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INFLUENCE OF CRYOGENIC TREATMENT ON THE ELECTRICAL AND THERMAL

PROPERTIES OF GRAY CAST IRON

Conference Paper · October 2018

DOI: 10.7449/2018/MST_2018_1049_1059

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 Contributed Papers from Materials Science and Technology 2018 (MS&T18)
October 14–18, 2018, Greater Columbus Convention Center, Columbus, Ohio, USA
Copyright © 2018 MS&T18®
DOI 10.7449/2018/MST_2018_1049_1059

INFLUENCE OF CRYOGENIC TREATMENT ON THE ELECTRICAL

AND THERMAL PROPERTIES OF GRAY CAST IRON
Deepak Joshi, Susil Putatunda1 and James Boileau2
1
Department of Chemical Engineering and Materials Science, Wayne State University,
Detroit, MI 48202 USA
2
Ford Motor Company Research and Innovation Center, Dearborn, MI 48124
sputa@eng.wayne.edu
313-577-3808

ABSTRACT

An investigation was carried out to examine the influence of cryogenic treatment on the
microstructure as well as the thermal and electrical properties of gray cast iron. The
microstructure was characterized using optical and SEM microscopy, X-Ray Diffraction, and
TEM analysis. The results of this investigation indicate that cryogenic treatment does not
significantly change the observable microstructure but does enhance the electrical and thermal
properties of gray cast iron. A mechanism based upon the decomposition of cementite at
cryogenic temperatures is hypothesized to explain these property improvements.

INTRODUCTION

Cast irons are a class of ferrous alloys with a carbon content above 2 wt%. Cast irons possess a
wide range of properties [1] including strength, ductility, machinability, hardness, damping
capacity, thermal conductivity, castability, wear resistance and corrosion resistance as well as
being low in cost. Generally, cast irons are divided into various categories based upon the form
of the graphite phase. Each cast iron alloy can also undergo different heat treatments, which will
yield different microstructures and mechanical properties [2]. One common type of cast iron is
gray cast iron. Having a carbon content between 2.5 – 4 wt%, the microstructure of the gray cast
iron consists of graphite flakes surrounded by ferritic or pearlitic matrix [3]. Gray cast iron
exhibits high damping capacity, high thermal conductivity, high wear resistance, moderate
strength. Because of these properties, gray cast iron is commonly used in vehicular applications
such as heavy-duty engine blocks and cylinder heads, liners in cast aluminum engine blocks,
control arms, and brake rotors.

In the past two decades, the use of cryogenic heat-treatments has been investigated as a means of
improving the wear resistance in ferrous alloys. Conventionally, a cryogenic heat treatment
processes consists of a series of steps, including a ramped cooling to liquid nitrogen temperatures
(-184 C), a sustained hold at this temperature for a length of time, and a ramped heating to room

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temperatures. In the final stage, the ferrous material is tempered at a temperature slightly
elevated over room temperature.

There have been a limited number of studies examining the effect of cryogenic treatments on the
mechanical properties of cast iron alloys. In one study focusing on gray cast iron used in brake
rotors [4], the microstructure and pin-on-disk wear resistance of cryogenically-treated G3000
gray iron were evaluated and compared to samples that were not cryogenically-treated. This
study found a significant, but highly variable, increase in wear resistance occurred following
cryogenic treatment. It was also observed that there were no significant differences in the
hardness or in the optically-observable microstructure of the two materials.

Another study performed on spheroidal graphite iron [5] found that cryogenic treatments yielded
slight improvements in the hardness, tensile strength, and impact resistance. In addition, a post-
cryogenic heat-treatment at 200 C for 1 hours was also found to further improve these properties.
Pin-on-disk wear tests found that found a significant, but highly variable, increase in wear
resistance occurred following cryogenic treatment. Similar results were found in studies on
cryogenically-treated austempered ductile iron [6-8], white cast iron [9], 410 stainless steel [10],
and in tool steels as well [11-15].

The root cause for the improvements present after cryogenic treatment is the source of
uncertainty at this time. As reviewed in [16], three major factors influencing the increase in
strength are:

 Reduction/elimination of the amount of retained austenite by a more complete conversion

to martensite (as in [5,8,10]);
 An increase in the precipitation, dispersion, and/or refinement of secondary carbides (as
in [8,10, 12]; and/or
 An increase in the hardness of the matrix due to the refinement of the microstructure
resulting from the cryogenic treatment (as in [8]).

Thus, the published literature has observed that cryogenic treatment induces changes that result
in a significant increase in wear resistance and a noticeable change in hardness of ferrous alloys.
However, there has been limited study to verify whether cryogenic treatment on tool steel or cast
iron can result in increase of its thermal and electrical properties. Therefore, the current study
was conducted with the primary objective being to examine the effect of cryogenic treatment on
the microstructure, thermal and electrical properties of gray cast iron.

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 EXPERIMENTAL PROCEDURE

Material

The material used in this investigation was a commercially-available SAE J431 G10 gray cast
iron; this alloy is used extensively in automotive brake rotors. The chemical composition of the
cast iron used is presented in Table 1.

TABLE 1: Chemical Composition of the SAE J431 G10 Gray Cast Iron

Element C Si Mn P S
Weight % 3.6 2.5 0.4 0.010 0.015

Cryogenic Treatment

The cast iron samples were divided into two groups. The first group, designated “Untreated”,
was set aside and was not given any cryogenic treatment. The second group of samples were
them taken and continuously cooled from room temperature to -73°C over a time period of 3
hours. The samples were then cooled to -184°C using a sequence of steps that decreased the
temperature by -51°C; a dwell time of 1 hour at each step was present. The sample were held at -
184°C for 24 hours. Finally, these samples were heated to -73°C over a period of 10 hours;
following this, the samples were allowed to warm to room temperature.

Microstructural Characterization

Hardness tests were conducted on both untreated and cryogenically-treated samples using a
Buehler Macromet Rockwell Hardness tester. A 100 kg load and a 1/8” ball indenter were used
to make measurements for the Rockwell B scale; a minimum of four points per sample were
taken and averaged.

Metallographic specimens approximately 0.5” x 0.5” were cut from both the untreated and
cryogenically-treated samples to examine the microstructure under both optical and scanning
electron microscopy. For optical metallography, the samples were mounted and polished using
standard metallographic techniques; they were etched with a 5% Nital solution. Scanning
electron microscopy was performed on the mounted specimens using a JEOL JSM-6510LV-LGS
SEM equipped with a Pegasus Apex 2 EDS analysis unit.

X-Ray Diffraction (XRD) samples were characterized using a Bruker Phaser II diffractometer;
copper Kα radiation was used at 40KV and 100mA. Samples for TEM analysis were cut,
ground, polished, and subsequently ion milled to 100nm thickness for analysis. TEM analysis
was carried out using JEOL 2010 (LaB6 Filament Gun) transmission electron microscope at an
accelerating voltage of 200 keV.

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The electron diffraction pattern obtained from both the untreated and cryogenically-treated
samples was indexed for phase identification. Each diffraction pattern was indexed using the
equation:

𝑑ℎ𝑘𝑙 𝑅ℎ𝑘𝑙 = 𝜆𝐿 (1)

where:

 dhkl is the lattice spacing of plane (hkl) (units of Å);

 Rhkl is the distance of the spot being measured from the center beam spot (image pixels);
 λ is the wavelength of electron beam (Å units); and
 L is the camera length (in image pixels).

The value of λL was calibrated using a standard aluminum powder sample with known lattice
spacings; at the operating voltage of 200keV, this yielded λL = 117.57Å-pixels. The Gatan
Digital Micrograph Software (v. 3.7.4) was used to measure the distance between the center spot
and each other diffracted spot. Using equation (1) the lattice spacing (dhkl) associated with each
spot was obtained and indexed according to the data given in [17,18].

Thermal and Electrical Parameter Tests

Both the untreated and cryogenically-treated samples were tested to determine the thermal and
electrical conductivity using a Quantum Digital P670 Thermal Transport (TTO) System. The
TTO system measures thermal conductivity and the thermoelectric Seebeck effect by measuring
the temperature and voltage drops across a given sample as a heat pulse is applied to one end.
Grey iron samples were mounted on the copper leads of the TTO system using epoxy bond. The
copper leads were connected to the thermometer and the heating section. For the thermal
conductivity and Seebeck coefficient measurements, heat was applied to one end of the sample
by running current through the heater. The temperatures, Thot and Tcold, are measured at the
thermometer shoes. The thermal conductivity measurements are accurate to + 1 W/mK and the
Seebeck coefficient measurements are accurate to + 0.5V/K at room temperature.

RESULTS AND DISCUSSION

Hardness

Table 2 details the hardness values of the untreated and the cryogenically-treated samples. As
this table shows, the hardness of the cryogenic-treated sample is slightly greater than that of non-
cryogenic sample; this result is consistent with those results seen in the literature [5 - 10].

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 Table 2: Rockwell B Hardness Values of the Iron Alloys Examined in This Study

Rockwell “B” Hardness

Cryogenically-Treated Gray
Untreated Gray Cast Iron
Cast Iron
86 + 2 93 + 2

Microstructure

The microstructures of the untreated and cryogenically-treated gray cast iron samples are shown
in Figures 1 and 2. As Figure 1 details, the optical microstructures are similar for both sets of
specimens, consisting of a fine pearlitic matrix as well as a limited amount of ferrite. The
microstructure also contains distributed Type “A” graphite flakes with an average maximum
length of 60 ± 20 μm. Optically, no observable amount of retained austenite or martensite was
observed.

(a) Untreated (b) Cryogenically-Treated

Figure 1: Typical Microstructural Features Observed in the Gray Cast Iron (Scale is 25 m)

Similarly, the scanning electron microscopic images also show no difference between the
untreated and cryogenically-treated samples. The lack of difference can be seen by comparing
the microstructures in the SEM images in Figure 2. Again, the dominant microstructural phase
that is observed is pearlite, with large flakes of Type “A” graphite being present. From the SEM
images, the fineness of the pearlitic structure can be seen, with the intercolony spacings being on
the order of 0.5 -2 m.

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 (a) Untreated (b) Cryogenically-Treated

Figure 2: Typical Microstructural Features Observed in the Pearlite Phase

X- Ray Diffraction

Figures 3(a) and (b) shows the XRD pattern of the untreated and cryogenically-treated gray cast
iron samples. The XRD pattern of untreated cast iron sample (Figure 3(a)) contains the typical
peaks expected for a material primarily composed of Ferrite (α-Iron). this pattern also confirms
that no retained austenite is present. Additionally, there is a slight bump in the XRD pattern
between 2θ values of 25° - 30°, which is believed to be due to minute quantities of dispersed
metallic carbides.

(a) Untreated (b) Cryogenically-Treated

Figure 3: XRD Patterns Observed in the Gray Cast Iron

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In general, the XRD pattern of cryogenically-treated sample (Figure 3(b)) has many similarities
to that seen in Figure 3(a)). The exception in this case is the presence of a peak at 2θ = 26.5°.
An XRD peak at a position of 26.5° indicates that graphite is present in the matrix [18]. The
authors hypothesize that this graphite is a result of the decomposition of cementite that results
from the cryogenic processing as illustrated in Equation (2):

Fe3C → (FexCy + Fe) + C(graphite) (2)

where FexCy represents an as-yet undefined non-stoichiometric carbide that arises due to the low
kinetics associated with the cryogenic decomposition of cementite. This proposed
decomposition is supported by the XRD data shown in Figure 3. A comparison of the relative
intensities of Feα (110) plane in the untreated and cryogenically-treated cast iron (Figures 3(a)
and 3(b)) shows an increase in the intensity of Fe for the cryogenically-treated cast iron. In
addition, a comparison of the two figures shows that only in the cryogenically-treated sample
does a peak for C arise. These results appear to confirm that cementite is decomposing into
graphite, iron, and possibly off-stoichiometric metallic carbides. This is an interesting
observation, and additional TEM studies focused on EDS analysis of the carbides are being
planned to understand what definite conclusion can be drawn.

Selected Area Diffraction Pattern

Figure 4 shows the indexed electron diffraction patterns of the untreated and cryogenically-
treated cast iron samples. As expected, the electron diffraction pattern of the untreated cast iron
sample along the [0 0 -2] zone axis was found to be strongly indexed with just the primary Feα
(002) planes (Figure 4(a).)

(a) Untreated (Zone Axis is [0 0 -2]) (b) Cryogenically-Treated

(Zone Axis is [1 5 -3])

Figure 4: Electron Diffraction Patterns in the Gray Cast Iron

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Additionally, the electron diffraction patterns of the cryogenically-treated cast iron sample were
found to be strongly indexed along the [1 5 – 3] zone axis with both the Feα (112) and Carbon
(002) planes (Figure 4(b).) The carbon was determined from the measurements of the distances
between the spots on the pattern. The distances averaged approximately 3 A, which was very
close to the reference interplanar spacing values for the (002) planes in graphite [17].

Thus, the results from the electron diffraction patterns of the untreated and cryogenically-treated
cast iron samples confirm the results seen in the XRD analysis. This further strengthens the
hypothesis that cryogenic treatment of cast iron causes decomposition of the cementite into
graphite, iron, and possibly off-stoichiometric metallic carbides.

Thermal and Electrical Properties

Table 3 illustrates the thermal conductivity and Seebeck coefficient for the untreated and
cryogenically-treated cast iron samples at ambient temperature. The results in the table show that
that average value of each of the parameters is higher for the cryogenically-treated samples
compared to the untreated samples.

TABLE 3: Thermal and Electrical Measurements of the Gray Cast Iron

Average Thermal Average Seebeck Coefficient

Sample Condition
Conductivity (W/mK)* (V/K)*
Untreated 14.05 2.52
Cryogenically-Treated 27.44 4.54
*Overall average of all measurements in the time interval shown in Figures 5 and 6

Similarly, Figures 5 and 6 show that there is a noticeable increase in the thermal and electrical
properties of cryogenically-treated samples compared to the untreated samples across the entire
measurement time range. These results are consistent with those published in the literature; in
general, increased graphite content will yield increased thermal and electrical conductivity in an
iron alloy [20-22]. Thermal conductivity is an especially important property for a component
like a cast iron brake rotor. Thus, the reported increase in lifetime of a cryogenically-treated
rotor may be due, in part, to the decomposition of the cementite into graphite. This will improve
the thermal conductivity and decrease the number of hot spots on the rotor surface, leading to a
lower rate of rotor wear and NVH issues.

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 Figure 5: Thermal Conductivity of the Figure 6: Seebeck Coefficients of the
Untreated and Cryogenically-Treated Gray Untreated and Cryogenically-Treated Gray
Cast Iron Cast Iron

Conclusions

An investigation is carried out to study the effect of cryogenic heat treatment on the
microstructure, thermal conductivity, and electrical conductivity of a SAE J431 G10 gray cast
iron alloy. From this investigation the following conclusions can be drawn:

1) Cryogenic heat treatment does not appear to affect the observable microstructure as
viewed optically or using scanning electron microscopy.
2) X-Ray Diffraction detects a peak at 2θ = 26.5°; this most probably corresponds to the
presence of carbon in form of graphite.
3) Selected Area Diffraction Pattern analysis found that only the cryogenically-treated cast
iron strongly indexed the (002) planes associated with carbon.
4) The Thermal and Electrical properties of the cryogenically-treated sample were found to
be greater than those of the untreated samples.

The results detailed above support the hypothesis that cryogenic treatment will result in the
decomposition of cementite into graphite, iron, and (possibly) off-stoichiometric metallic
carbides. Thus, this decomposition may help explain why cryogenically-treated iron components
(like brake rotors) exhibit both increased hardness (off-stoichiometric metallic carbides) and
increased wear resistance (more graphite). In addition, the current investigation also indicates
that there are multiple opportunities to further study the influence of cryogenic heat treatments
on cast iron alloys that can be used in industrial applications.

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