Scripta Materialia

Lattice parameter of cementite phase in pearlite structure

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Manuscript Number: SMM-20-1661

Article Type: Regular article

Section/Category: Opt in to First Look

Keywords: lattice parameter, neutron diffraction, pearlitic steels, internal stresses, thermal
conductivity.

Abstract: The lattice parameter of cementite in a pearlite structure was measured using the in
situ heating neutron diffraction method. The lattice parameters of the cementite phase
of the b- and c- axes in the pearlite structure were smaller than those in the martensite
structure and Reed’s results [3]. The lattice parameter of the a-axis in the pearlite
structure was almost equal to that in the martensite structure and Reed’s results [3].
The thermal and misfit strains, caused by the differences between the thermal
expansion rate and lattice parameter of the cementite and ferrite phases, should affect
the lattice parameter of cementite in the pearlite structure.

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Graphical Abstract

(a) 4.575 (b) 5.140

Cementite in pearlite
Cementite in Pearlite
Lattice parameter, a / Å

4.565 Cementite in martensite 5.130

Lattice parameter, a / Å
Cementite in Martensite
4.555 Reed’s results [3] 5.120 Reed’s results [3]

4.545 5.110
c
5.100 c
4.535
Cementite phase
5.090 Cementite phase
Fe atom
4.525 C atom Fe atom

a
b 5.080 C atom

b
4.515 a

5.070
300 400 500 600 700 800 900 1000
300 400 500 600 700 800 900 1000
Temperature, T / K
Temperature, T / K
(c) 6.840 (d) 160
6.830 Cementite in Pearlite 159.5 Cementite in Pearlite

Volume of unit cell, V / Å3

Lattice parameter, a / Å

6.820 Cementite in Martensite 159 Cementite in Martensite

6.810 Reed’s results [3] 158.5 Reed’s results [3]
6.800 158
6.790 157.5
6.780 c 157
6.770 156.5
Cementite phase
6.760 Fe atom
156
C atom
6.750 b
155.5
a
6.740 155
300 400 500 600 700 800 900 1000 300 400 500 600 700 800 900 1000
Temperature, T / K Temperature, T / K

Figure 2 Lattice parameter of the cementite phase of (a) a-axis, (b) b-axis and (c) c-axis and
(d) volume of unit cell as a function of temperature.
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1
2 Lattice parameter of cementite phase in pearlite structure
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4
5 Norimitsu Kogaa*, Liangwei Yinb, Osamu Umezawac, Takayuki Yamashitad, Satoshi Morookad,
6 Takuro Kawasakid, Stefanus Harjod
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9 a) Division of Mechanical Science and Engineering, Kanazawa University, Kakuma-machi
10 Kanazawa Ishikawa 920-1192 Japan.
11 b) Graduate School of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya,
12
13 Yokohama, 240-8501 Japan.
14 c) Faculty of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya, Yokohama,
15 240-8501 Japan.
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17 d) J-PARC center, Japan Atomic Energy Agency, 2-4 Shirakata, Tokai, Naka, Ibaraki, 319-1195,
18 Japan
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20
*Corresponding author
21
22 E-mail address: koga-norimitsu@se.kanazawa-u.ac.jp
23 Phone: +81762344729
24
25
26 Abstract
27 The lattice parameter of cementite in a pearlite structure was measured using the in situ heating neutron
28 diffraction method. The lattice parameters of the cementite phase of the b- and c- axes in the pearlite
29
structure were smaller than those in the martensite structure and Reed’s results [3]. The lattice
30
31 parameter of the a-axis in the pearlite structure was almost equal to that in the martensite structure and
32 Reed’s results [3]. The thermal and misfit strains, caused by the differences between the thermal
33 expansion rate and lattice parameter of the cementite and ferrite phases, should affect the lattice
34
35 parameter of cementite in the pearlite structure.
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37 Keywords: lattice parameter, neutron diffraction, pearlitic steels, internal stresses, thermal
38
conductivity.
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2 Cementite is a compound of iron and carbon and one of the constituent phases of the pearlite structure
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4 in steel. The crystal structure and mechanical properties of cementite were thoroughly investigated
5 [1,2], and cementite was found to have an orthorhombic crystal structure, as well as high hardness and
6 brittleness. Reed et al. [3] demonstrated the temperature dependence of the lattice parameter of
7
8
cementite by applying the in situ heating neutron diffraction method on the Fe-2.77 mass%C alloy.
9 The proeutectoid cementite was dominant in the cementite in Fe-2.77 mass%C, and only a few of
10 these exhibited a pearlite structure. Therefore, the temperature dependence of the lattice parameter of
11 cementite in the pearlite structure has not been established yet.
12
13 Pearlitic steel has a ferrite and cementite lamella structure. Koga et al. [4-5] revealed that the
14 continuous crystal rotation within a pearlite structure is caused by the misfit strain resulting from the
15 difference in the lattice spacing between the ferrite and cementite phases. The misfit strain was
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17 calculated in some orientation relationships (ORs) between the ferrite and cementite, such as Isaicheiv
18 OR [6], Burgers OR [7], and Pitsch-Petch OR [8-9], and the result stated that a significant amount of
19 the lattice misfit strain occurs in any OR [10]. Nakada et al. [11] calculated the accommodation of the
20
misfit strain by a misfit dislocation and concluded that a certain misfit strain remains after the pearlitic
21
22 transformation, although the misfit strain is partly accommodated via a misfit dislocation and
23 structural ledge at the ferrite/cementite interfacial boundary introduced during transformation. These
24 results indicate that the cementite phase has a certain amount of lattice misfit strain—that is, elastic
25
26 strain, and that the lattice parameter in the cementite should differ from that in the proeutectoid or bulk
27 cementite. In this study, the temperature dependence of the lattice parameter of cementite in a fully
28 pearlitic structure was revealed, and thereafter, the contribution of the thermal strain and the misfit
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strain to the lattice parameter of cementite phase was discussed.
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31 Commercial eutectoid steel (Fe-0.85mass%C-0.3mass%Mn) was used. The specimen was heat-
32 treated at 1123 K for 1.8 ks and subsequently furnace-cooled to form a fully pearlitic structure or heat-
33 treated at 1023 K for 1.8 ks and subsequently water-quenched to form a martensitic structure. In situ
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35 neutron diffraction measurements were carried out during heating from 300 K to 1000 K using
36 “TAKUMI”, a time-of-flight engineering material diffractometer at the Japan-Proton Accelerator
37 Research Complex. A plate-type specimen with a length of 30 mm, width of 10 mm, and thickness of
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4 mm was used for the measurement, and the heating rate was 0.05 K/s. The lattice parameters were
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40 obtained via Pawley refinement using the Z-Rietveld software [12]. The thermal strain generated
41 during cooling was calculated using a 2D plane strain finite element model (FEM) in Abaqus. The
42 eight-node CPE8R element was adopted with an element size of 0.0001mm.
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44 Figure 1 shows a part of the diffraction profile in the (a) pearlite and (b) martensite structures at
45 various temperature levels. Diffraction peaks of the cementite phase clearly appeared in the pearlite
46 structure at all temperatures, and high intensity is maintained even at high temperatures. However, the
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peaks of the cementite phase were not detected in the martensite structure at 300 K, but the austenite
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49 peak was detected. The austenite decomposed to the ferrite and cementite until a temperature of 873
50 K was reached, and the peaks of the cementite phase clearly appeared at 873 K. The intensity of
51 cementite in the martensite structure at 873 K was almost identical to that of the pearlite structure,
52
53 meaning that the volume fractions of their cementite were almost equal. The phase fraction of austenite
54 in the martensite structure was approximately 6%; therefore, almost all the cementite in the martensite
55 structure was precipitated from the martensite matrix, which possessed supersaturated carbon at room
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temperature.
58 Figure 2 shows the lattice parameter of the cementite phase of each axis and the volume of unit cell
59 as a function of temperature. Reed’s results are also plotted in Figure 2. Each axis of the cementite
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2 phase is defined as described in the schematic in Figure 2. The error of the lattice parameter of
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4 cementite at each temperature calculated using the Z-Rietveld software was less than 0.006% in all
5 axes, indicating that a high-accuracy experiment could be performed. The temperature dependence of
6 the lattice parameter of the cementite phase of the a-axis in the pearlite structure was almost equal to
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that in Reed’s results (Figure 2 (a)), and the cementite in the martensite structure had a slightly larger
9 lattice parameter than the cementite in the pearlite structure at all temperatures. The lattice parameters
10 of the cementite phase of the b-axis (Figure 2 (b)) in the martensite structure and Reed’s results were
11 almost equal, while those in the pearlite structure were slightly smaller than those in the martensite
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13 structure and Reed’s results. The lattice parameter of the cementite of the c-axis (Figure 2 (c)) in the
14 pearlite structure was significantly smaller than that in the martensite structure and Reed’s results. The
15 volumes of the unit cell of cementite (d) in the martensite structure and Reed’s results were identical,
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17 while the pearlite structure had a significantly smaller volume of the unit cell of cementite than the
18 martensite structure and Reed’s results. These results indicate that the experiment is high accuracy and
19 that the cementite phase in the pearlite structure has significant compressive internal stress.
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Figure 3 shows the thermal expansion of the cementite and ferrite phases at (a) 473 K and (b) 273 K
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22 in the pearlite structure calculated from Figure 2, and the lines in Figure 3 (a) indicate that the same
23 in Reed’s results. The thermal expansion of each axis in the pearlite structure is almost similar to that
24 in Reed’s results, although the thermal expansion in Reed’s results deviates when the temperature of
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26 900 K is exceeded. The thermal expansion of the cementite phase of the c-axis above 473 K in the
27 pearlite structure is identical to that of the ferrite. However, below 473 K, which is the Curie
28 temperature of the cementite phase [13], the thermal expansion of cementite significantly differs from
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that of the ferrite (Figure 3 (b)), namely, the thermal expansion in each axis of cementite is small
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31 compared to that of the ferrite.
32 There are two possibilities for the origin of the internal strain in the cementite phase in the pearlite
33 structure: (i) the misfit strain between the ferrite and cementite and (ii) the thermal strain introduced
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35 during cooling after the pearlitic transformation. The value of the misfit strain assuming Pitsch-Petch
36 OR, (001)cementite//(5-2-1)ferrite, [010]cementite // 2.6° from [113]ferrite, and [100]cementite // 2.6° from [13-
37 1]ferrite [8-9], depends on the crystal orientation. For example, the compressive and tensile misfit strains
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are introduced into the cementite phase of [100]cementite and [010]cementite, and corresponded to the a and
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40 b axes, respectively. The change of lattice parameter of the cementite phase just after pearlitic
41 transformation had been demonstrated, which is corresponded to the release of the misfit strain [14].
42 According to the result, the change of lattice parameter was stopped at approximately 3 ks. In this
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44 study, the heating rate was sufficiently slow to release of misfit strain, however, the lattice parameter
45 was significantly different between pearlite structure and martensite structure or Reed’s work even at
46 high temperature. Therefore, the thermal strain should be introduced during cooling after pearlitic
47
transformation. The thermal expansion of the cementite phase of the c-axis was identical to that of the
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49 ferrite phase above 473 K and smaller than that of the ferrite phase below 473 K. Therefore, the thermal
50 strain may have been generated during the cooling process from 473 K to room temperature. In this
51 study, the thermal strain generated during cooling from 473 K to 273 K was estimated using FEM.
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53 Figure 4 shows the (a) simulation model and (b) εx and (c) εy strain profiles along the white line in (a).
54 The coefficients of thermal expansion were measured from Figure 3 (b) to be 12.5 × 10-6 K-1 in ferrite,
55 5.2 × 10-6 K-1 in the c-axis of cementite, and 8.4 × 10-6 K-1 in the a-axis of cementite. The volume
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fraction of cementite was 12%, and the lamellar spacing was 200 nm. The εx strain, which
58 corresponded to the a-axis of the cementite, was compressive and equal in the ferrite and cementite
59 phases as shown in Figure 4 (b). Because the coefficient of thermal expansion in the b-axis of the
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2 cementite is almost identical to that in the a-axis, the same level of compressive strain should be
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4 introduced along the b-axis. The εy, which corresponds to the c-axis of the cementite, exhibits
5 compressive strain in both phases, although the ferrite phase has a much higher compressive strain
6 than the cementite phase. The average estimated εy strain within the cementite phase was -0.037%.
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The calculated strain in the cementite from the difference in the lattice parameter of the pearlite
9 structure at 800 K was approximately -0.125%, which is higher than the estimated value from FEM.
10 However, the strain levels of the estimated and calculated value were approximately identical.
11 Therefore, it can be concluded that the difference between the thermal expansion rate of the cementite
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13 and ferrite introduces compressive strain on the c-axis of cementite. The a and b axes should have both
14 the misfit strain and thermal strains. The tensile and compressive misfit strains were generated along
15 the a-axis and b-axis, respectively. Because the lattice parameter in the a-axis of cementite in the
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17 pearlite structure is identical to that in Reed’s results as shown in Figure 2(a), the lattice misfit and
18 thermal strains must be balanced along the a-axis. However, the lattice parameter in the b-axis of
19 cementite in the pearlite structure was smaller than that in Reed’s results (Figure 2 (b)), meaning that
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the misfit and the thermal strain were superimposed along the b-axis. In the ferrite of the pearlite
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22 structure, the thermal strain was compressive. In fact, the lattice parameter of ferrite in the pearlite
23 structure was smaller than that of the ferrite in an annealed single-phase polycrystalline structure,
24 while the misfit strain in the ferrite of the pearlite structure increases the full width at half maximum
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26 of diffraction peak, as demonstrated in some studies [4-5, 15].
27 The temperature dependence of the lattice parameter of cementite in the fully pearlitic structure was
28 revealed, and thereafter, the contribution of the thermal and lattice misfit strains to the lattice parameter
29
was discussed. The main results are summarized as follows:
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31 (1) The lattice parameter of cementite of the a-axis in the pearlite structure was almost equal to that
32 of the cementite in the martensite structure and Reed’s results. The b and c axes of cementite in
33 the perlite structure had smaller lattice parameters than those in the martensite structure and Reed’s
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35 results, indicating that compressive strain occurs along the b and c axes.
36 (2) The thermal expansion of cementite in the pearlite structure above 473 K was almost equal to that
37 in Reed’s results, and the thermal expansion of the c-axis of cementite was identical to that of the
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ferrite phase in the pearlite structure. Below 473 K, the cementite exhibited a smaller thermal
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40 expansion than the ferrite phase.
41 (3) The estimated thermal strain in the cementite phase generated during cooling from 473 K to 273
42 K using the finite element method was compressive along all axes. Therefore, it can be concluded
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44 that the thermal strain decreases the lattice parameter of the cementite of the c-axis in the pearlite
45 structure. The lattice parameters of the a and b axes of cementite in the pearlite structure must be
46 determined by superimposing the thermal and misfit strains between cementite and ferrite in the
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pearlite structure.
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50 Acknowledgment
51 The neutron diffraction experiments were performed at BL19 in the Materials and Life Science
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53 Experimental Facility (MLF) of J-PARC following the proposals of 2018B0213.
54 Authors grateful to Yamamoto Scientific Tool Laboratory Co., LTD for providing the pearlitic and
55 martensitic steels.
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2 References
3
4 [1] M. Umemoto, K. Tsuchiya, Tetsu-to-Hagane 88 (2002) 117-128.
5 [2] H.K.D.H. Bhadeshia, Int. Mater. Rev. 65 (2020) 1-27.
6 [3] R.C. Reed, J.H. Root, Scr. Mater. 38 (1997) 95-99.
7
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[4] N. Nakada, N. Koga, T. Tsuchiyama, S. Takaki, Scr. Mater. 61 (2009) 133-136.
9 [5] N. Koga, N. Nakada, T. Tsuchiyama, S. Takaki, M. Ojima, Y. Adachi, Scr. Mater. 67 (2012)400-
10 403.
11 [6] I.V. Isaichev, Zh. Tekh. Fiz. 17(1947) 835-838.
12
13 [7] Y.A. Bagaryatsky, Dokl. Akad. Nauk SSSR. 73(1950) 1161-1164.
14 [8] N.J. Petch, Acta Cryst. 6 (1953) 96.
15 [9] W. Pitsch, Acta Metall. 10 (1962) 79-80.
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17 [10] D.Z. Zhou, G.J. Shiflet, Metall. Trans. A 23A (1992) 1259-1269.
18 [11] N. Nakada, M. Kato, ISIJ Int. 56 (2016) 1866-1873.
19 [12] R. Oishi, M. Yonemura, Y. Nishimaki, S. Torii, A. Hoshikawa, T. Ishigakib, T. Morishima,
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K. Morid, T. Kamiyama, Nucl. Instr. Methods Phys. Res A 600 (2009) 94-96.
21
22 [13] A. Kagawa, T. Okamoto, Trans. Jpn. Inst. Met. 20 (1979) 559-666.
23 [14] Y. Amemiy, N. Nakada, S. Morooka, M. Kosaka, M. Kato: Tetsu-to-Hagane 105 (2019) 314-323.
24 [15] Y. Tomota, Y. X. Wang, T. Ohmura, N. Sekido, S. Harjo, T. Kawasaki, W. Gong, A. Taniyama,
25
26 ISIJ Int. 58 (2018) 2125-2132.
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10 (a)
11 Ferrite
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Cementite
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Intensity, I/ -

16 973 K
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873 K
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21 350 K
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23 1.75
0.175 1.85
0.185 1.95
0.195 2.05
0.205 2.15
0.215
24 Lattice spacing, d / Å
25 (b)
Ferrite or martensite
26 Cementite
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Austentite
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Intensity, I/ -

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30 973 K
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32 873 K
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300 K
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36 1.75 1.85 1.95 2.05 2.15
0.175 0.185 0.195 0.205 0.215
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Lattice spacing, d / Å
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40 Figure 1 Part of the diffraction profile at various temperatures in the (a) pearlite and (b) martensite
41 structure.
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12 (a) 4.575 (b)
13 Cementite in pearlite
5.140
Cementite in Pearlite
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Lattice parameter, a / Å

4.565 Cementite in martensite 5.130

Lattice parameter, a / Å
Cementite in Martensite
15 Reed’s results [3]
4.555 5.120 Reed’s results [3]
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17 4.545 5.110
18 c
5.100 c
4.535
19 Cementite phase
5.090 Cementite phase
20 4.525
Fe atom
C atom Fe atom

21 a
b 5.080 C atom

b
4.515 a
22 300 400 500 600 700 800 900 1000
5.070
23 300 400 500 600 700 800 900 1000
Temperature, T / K
Temperature, T / K
24 (c) 6.840 (d) 160
25 6.830 Cementite in Pearlite 159.5 Cementite in Pearlite
Volume of unit cell, V / Å3

26
Lattice parameter, a / Å

6.820 Cementite in Martensite 159 Cementite in Martensite

27 6.810 Reed’s results [3] 158.5 Reed’s results [3]
28 6.800 158
29 6.790 157.5
30 6.780 c 157
31 6.770 156.5
Cementite phase

32 6.760 Fe atom
156
C atom
6.750 155.5
33 a
b

6.740 155
34 300 400 500 600 700 800 900 1000 300 400 500 600 700 800 900 1000
35 Temperature, T / K Temperature, T / K
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37 Figure 2 Lattice parameter of the cementite phase of (a) a-axis, (b) b-axis and (c) c-axis and (d) volume
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of unit cell as a function of temperature.
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10
0.01
11 c axis Cementite in Pearlite
12 b axis Cementite in Pearlite
Thermal expansion from

13 0.008 a axis Cementite in Pearlite

14 c axis Cementite in Reed’s results
15 b axis Cementite in Reed’s results
0.006
16 a axis Cementite in Reed’s results
17 Ferrite in Pearlite
473 K, ε/ -

18 0.004
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20
0.002
21
22
23 0
24 400 500 600 700 800 900 1000
25 Temperature, T / K
26 0.003
27 Ferrite in Pearlite
28 c axis cementite in Pearlite
Thermal expansion from

0.0025
29 b axis cementite in Pearlite
30 a axis cementite in Pearlite
0.002
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32 0.0015
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273 K, ε/ -

34 0.001
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36 0.0005
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38 0
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300 350 400 450 500
40 Temperature, T / K
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42 Figure 3 Thermal expansion of the cementite phase from (a) 473 K and (b) 273 K in the pearlite
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44 structure calculated from Fig.2
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7 (b) 0
8
9 -0.0005

Strain in x direction, εx/-

10 -0.001
11
12 -0.0015
13 (a) -0.002
14 S
15 -0.0025
16 -0.003 S F
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18 -0.0035
0
0 0.4
0.1 0.8
0.2 1.2
0.3 1.6
0.4 2.0
0.5
19 Distance, d/μm
20 (c) 0
21 F
22 -0.0005
Strain in y direction, εy/-

23 -0.001
24 F
-0.0015
25
26 -0.002
Cementite c y
27 -0.0025
28 Ferrite a x
-0.003
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30 -0.0035 S
31 -0.004
32 0
0 0.4
0.1 0.8
0.2 1.2
0.3 1.6
0.4 2.0
0.5
Distance, d/μm
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35 Figure 4 (a) simulation model, (b) εx and (c) εy strain profile along the white line in (a).
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