Materials Today: Proceedings 43 (2021) 2242–2244

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Materials Today: Proceedings

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Fe-Ni Invar alloys: A review

A. Sahoo, V.R.R. Medicherla ⇑
Department of Physics, ITER, Siksha O Anusandhan Deemed to be University, Bhubaneswar 7510303, India

a r t i c l e i n f o a b s t r a c t

Article history: Fe-Ni alloys with face centred cubic structure having Ni concentration around 36% exhibit extremely low
Received 23 August 2020 or no coefficient of thermal expansion over a wide range of temperatures around room temperature
Received in revised form 1 December 2020 which is called Invar behaviour. The Invar behaviour was first observed in Fe-Ni alloys by Charles
Accepted 13 December 2020
Édouard Guillaume in the year 1896 and was awarded Nobel prize in physics in the year 1920. The
Available online 7 February 2021
observed Invar behaviour was puzzling and elusive for physicists. The origin of Invar phenomena has
been the subject of serious concern for physicists since the observation of the phenomenon. The first
Keywords:
model explained the Invar behaviour is called two gamma state model suggested by Weiss, considers
Invar alloy
Thermal expansion
two magnetic states of Fe in Invar alloys one with high spin high volume and another with low spin
Two gamma state model low volume states. When the temperature is increased low spin low volume states get populated at
Moment volume instability the cost of high spin high volume states and thus compensate the expected thermal expansion.
However, this was shown to be incorrect and it seems that high moment to low moment transition is pre-
ceded by a frustrated ferromagnetic state. The moment volume instabilities in Invar alloys also lead to
anomalous elastic properties. The Invar alloys find applications in the fabrication of watches, cryogenic
storage dewars and aerospace engineering parts.
Ó 2020 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Confer-
ence on Advanced Materials Behavior and Characterization.

1. History of Invar alloys
Mankind is in search of new materials all the time for fabrica-
tion of house hold items, vehicles for transportation, weapons for
war fare & protection and for improvement of living standards
since the inception of human life on planet earth. The discovery
of most of the materials occurred as per the needs and demands
of the progressive human society. The Invar alloy is one such mate-
rial which was invented in the process of finding a length standard
that maintains same length at different atmospheric temperatures
across the globe. The Invar alloy has a very special property that it
has very low or no thermal expansion over a wide range of temper-
atures around room temperature. The measuring tapes fabricated
using such alloy maintains same length at different temperatures.
Invar actually refers to invariance of thermal expansion. The Invar
alloy became one of the most important materials for precision
measurements in the development of science and technology.
Charles Edouard Guillaume, the scientist who discovered Invar
alloy was born in Switzerland in the year 1861. He worked with
⇑ Corresponding author.
E-mail address: venkatamedicherla@soa.ac.in (V.R.R. Medicherla).
Heinrich Friedrich Weber for his doctorate after completion of
which in the year 1883, he joined International Bureau of Weights
and Measures as an assistant. He was given the task of finding a
cost effective material that would not change in length or volume
when subjected temperature variations around room temperature.
He succeeded in his research and discovered iron – nickel36% alloy
with extremely low thermal expansion coefficient (Invar) and a
temperature independent elastic modulus (lInvar) in the year
1897 [1]. The discovery of the alloy and subsequent research has
played crucial role in making surveying tapes and wires, pendu-
lums for grandfather clocks, thermostats and astronomical & other
precision instruments. Fe-Ni Invar alloys replaced expensive plat-
inum use in glass sealing. Technological development during world
war II extensively used Fe-Ni Invar alloy. In those days electronic
industry was benefited in using Invar alloy for vacuum tubes and
other products. Fe-Ni Invar is used as bimetals for circuit breakers,
motor controls, TV temperature compensating springs, appliance
and heater thermostats, aerospace and automotive controls, heat-
ing and air conditioning. Thermal characteristics of Fe-Ni Invar is
closer to glass and ceramics and thus were useful for glass-metal
and ceramic to metal joints. This alloy is used in containers used
for transport liquid natural gas on tankers as the alloy has mini-
mum cryogenic shrinkage. Fe-Ni Invar has more advanced applica-

https://doi.org/10.1016/j.matpr.2020.12.527
2214-7853/Ó 2020 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the International Conference on Advanced Materials Behavior and Characterization.
A. Sahoo and V.R.R. Medicherla
tions in precision laser optical measuring systems, aerospace
industry and in orbiting satellites. Charles Edouard Guillaume
received Nobel prize in Physics for the discovery of Invar alloy in
the year 1920.
Charles Edouard Guillaume used Fe64Ni36 alloy to record the
changes of height of the Eiffel tower in the year 1912. He fixed a
long thin wire of Fe-Ni Invar along the height of the Eiffel tower.
The Eiffel tower expands or contracts when there is a change in
atmospheric temperature, but the change in length of the Invar is
negligible. When there was a sudden drop in temperature due to
a shower in the evening of certain day, the Eiffel tower contracted
but the Invar wire remained same in length.
2. Fe-Ni alloys
With the discovery of Invar property by Guillaume, Fe-Ni alloys
have come into lime light and soon have become important materi-
als for research investigations. The Invar behavior was observed for
Fe1-xNix alloys with Ni concentrations from 30 to 45% [2,3]. It has
been observed that Fe1-xNix alloys are soft ferromagnetic materials
for all compositions with very high curie temperature. The Fe metal
is of bcc structure (a phase) whereas the Ni metal is of fcc structure
(c phase). The alloy series exhibits a structural transition from bcc to
fcc at around Ni concentration of 25% [4]. Upto 25%Ni concentration,
alloys are of bcc type and for Ni concentrations above 30% are of fcc
type and thus Ni is called the c stabilizer of iron. The Ni concentra-
tion in the range from 25% to 30%, Fe-Ni alloys are in mixed phase
containing both bcc and fcc phases. The alloy series exhibits a com-
plicated phase diagram [5] which was derived by Wassermann using
the published data [6,7]. The Fe-Ni alloys in the bcc region exhibit
martensitic transformation [8,9].
In the c phase of Fe1-xNix alloys, TC becomes maximum at
around a Ni concentration of 66%, on the other hand in the a region
TC is somewhat stable. The magnetic permeability in the c phase
increases linearly following Slater-Pauling curve when Ni concen-
tration decreased gradually to 40%. Further decrease of Ni content
strongly depletes permeability thus deviating from Slater-Pauling
curve. Such a depletion in permeability is associated with the
decrease of TC. The alloys in the a phase exhibit martensitic trans-
formation [10]. The AC susceptibility measurements suggested
mixed magnetic phase for Fe1 xNix (0.3 < x < 0.45) below 30 K tem-
perature [11]. The mixed ground state may be associated with the
formation of either spin glass like phase or antiferromagnetic
behavior. The observed Invar behavior in the alloy system led to
many further discoveries and possible theoretical explanations.
Thermal expansion of solids is associated with the temperature
dependence of lattice parameter which naturally increases with
increase of temperature and thus the solid expands thermally. It
is quite astonishing to the scientific community those days how
the thermal expansion is compensated by mechanism taking place
at microscopic level.
3. 2c state model
The first model describing the Invar anomaly proposed by J.
Weiss is called two c state model [12]. According to this model
Fe in the c phase can have two magnetic states with two different
atomic volumes: a low moment low volume (c1) state and a high
moment high volume (c2) state. In Fe-Ni Invar alloys, c2 state is
stabilized in the ground state and c1 state is a consequence of ther-
mal excitation of c2 state. The c1 state has a magnetic moment of
0.5 mB with a lattice parameter 3.54 Å whereas the c2 state has a
magnetic moment with 2.8 mB with a lattice parameter 3.64 Å in
pure iron as obtained by extrapolation of alloy data [12]. The differ-
ence between the two c states can be viewed as the excitation of
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Materials Today: Proceedings 43 (2021) 2242–2244
an electron from lower half of the 3d band to upper half. Such a
spin flip transition approximately accounts for a difference of mag-
netic moment of about 2.0 mB. When the temperature is increased,
high volume c2 state gets converted to low volume c1 state com-
pensating the change in volume occurring by normal thermal
expansion causing apparently very low or zero expansion of the
alloy due to temperature increase. If the temperature is decreased,
c1 state gets converted to c2 state compensating the contraction
occurring due to decrease in temperature. Thus the model pro-
posed by Weiss for Invar anomaly is based on moment volume
instabilities in the alloys. The Stoner theory supported the two c
state model for c iron [13]. In non Invar high Fe concentration
alloys, c1 state is stabilized in the ground state and c2 state is
excited thermally causing large thermal expansion [12].
4. Non collinear magnetism in Fe-Ni Invars
The two magnetic states suggested by Weiss in Invar Fe-Ni
alloys motivated many researchers to extend the idea to other
materials. The theoretical calculations carried out on ferromag-
netic c-Fe, ordered Fe3Ni and fcc Fe1 xNix alloys indicated the pres-
ence of two magnetic phases [13–23]. The model calculations
based on local moments [24–28] were carried out to understand
the Invar anomaly. The presence of local moments was supported
by Mossbauer experiments [29]. Non collinear Fe magnetic
moments were predicted by some model calculations [26]. More
recent and advanced calculations suggested that the Invar property
may be associated with a continuous magnetic phase transition in
Fe-Ni alloys involving a family of complex magnetic states [30].
The researchers working in physical sciences and engineering
focused their attention on materials exhibiting Invar property
and investigated new Invar materials such as Fe-Pt, Fe-Co and
Fe-Pd alloys [31–34]. Most of the Invar materials are iron based
alloys except few.
Invar alloys exhibit anomalous magnetic properties. The latent
antiferromagnetism hypothesis was proposed in the year 1960 to
explain the magnetic anomalies of the Invar alloys [35]. The
hypothesis assumes that in the c phase of the Fe-Ni invar alloys,
Ni-Ni and Fe-Ni exchange interaction are of opposite sign, but
the Fe-Fe has negative exchange interaction. It was confirmed from
susceptibility [36,37] and Mossbauer measurements [38,39] that
there is a possibility for c-iron to possesses antiferromagnetism.
5. Mixed ground state in Fe-Ni Invar
The ground state of Fe-Ni Invar alloys was investigated exten-
sively through theoretical and experimental techniques. A inhomo-
geneous or mixed ground state has been reported several
researchers [29,37–38,40–41]. Mossbauer studies on the Invar
alloy, Fe65Ni35 indicated a mixed ground state with 90% of Fe atoms
in ferromagnetic state and the remaining 10% either in antiferro-
magnetic state or in frustrated antiferromagnetic state [42–45].
On the other hand, Mossabauer studies by Abd-Elmeguid et al. sug-
gested only 30% of Fe sites of Fe65Ni35 are antiferromagnetic below
30 K and flip their spins favouring ferromagnetic order above 30 K
[43]. Miyazaki et al. proposed a reentrant spin glass behavior for
Fe1 xNix (0.3 < x < 0.45) below 30 K using AC susceptibility data
[46]. The physical properties of Fe-Ni Invar alloys were found to
be anomalous at low temperatures due to the occurrence of mixed
ground state [47,48].
6. Conclusion
The history of the discovery of Invar alloys is briefly discussed
with a mention of great Eiffel tower experiment conducted by
A. Sahoo and V.R.R. Medicherla
Guillaume to demonstrate the Invar property of FeNi36% alloy. The
2c state model proposed by Weiss is revisited to understand the
Invar anomaly. The possibility of non-collinear magnetism in Fe-
Ni Invar is reviewed. The mixed ground state in Fe-Ni Invar is
described. The variation in experimental results by different
groups could be related to the method of preparation and anneal-
ing of the alloys.
CRediT authorship contribution statement
A. Sahoo: Conceptualization, Supervision, Validation, Writing -
review & editing. V.R.R. Medicherla: Conceptualization, Supervi-
sion, Validation, Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
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