Materials Letters 70 (2012) 710

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Materials Letters
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Microstructural evolution of high manganese steel solidied under superhigh pressure

Bo Han, Sujun Wu
School of Materials Science and Engineering, Beihang University, Beijing, China

a r t i c l e

i n f o

a b s t r a c t
The microstructure of high manganese steel solidied under 6 GPa was examined by using OM, FEGSEM and TEM for analysis of inuences of high pressure on phase transformation and the morphology of carbides. The results indicate that the microstructure consisting of complete equiaxed dendrites, the mean dendrite arm spacing of which was ~ 18 m, was remarkably rened under 6 GPa. The change of the morphology of carbides from needle-like and rhombic carbide (M3C) to nodulized cubic carbide (M23C6) was observed by TEM, which is associated with the undercooling and distribution of trace elements of manganese. The diameter of spheroidal carbides is approximately between 150 nm and 200nm. 2011 Elsevier B.V. All rights reserved.

Article history: Received 29 June 2011 Accepted 13 August 2011 Available online 27 November 2011 Keywords: High pressure High manganese steel Solidication Microstructure Carbide

1. Introduction Solidication microstructure is a complex function of the rate of solidication, temperature gradients, composition and several material characteristics [1]. When taking pressure into consideration, solidication microstructure will become more complex. Due to some limitations of theory and technology, however, the investigation of pressure on solidication has not been popular [2]. Solidication of metals under superhigh pressure can result in ne and non-equilibrium microstructures [3]. Signicant changes can occur in solid solubility of alloy elements, solidliquid interface feature and formation of new phases [4]. For example, the transition from -phase to -phase was observed in the iron under superhigh pressure [5]. Diamond can be made from graphite at high temperature and high pressure [6]. Some investigations for the effects of pressure on the nucleation process and solidication microstructure of light alloys, such as AlZn, AlMg, AlSi, AlNiY and AlGe have been carried out [4,79]. Yu et al. [4] studied the non-equilibrium microstructure of AlSi alloy formed under superhigh pressure, and indicated that high pressure can signicantly enhance the solid solubility of Si and Al in primary phase. Straumal et al. [7] reported that nanograined structure of binary AlZn and AlMg alloys can be formed under high pressure torsion. Jie et al. [8] showed that high pressure can change the amount of Al3Mg2 and a new way to prepare supersaturated Al(Mg) solid solution has been provided. Xu studied the microstructure of AlNiY [2] and AlGe [9] alloys

solidied under high pressure and found that the grains and the secondary phases are greatly rened. The change of the eutectic Ge growth mode from facet to no-facet was observed using TEM in the AlGe alloy solidied under 5 GPa. Above-mentioned analysis is mainly about eutectic or hyper-eutectic alloy with low melting point. However, the effects of pressure on the solidication of metal with high melting point, such as ferrous metals, are seldom-reported. High manganese steel has been widely used in industry due to its high wear-resistance. During normal solidication, however, dendrites can easily grow to columnar crystals owing to wide solidication temperature range, low thermal conductivity and solidication velocity, which will reduce the toughness of the steel. Solidication under high pressure may have some effects on the microstructure and properties of steels. In this work, microstructural evolution and carbide formation were investigated for high manganese steel solidied under a pressure of 6 GPa. 2. Method The chemical composition (wt.%) of the commercial high manganese steel used in this work is 1.25C, 16Mn, 0.4Si, 0.0025S, 0.0025P, and Fe (bal.). The sample is a cylinder of 5 5 mm which was packed in BN ux during experiment. The sample was heated to 1750 C for 15 min to melt and then cooled down to room temperature at a cooling rate of 25 C/s through circulated cooling agent. A constant pressure of 6 GPa was applied to the cylindrical sample during heating and cooling. The pressure calibration was carried out at room temperature by means of the known pressure-induced phase transitions of Bi and ZnTe at 2.55, 7.7, 9.6 and 12.0 GPa. The cell temperature under 6 GPa was measured up to 1750 C by WRe3WRe25

Corresponding author. Tel.: + 86 10 82316326; fax: + 86 10 82317108. E-mail addresses: hmeng521@126.com (B. Han), wusj@buaa.edu.cn (S. Wu). 0167-577X/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2011.11.057

B. Han, S. Wu / Materials Letters 70 (2012) 710

thermocouple. To compare microstructural evolution, water toughening heat treatment was carried out for the sample. The observation of microstructure was carried out using optical microscope and a Hitachi S-3400 eld emission gun scanning electron microscopy (FEGSEM) operated at 20 kV equipped with an energy dispersive spectrometer (EDS). The phase constituent was analyzed on a D/max-2500/PC X-ray diffractometer (XRD) with CuK radiation and a JEM-2100 transmission electron microscope (TEM) operated at 200 kV.

from cast ingots strongly depend on dendrite arm spacing [10]. The mean dendrite arm spacing of equiaxed dendrites formed under 6 GPa pressure is ~18 m, which is greatly less than that (about 170 m) solidied under normal pressure. According to Frenkel [11], when the pressure is close to GPa, the diffusing coefcient of solute, DL, is as follows: DL D0 expPV =RT 1

3. Results and discussions As is well known, the microstructure of the as-cast high manganese steel possesses austenitic matrix and discontiguous net-like carbides distributed in the interface between phases. Signicant changes occurred, however, in the microstructure of the high manganese steel solidied under high pressure. The microstructure of high manganese steel solidied under 6 GPa is given in Fig. 1a, which shows a distinctive solidication microstructure consisting of ne equiaxed dendrites. It can be seen that the rened equiaxed dendrites have complete dendritic arms, in which the length of the second dendrite arms is much smaller than the long major primary dendrites. Since the equiaxed dendrites were surrounded by subcooled liquids and the latent heat can hardly be released during solidication, some second dendrite arms were therefore formed as rod-like structure. It was found that the mechanical properties of various cast alloys and wrought material produced

where, D0 is the diffusing coefcient of solute at normal pressure, P is pressure, R is gas constant, T is the temperature of molten metal (K), V is initial volume of a liquid. It can be found that diffusing coefcient of solute reduces markedly under high pressure. The constitutional supercooling criterion under normal pressure is expressed as follows [12]. GL = mL C 0 =DL 1k0 =k0 : 2

Fig. 1. Optical micrographs of high manganese steel under different states. (a) Original structure of the sample solidied under 6 GPa; (b) Water toughened structure of the sample solidied under 6 GPa.

Where, GL is the actual temperature gradient, is the solidication rate, mL is the slope of liquid line, C0 is the original alloy concentration, k0 is the equilibrium partition coefcient, DL is the diffusing coefcient of solute in liquid. In Eq. (2), the left side represents external conditions, whereas the right hand side is determined by the parameters of alloys. It can be seen, from Eqs. (1) and (2), that when the applied pressure increases, the tendency of constitutional supercooling in the solidliquid interface increases due to the decrease of DL. Under high pressure, the crystalloids of the alloy can grow along threedimensions to form dendrites in the supercooled liquid metals and the dendrite arm length is limited because of the reduction of the diffusing coefcient. A small DL can result in the formation of a stable solute-rich layer in front of the liquidsolid interface, and a relatively wide range of constitutional supercooling. When the constitutional supercooling is bigger than the supercooling degree of nucleation, new nucleus can be formed, which will further limit the growth of the second dendrite arms. As a result, equiaxed dendrites become the main characteristic of the solidication microstructure of metals solidied under high pressure, as shown in Fig. 1a. Jie [8] has reported that the amount of phase decreases and the microstructure is rened with increasing pressure. The grain sizes of the high manganese steel solidied under 6 GPa are also much smaller than that under normal pressure. To reveal the effect of the treatment on the microstructure of the steel concerned, the specimen was heated to 1050 C for 30 min and then quenched in water. An optical micrograph illustrating the microstructure of the water toughened specimen solidied under 6 GPa is presented in Fig. 1b. It can be seen that the dendrites become short and incomplete. Metallographic analysis showed that the treatment has no signicant inuence on the dendrite arm spacing of equiaxed dendrites and there were no grain boundaries of austenite after the specimen subjected to austenitization at 1050 C (Fig. 1b), which indicates that the mechanism of nucleation and growth under high pressure is different from the classical nucleation theory. The FEGSEM image of the morphology and the EDS compositional analysis of equiaxed dendrites were shown in Fig. 2a and b. The results showed that the average concentration of Mn in the interfacial area between the equiaxed dendrites is much higher than that in other sections, twice of the content in primary dendrite. During the solidication, redistribution of Mn in the austenite will occur. Mn gradients may be present especially in the austenite where diffusion is much slower and the diffusing coefcient of solute elements will be further decreased under 6 GPa pressure, which may be the reason of the high Mn concentration in the late solidied interfacial area. The mean microhardness value of the interfacial area is ~ 845 HV, and the hardness of the dendrites is ~230 HV under 6 GPa, which is

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b
Fig. 3. X-ray diffraction of high manganese steel under different states. (a) Solidied under normal pressure; (b) Solidied under 6 GPa; (c) Water toughened after solidication under 6 GPa.

Fig. 2. Typical FE-SEM image of high manganese steel solidied under 6 GPa (a) and distribution of Mn in different sections (b).

higher than that of the specimen solidied under normal pressure. The high hardness of the interfacial area may be attributed to the high content of the alloying element Mn or its compounds, which may play a role in the improvement of the wear resistance of the steel. Fig. 3 shows the result of X-ray diffraction patterns of the high manganese steel specimens under different states. It can be found that a new carbide phase exists in the specimens solidied under 6 GPa, different from the M3C carbide formed in the steel solidied under normal pressure. The carbide has been identied as M23C6 through calibration. The main peak of the -Fe phase shifts to the high angles, indicating the lattice parameter changed due to high pressure. The M23C6 phase disappeared after water toughening treatment. Fig. 4 demonstrates the TEM microstructure and the corresponding selected area diffraction (SAD) pattern of the carbide in high manganese steel solidied under 6 GPa. The diffraction pattern shows that it is complex cubic carbide (M23C6) with lattice parameter a= 10.333 nm. As shown in Fig. 4a, it is a nodular shape carbide different from the needle-like and network-like carbides in high manganese steel solidied under normal pressure. The size of these ne carbides is about 150 nm200nm. The constitutional undercooling under high pressure is useful to carbide nucleation. Since the probabilities of obtaining carbon in different orientations are equivalent, the carbides therefore grow into a spherical shape. Generally, modication is used to change the morphology of carbides from networklike to spherical shape which can improve toughness and wear resistance of the high manganese steel. The results of XRD and TEM showed, however, that the spheroidal M23C6 phase can be obtained under the condition of high pressure solidication, which may have the similar benecial effect on the wear resistance of the steel, without modication.

M 23C6

Z =[2,2,4];Z 1 = [0,1,1];Z 2 = [1,2,3];

Fig. 4. TEM micrograph of spheroidal carbides in high manganese steel (a) and the corresponding SAD pattern (b).

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B. Han, S. Wu / Materials Letters 70 (2012) 710

4. Conclusion Effect of high pressure on the solidication microstructure of high manganese steel and the nature of carbides were studied. Main conclusions were drawn as follows: (1). During the solidication process of high manganese steel under 6 GPa, a distinctive solidied microstructure consisting of equiaxed dendrite was obtained, with a mean dendrite arm spacing of ~18 m. (2). There are no austenitic grain boundaries in the microstructure of high manganese steel solidied under 6 GPa and that after water toughening treatment, which indicates that the mechanism of nucleation and growth under high pressure is different from the classical nucleation theory. (3). The mean hardness of the interfacial area in the microstructure solidied under 6 GPa is much higher than that of the dendrites, which may be benecial to the wear resistance. (4). Complex cubic spheroidal ne carbides (M23C6) formed in the steel solidied under 6 GPa.

Acknowledgments The authors are grateful to the School of Earth and Space Sciences, Peking University, and the School of Materials Science and Engineering, Beihang University, for the support of this research and for the provision of laboratory facilities.

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