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Low Thermal Expansion Coefficient Fe-Ni-Co Alloys-Plastic Deformation, Alloy

Composition and Martensitic Transformation Relationships

Conference Paper · February 2007

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 Advanced Metallic Composites and Alloys for High Performance Applications
Edited by: Awadh Pandey, Kevin L. Kendig, and John Lewandowski
TMS (The Minerals, Metals & Materials Society), 2007

LOW THERMAL EXPANSION COEFFICIENT Fe-Ni-Co ALLOYS - PLASTIC

DEFORMATION, ALLOY COMPOSITION and MARTENSITIC TRANSFORMATION
RELATIONSHIPS

Deniz Sultan Temur1, Ali Arslan Kaya1, Gurler Kaya2 and Murat Kurtulus2
1
TUBITAK MRC, Materials Institute, P.O.B. 21, Gebze, Kocaeli 41470, TURKEY
2
ROKETSAN Missiles Industries Inc., Elmadag, Ankara 06780, TURKEY

Keywords: Invar, Plastic Deformation, Martensite

Abstract

Alloy composition, heat and mechanical treatments are factors affecting linear thermal expansion
coefficient in Fe-Ni-Co alloys. Although deformation lowers the expansion coefficients of these
alloys, an increasing deformation can lead to partial transformation to martensite upon cooling
and increase the thermal expansion coefficient. Therefore, in order to obtain a low expansion
coefficient, the alloy composition, which affects the transformation temperature, has to be
controlled critically. Alloying elements generally suppresses the martensite start temperature.
Carbon is very effective in this respect. However, it creates instability in terms of expansion
behavior and increases linear thermal expansion coefficient. A series of stabilization heat
treatments hinder this instability problem allowing for controlled use of carbon in these alloys.
This study focuses on the method of obtaining low expansion coefficients by applying plastic
deformation in Fe-Ni-Co alloys while controlling the partial martensitic transformation as a
result of composition and applied deformation.

Introduction

Invar alloys, following their Nobel prize-earning discovery by Guillaume in 1896, have found
increasing use in areas like metrology, instrumentation, precision optical structures, aerospace
etc. due to their extremely small or even negative thermal expansion coefficients [1, 2]. Since
then the word ‘Invar’ which is a derivative from ‘invariant’ has come almost to mean ‘low
coefficient of thermal expansion (CTE)’. This feature of the basic Fe-36Ni alloy composition is
attributed to what is known as ‘magnetostriction effect’. This essentially magnetic property
counteracts to the forces of expansion or contraction during temperature changes within a certain
range thus leading to a very low thermal expansion coefficient [2]. The degree of
magnetostriction as well as the temperature range over which a low thermal expansion is
observed can be changed by controlled application of deformation, and modifications of the alloy
composition. Such alterations also change both the mechanical and the physical properties of
Invar alloys. The lowest linear thermal expansion coefficient is obtained when the alloy is
deformed. In that process, especially if cold deformation is employed, there exists a risk of
partial transformation of austenite phase into the martensite phase which does not exhibit the
invar effect [3]. Likewise, cobalt addition also promotes the martensite formation by increasing
the martensite start temperature (Ms) [3, 4]. Despite the martensite-promoting effect, cobalt is
added to Invars due to its beneficial attributes in imparting lower thermal expansion and raising
the Curie temperature of the alloy [3, 4]. This adverse effect of plastic deformation and cobalt

55
can be counterbalanced by controlled addition of some alloying elements, most notably carbon.
Although it is a way of suppressing the martensitic phase transformation carbon addition creates
instability in terms of expansion behavior and increases CTE. This instability problem should be
interpreted as small and unpredictable spontaneous changes in CTE that can be avoided through
a succession of heat treatment steps.

Tailoring of the ‘’Invar’’ property thus becomes an interplay between several parameters,
namely composition, the type and amount of deformation, and stabilization heat treatments that
are all individually well established [2, 3, 5, 6]. The range of CTE can vary from very low
(∼0.1x10-5) to negative values. The present study focuses on the combined effect of cold plastic
deformation, martensitic transformation, addition of carbon and stabilization heat treatments on
thermal expansion coefficient of Invar alloys based on long-term CTE measurements.

Experimental

Elements such as Fe, Ni, Co, Mn, Si, Al, S and P were kept nominally constant, and carbon was
varied for three alloys as shown in Table 1. The compositions of the samples were determined
via optic emission spectrometry. The elements other than Fe, Ni, Co and C were all considered
as undesired impurities and therefore their total amount were kept below a figure of about 1%
inclusive of carbon.

Deformation is known to lower CTE values [6]. Therefore, in order to determine the potential of
these alloys in terms of low CTEs two different deformation ratios were employed, i.e. 25% and
30%, as shown in Table 1. The stress relieving, the following three successive stabilization heat
treatments and corresponding subsequent cooling procedures were conducted in the following
manner as suggested in the literature [6]. i) Step one:1h at 815ºC, water quenching; ii) Step two:
1h at 315ºC, air cooling; and iii) Step three: 48h at 98ºC, air cooling. When all three of these heat
treatments were employed the condition was described as ‘full stabilization’ and designated with
the letters ‘FS’.

Samples for dilatometer measurements were prepared mechanically with the dimensions of 25
mm length and 4 mm radius. Netzch DIL 402C type dilatometer was used with a heating and
cooling rate of 2ºC/min. The measurements were performed under helium inert gas condition.
CTE measurements were done between the temperature range of -90ºC and +100ºC by using
fused silica rod type sample holder. These measurements also indicated the initiation
temperature, Ms, of martensitic phase transformation. The effects of carbon content as well as
deformation were thus followed by observing the sharp changes in the slope of the cooling
curves obtained from dilatometer.

Table 1. Deformation (%), nominal compositions of the samples (wt %).

Sample Composition (nominal wt%) Deformation Carbon Content
No. (%) (wt %)
Fe Ni Co others
Sample 1 25 -
25
Sample 2 62.0 32.0 4.5 1.5 0.18
30
Sample 3 25 0.28

56
 Results and Discussion

Plots obtained from the dilatometer within the temperature range of –90ºC to +100ºC revealed
the martensite start temperatures to be about –14ºC for Sample-1, -77ºC and -72ºC for Sample-2
corresponding to 25 and 30% deformation ratios, respectively. Whereas no martensitic
transformation was observed for Sample-3 within the temperature range of measurements as seen
in Fig.1(b). The CTE values of the martensite-containing samples were 5.06E-06 for Sample-1,
and 0.77E-06 for Sample-2 with 25% deformation. The CTE of non-martensitic Sample-3 was
0.68E-06. The Ms temperatures and CTE values are summarized in Table 2.

●Carbon + %25 Deformation+FS

Carbon + %30 Deformation+FS Sample 1, %25
▲ No Carbon + %25 Deformation+FS Deformation+FS
(Martensitic Transformation)
Temp. / oC T. Alpha / (1/K)
-70.0, 100.0: 5.0640E-06
Sample 3, %25 Deformation+FS
(No Martensitic Transformation)
Sample 2, Temp. / oC T. Alpha / (1/K)
%25 -70.0, 100.0: 0.6815E-06
Deformation+FS Sample 2, %25 Deformation+FS
MS : -76.6oC Sample 1,
(Martensitic Transformation)
Sample 2, %25 Deformation+FS Temp. / oC T. Alpha / (1/K)
%30 MS : -14.1oC -70.0, 100.0: 0.7779E-06
Deformation+FS
MS : -72.3oC
● ▲

a b
Figure 1. (a) Cooling curves from dilatometer revealing the MS temperatures (ºC) for Sample-1
and Sample-2 for two deformation ratios. (b) Heating curves from dilatometer showing CTE
values all three samples. (Note that ‘FS’ means ‘full stabilization’ treatment received.)

The effect of martensitic constituent in the microstructure as an increment of CTE can be

deduced by comparing the CTE values of the Samples 1 and 2 for the same temperature range
before the onset of and after the martensitic transformation. The CTE values before the onset of
martensitic transformation were obtained from the dilatometer plots during the cooling course at
the beginning of the measurements as shown in Fig.2. The plots of the heating course (Fig.2) for
the same temperature range corresponds to the last portion of the whole measurement cycle over
the temperature range from –90ºC to +100ºC. Thus the curves of the heating course were
obtained from materials that have already gone through the martensitic transformation during the
cooling to –90ºC at the beginning of the measurements, and thus involved martensitic constituent
in their microstructure. It can be seen that the CTE value of Sample-1 for the same temperature
range increased from 0.53E-06 to 4.86E-06 during cooling and heating, respectively. Likewise, a
very large increase in CTE was also observed for Sample-2 from 0.001E-06 to 0.5E-06 due to
the martensitic constituent of the microstructure during the heating course of the measurement.

Expectedly, carbon-free Sample-1 showed the highest MS temperature compared to the carbon
containing samples. MS temperature is greatly affected by the level of carbon content and
suppressed to lower temperatures as carbon increased (Fig.1). Increased deformation also shifted
the MS temperature for Sample-2 to a higher temperature. This is also an expected phenomenon
since the martensitic reaction, being a diffusionless phase transformation, is known to be
facilitated by the existing stresses within the material [7, 8, 9].

57
 Heating Step
Cooling Step

Sample 1, (No Carbon)

Temp. range: T. Alpha / (1/K)
0-10oC : 4.866E-06
Sample 2, Carbon(%0.18)
Temp. range: T. Alpha / (1/K)
Temp. range: T. Alpha / (1/K) 0-10oC : 0.5327E-06
-70-0 oC : 0.5044E-06
Temp. range: T. Alpha / (1/K)
-70-0 oC : 0.0011E-06

-76.6oC -14.1 0C

Figure 2. Plots obtained from dilatometer showing the CTE values of the Samples 1 and 2 for
the same temperature ranges before the onset of and after the martensitic transformation. Note
that the cooling plots correspond to a non-martensitic structure while the heating plots illustrate
the contribution to CTE of the martensitic constituent in the microstructure.

Table 2 gives the Ms temperatures and CTE values for the samples. As shown in Fig.1 and Table
2 carbon-free sample displayed the highest CTE value. Although carbon as an alloying element
increases CTE, this seemingly contradictory result can be explained by the martensitic
transformation in the carbon-free sample at relatively high cryogenic temperatures over the
whole range of measurements from –90ºC to +100ºC. This early transformation creates a large
amount of martensite in Sample-1. Martensitic phase does not possess Invar characteristics and it
increases the thermal expansion coefficient as observed in Sample 1 and 2. Thus the large CTE
difference between Sample-1 and the other martensite containing samples can be attributed to the
greater amount of martensite in Sample-1 (see Fig.3). Likewise, based on carbon contents, a
similar contradiction is apparent between the CTE values of Sample-2 with 25% deformation
and Sample-3. Contrary to its higher carbon content Sample-3 with identical deformation ratio
has a lower CTE value simply due to lack of martensitic component in its microstructure. In the
light of these evaluations it may be suggested that elimination of martensite from the
microstructure is more effective in lowering CTE that reducing the carbon content.

Table 2. CTE (mm/mmK) and MS Temperature (ºC) values.

Sample MS (ºC) CTE (mm/mmK)
Sample 1-%25 Deformation-
-14.1 5.0640E-06
No Carbon
Sample 2-%25 Deformation -76.6 0.7779E-06
Sample 2-%30 Deformation -72.3 0.5919E-06
Sample 3-%25 Deformation No martensitic transformation 0.6815E-06

It is also worth considering why despite the expected slightly greater an amount of martensitic
transformation, and in turn, a greater CTE value, Sample-2 with 30% deformation showed a
lower CTE value compared to the 25% deformation case. This result may be taken to imply that
the effect of deformation in lowering the CTE value is greater than the adverse effect of a slight
increase in the amount of martensite phase in the microstructure.

58
Above-mentioned analysis of the results shows that low CTEs can be achieved by applying cold
deformation. Martensite-promoting effect of cold deformation can be suppressed and a low CTE
can be maintained over a wider temperature range by employing carbon in the alloy composition.
This approach, however, brings about a stability problem due to the mobility of small carbon
atoms in the microstructure. The instability problem can be observed as a time dependent
dimensional change, and in other words as a change in CTE (Fig. 4). Second measurement on
Sample-2 showed that the CTE of carbon containing alloy changed with time. Repeated
measurements with long intervals indicated that this problem could be remedied by a series of
successive heat treatments as mentioned in the experimental section.

50μm 50μm

50μm 300μm

Figure 3. Light micrographs from dilatometer samples cooled to cryogenic temperatures

following cold deformation: (a) Sample–1, %25 Deformation with no carbon content (b)
Sample–2, %25 Deformation, (c) Sample–2, %30 Deformation, (d) Sample–3, % 25
Deformation. Please note the partial martensitic transformation in (a), (b) and (c), and that
comparison of micrographs in (b) and (c) do not necessarily reflect the amount of martensitic
phase constituents in the microstructures.

59
 1st measurement Temp. / oC T. Alpha / (1/K)
-70.0, 100.0: -0.3076E-06
2nd measurement- Temp. / oC T. Alpha / (1/K)
● 30 days later -70.0, 100.0: -0.0463E-0 x
●
x x
● ●
x
● ●
●
●
x
x

Temp. / oC T. Alpha / (1/K) 1st measurement

-70.0, 100.0: 0.6233E-06
x nd
Temp. / oC T. Alpha / (1/K) 2 measurement-
-70.0, 100.0: 0.6289E-06 40 days later
x Temp. / oC T. Alpha / (1/K) 3rd measurement-
-70.0, 100.0: 0.6010E-06 100 days later

Figure 4. CTE measurements on Sample-2 with time intervals indicating the effect of
stabilization treatments to remedy the instability due to carbon. The plots marked with full
circles belong to the case without the stabilization heat treatments. Other plots belong to the
measurements taken after ‘full stabilization’

References

1. C. E. Guillaume, C.R. Acad. Sci. 125, 235 (1897).

2. J. Wittenauer, D.L. Yaney, and R.E. Lewis, “Microyielding in Fe-36Ni: Role of Carbon
and Thermal Processing”, Scripta Metallurgica e t Materialia, 31 (11) (1994), 1531-
1536.

3. K. Sridharan, F. J. Worzala and R. A. Dodd, “Martensitic Transformation and Invar

Effect in Fe-Ni-Co Alloys”, Material Chemistry and Physics, 30 (1991) 115-119.

4. A. J. Goldman and W. D. Robertsons, “Elastic Properties of Austenite and Martensite in

Iron-Nickel Alloys” , Acta Metallurgica, 12 (1964), 1265-1275.

5. Z. Eliezer and J. T. Hoggins, “Elastic Deformation of Invar Alloys”, Mat. Res. Bull. 12
(1977) 227–234.

6. G. Hausch, R. Bacher and J. Hartmann, “Influence of Thermomechanical Treatment on

the Expansion Behavior of the Invar and Superınvar”, Physica B, 161 (1989) 22-24.

7. C. M. Wayman, “Overwiew And Nucleation Of Martensite / Martensitic

Transformations” (An Overwiew. Proceedings Of An Conference on Solid-Solid Phase
Transformations / The Metallurgical Society of AIME 1, 1119–1144, 1981).

8. G. B. Olson; M. Cohen, “Overwiew and Nucleation Of Martensite / Theory of

Martensitic Nucleation” ( A Current Assessment. Proceedings of an International

60
 Conference on Solid-Solid Phase Transformations /The Metallurgical Society of AIME 1,
1145–1164, 1981).

9. S. R. Honeycombe; H.K.D.H. Bhadeshia (Eds.), Steels / Microstructure and

Properties/Kinetics of Transformation to Martensite / Effect of Alloying Elements.
Second ed. Vol. 1. Edward Arnold, London, 1995.

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