansion mechanism
outlined in the previous section), while the
anomalies are due to the type 2 material. The
maximum amounts of type 1 and type 2 will
not occur at the same Ni concentration if
there is a finite thickness of type 2 material.
2. Effect of cold working
For well annealed alloys the thickness of
the type 2 regions is approximately inde-
pendent of further annealing, yet the size of
the ordered type 1 regions increases with
further annealing by growth of the more
favourable regions at the expense of others.
Therefore the type 3 regions will increase in
size with further annealing, while the volume
of the type 2 regions decreases.
In general, since both quenching and cold
working result in a reduction of the degree of
order in an alloy, both processes increase the
amount of type 2 material at the expense of
material of both t y p e s 1 and 3. Remembering
that the amount of type 2 material is a measure
of the magnitude of the anomalies, the model's
prediction of an increase of this with increase
i n t h e disordering of the alloy is in agreement
with experiment[4,49]. These assumptions as
ordered type 1 regions. The stability of the
alloy can be maintained only if a large inter-
face area is present. As we have just seen,
annealing reduces this. The Fe regions grow
until they become unstable, and then trans-
form to the b.c.c, phase. The alloys are
metastable up to 65-70 at.% Ni. The time
required for equilibrium is, however, extremely
long below 400~ as the necessary migration
of nickel atoms must occur by diffusion, a very
slow process at low temperatures.
From our model the low temperature
equilibrium is between b.c.c. Fe and the
ordered FeNia compound with some excess of
Fe. This is in good agreement with the
experimental phase diagram of Hansen[52]
(Fig. 3) and with the more recent delineation
of the phase boundaries of the ordered regions
o f the Fe-Ni system by Kneller[53]. The
phase diagram of Ananthanarayanan and
Peavler[54], obtained with very fine particles,
extends the region of stable ordered f.c.c.
alloy to - 5 7 a t . % Ni. At concentrations
below 65 at.% Ni, this model is in accord with
the work of Kneller in assuming the lack of
strong FelNil ordering in the Fe-Ni system.
160C
UID
140C
MINI~MUM
9"-'67ot % Ni

to the presence of FeNi3 ordering are suffi-

120C
cient to explain the effects of rolling on the
properties of invar single crystals observed by
Chikazumi et al.[49], which they could not IOOC
interpret on the basis of Fe3Ni ordering.
7" Fe Ni3
3. Stability and the phase diagram
:o 80C
I-
!
f.c.c. 3, iron is unstable below 1183 K, and ~ \ ~66~t % Ni

transforms to the b.c.c. ~ form. In finely I- 60C

divided form, f.c.c. Fe can be maintained

below this temperature through coherency
with a suitable lattice[50,51] although the
lattice match is rarely perfect, and there is in ^^:~o%
general a coherency strain at the interface. In 200 :F~uTo~\ I I I I ~l-, I I
I0 20 30 40 50 60 70 80 90 I00
the f.c.c. F e - N i alloys, the f.c.c. Fe regions ATOMIC PER-CENT NIC~C
are stabilized by coherency with nearby F i g . 3. T h e phase d i a g r a m o f t h e F e - N i system [52].
 A MODEL FOR THE INVAR ALLOYS
4. EXPLANATION OF INVAR PROPERTIES
1. General
Turning to application of these ideas to the
observed properties of the invar alloys, suffi-
cient mention has already been made of those
properties which depend on the inhomogen-
eity per se, such as the departure from
Vegard's Law.
A large class of anomalous properties
depend particularly on the amount of type 2
material present, since this is the fraction
whose behaviour is sensitive to external
influences. It may be stressed again that this
model explains in a natural way the persis-
tence of anomalies in properties like the
paraprocess susceptibility or thermal expan-
sion to high Ni alloys. The general nature of
the magnetic ordering with decreasing tem-
perature according to this model is as follows
-individual regions of the alloy interact more
strongly through common type 2 regions or
type I overlaps to form larger regions of
magnetic order, and eventually a macroscopic
Curie transition. The Curie transition is thus
quite broad, with a high temperature tail,
reflecting the inhomogeneity of the alloy
[4,55,56]. The continual increase of the
magnetic moment of the alloy due to both the
coupling of isolated regions and increased
induced magnetization in type 2 regions
results in a curve of magnetization vs. tem-
perature that falls considerably below a
Brillouin curve fitted at T = 0 and at To. This
flattened curve is a well known feature of the
invar alloys[I]. The large spontaneous
magnetostriction and hence the thermal
expansion anomaly below the Curie point are
a consequence of the increased induction of
Fe in type 2 regions due to increased ferro-
magnetism in the alloy.
2. Exchange coupling in the 35% Ni invar
In order to fully explain the results pre-
sented in the preceding paper[6], and other
data for invar alloys in the vicinity of 35 at.%
Ni, where all three types of regions are pre-
945
sent: pure f.c.c. Fe, ordered FeNia and the
type 2 transition region, one additional
assumption is necessary: as mentioned, it is
supposed that the type 3 regions are anti-
ferromagnetic at low temperatures, for in-
vestigations[57] have shown that f.c.c. Fe is
antiferromagnetic at low temperatures with a
Neel point below 100 K. Mossbauer results
for low Ni concentration alloys[2,58-61]
show that a paramagnetic line, which we attri-
bute to the type 3 regions, is prominent. It
broadens below 90 K[2,58,59], indicating an
antiferromagnetic transition in type 3 regions
to a magnetic state with low internal field.
Extrapolation of the N6el temperature of
antiferromagnetic F e - M n alloys[62-65] to
pure Fe also indicate that f.c.c. Fe should
become antiferromagnetic below - 80 K.
According to this model, the invar alloys
have a very unusual structure below this
transition. Type 1 and type 2 regions are
ferromagnetic, type 3 regions are antiferro-
magnetic, and the two types of magnetic
regions interact at the boundary between the
type 2 and type 3 regions. In this temperature
range both regions vie for control of the type 2
material and there is a very large area of
interface between the ferromagnetic and
antiferromagnetic regions. Kouvel[66] pro-
posed a mechanism of very strong coupling
between ferro- and antiferromagnetic regions
in f.c.c. Mn alloys to explain their magnetic
properties. These alloys are believed to have a
similar microstructure to that proposed here
for the F e - N i alloys. This type of strong
coupling between ferro- and antiferromagnetic
regions has been observed in other materials
[67] and is attributed to exchange of magnetic
electrons between atoms on opposite sides of
the boundaries of the regions. I n an ideal
ferromagnet and an ideal antiferromagnet the
direction of the magnetization at zero field
relative to the crystal axes is determined by
the magnetic anisotropy of the material. F o r
the antiferromagnet this refers to the sub-
lattice magnetization. Rotation of antiferro-
magnetic moments is comparatively difficult
946
and requires large magnetic fields to achieve
small rotations. Thus, if there exists an
exchange coupling between ferromagnetic and
antiferromagnetic atoms at the boundary
separating them, the antiferromagnetic atoms
can seriously affect the behaviour of the
ferromagnetic region.
We assume that this coupling energy has a
temperature dependence and magnitude
relative to the anisotropy energy of the anti-
ferromagnet as given in Fig. 4. Just below the
ANTIFERROMAGNETIC
ENERGY
~ISTROPY
tr
i ~ f~ ~ ~
t.~
z
I
I
o rE
Fig. 4. The relation assumedbetweenthe anisotropy energyof the antiferro-
magnetic regions and the exchangeenergy coupling these regions to neigh-
bouring ferromagnetic regions.
N6el temperature, the anisotropy energy of
the antiferromagnet is small and the ability of
the ferromagnetic regions to respond to a
magnetic field is only slightly reduced by the
constraint of the exchange coupling to the
antiferromagnetic regions. However, losses
can be expected in this region as the anti-
ferromagnetic moments are rotated against
their anisotropy energy. A peak in the ultra-
sonic attenuation has been reported for invar
alloys below 100 K by both Meincke and Litva
[68] and by Fletcher[69]. As the temperature
W. F. SCHLOSSER
TE, at which the couplingenergy is equal to
the antiferromagnetic anisotropy energy, is
approached, ferromagnetic and anti ferro-
magnetic regions become more tightly ccupled.
The antiferromagnetism of the type 3 regions
increasingly restricts the induction of ferro-
magnetism in adjoining type 2 regions. The
forced magnetostriction thus decreases in this
region, and the rigidity of the lattice increases
as less material can transform between the
low volume and the high volume states.
EXCHANGECOUPLING
~ ENERGY
TEMPERATURE
Experimentally an increased rigidity of the
m a t e r i a l - a decrease in the magnetoelastic
coupling-is observed below - 2 0 K. The
forced magnetostriction decreases by - 3 0
per cent below this temperature[6], the mag-
netic susceptibility exhibits a corresponding
decrease [70], the velocity of sound rises [68],
and the compressibility correspondingly falls
below ~ 40 K.
According to our model, cold worked and
annealed alloys are distinguished by the
amount of type 2 material present. As we have
 A MODEL FOR THE INVAR ALLOYS
seen, increased coupling of the antiferro-
magnetic regions to the lattice reduces the
ability of type 2 regions to respond to changes
in temperature or magnetic field. For very
strong coupling, i.e. below TE, cold worked
and annealed alloys can be expected to behave
identically, as has been observed experimen-
tally [6]. Despite large differences in the ther-
mal expansion coefficient above 2 0 K for
entirely different samples from different
manufacturers and of different purity, there is
remarkably little difference between the
values for these samples below 20 K. Similarly
the forced magnetostriction of annealed and
cold worked samples, from the same rod,
begin to converge to a common value at 20 K.
The response of such exchange coupled
magnetic systems to a rapid change in external
conditions is generally logarithmic in time. For
example, experiments on exchange coupled
C o - C o O and N i - N i O films by Schlenker [71]
have shown this time dependence of the
response of the magnetization to a change in
magnetic field. A logarithmic time dependence
of the rotational torque at high magnetic fields
was found in Fe65 (Nil-xMnx)35 alloys ex-
hibiting exchange coupling by Nakamura and
Miyata [21]. It is expected in view of the
observation of rotational torque hysteresis in
29-32 at.% Ni invar alloys by Nakamura,
Takeda and Shiga[59], which correlated with
the widening of the paramagnetic Mossbauer
line in these alloys at low temperatures, that
exchange coupling time effects would be found
in the higher Ni invar alloys. The observation
of a logarithmic time dependence of the
volume of a 33 at.% invar alloy following a
change in the magnetic field (above saturation
only) seems to confirm its presence. The
temperature dependence of this length re-
laxation is similar to the temperature depen-
dence of the torque relaxation reported for the
Fees(Nil-xMnx)a5 alloys[21]. This tempera-
ture dependence follows from Fig. 3, where
relaxation can only occur by thermal excita-
tion for temperatures within kT of TE (the
hatched regions) but with some broadening in
947
a real alloy due to the variable conditions
affecting different regions in the alloy. For a
change in magnetic field, the response of the
alloy, principally occurring at the boundary
between type 2 and type 3 regions and
involving a change in the state of Fe atoms,
relaxes through a volume creep because of the
strong magnetoelastic coupling. The slope of
the logarithmic creep curve and the extent of
the relaxation depend on the existence of a
well defined boundary between type 2 and
type 3 regions, which is favoured by annealing.
The temperature dependence of the rate of the
logarithmic creep thus reflects the shape of the
anomaly at 90 K [6].
The decrease in magnetoelastic coupling
observed below 20 K is a common feature of a
wide range of alloys, (up to 45% Ni). In the
alloy Fe65(Ni10.TMn0.3)35 there is a sharp drop
in the magnetic moment of the alloy below
20 K[19]. The magnetization results of
Cochrane and Graham[18] also show an
unexpected fall of the moment from the high
temperature extrapolated values below 20 K
(1 in 104). This similarity of the temperature
dependence of the magnetoelastic coupling,
despite a wide range of magnitude and alloy
compositions can be accounted for quite
readily by our model where the temperature
dependence of the coupling exhibits different
behaviour above and below a temperature
determined only by the antiferromagnetic
anisotropy energy of the pure Fe type 3
regions, which we assume occur in all of these
alloys, and the exchange coupling between
type 3 and type 2 regions, which does not
vary greatly with alloy composition.
CONCLUSIONS
In summary, we have proposed a model for
the F e - N i alloy system, which stresses the
atomic inhomogeneity. By assuming that this
inhomogeneity is due to short range atomic
order based on the FeNi3 compound, and that
the state of an Fe atom depends on the number
of Ni nearest neighbours, the model is made
sufficiently simple that it can be used to make
948 W. F. S C H L O S S E R
predictions of a wide variety of physical
properties that turn out to be reasonably in
accord with experiment.
It is possible to generalize this model to
other systems under the following conditions
for the appearance of invar properties.
(1) The alloy system must exhibit consider-
able short range atomic ordering based on a
magnetic compound in a paramagnetic or
diamagnetic matrix. The compound involved
in the invar properties will be the most stable
compound in an alloy system.
(2) The magnetic compound and matrix
must have the same or a similar crystal
structure, similar, though not equal, lattice
parameters and some degree of coherence
across the compound-matrix interfaces.
The invar anomalies will b e m o s t intense at
a composition approximately half-way be-
tween the composition of the matrix and the
stoichiometric composition of the compound
responsible for the short range order.
There are two other binary alloy systems
that exhibit invar anomalies: F e - P d and
Fe-Pt. They differ from the F e - N i system in
easily forming stable ordered I:1 ferromag-
netic compounds FePd[72] and FePt[73].
The invar anomalies are found in the iron-rich
disordered alloys of these systems, are most
intense in the region 2 5 - 2 7 at.% Pd or Pt
[74-78] and are destroyed by the Fe3Pt order-
ing in the F e - P t system[79,80]. Also, the
concentration dependence of the invar
anomalies is sharper for the F e - P d and F e - P t
systems, and the anomalies are stronger
[5,74-80].
Partial satisfaction of the above conditions
in other alloy systems may result in the
appearance of weak invar-like anomalies. We
have tried to show that the effects of inhomo-
geneous structure of the alloy must be con-
sidered as an essential part of the analysis of
data on such systems. These effects may even
dominate the behaviour of the material.
Although present knowledge of the con-
sequences of these structural features is
limited, a re-examination of existing data on
invar and related alloys should provide
further correlation of the physical and
metallurgical properties of these alloy systems.
Acknowledgements-The author wishes to thank Dr. G.
M. Graham, Dr. P. P. M. Meincke, and Dr. E. Fawcett
for their assistance in the preparation of this paper.
This work was supported by the National Research
Council of Canada.
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