Journal of Alloys and Compounds 650 (2015) 918e924
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Journal of Alloys and Compounds journal homepage: http://www.elsevier.com/locate/jalcom
Microstructure and properties of TiC-high manganese steel cermet prepared by different sintering processes Zhi Wang, Tao Lin*, Xinbo He, Huiping Shao, Jianshu Zheng, Xuanhui Qu Institute for Advanced Material & Technology, University of Science and Technology Beijing, Beijing 100083, China
a r t i c l e i n f o
a b s t r a c t
Article history: Received 18 June 2015 Received in revised form 6 August 2015 Accepted 7 August 2015 Available online 12 August 2015
In the paper, the TiC 50 wt.% high manganese steel cermet was made with different sintering processes including vacuum sintering, hot pressing, microwave sintering and spark plasma sintering (SPS). The microstructure, porosity and fracture morphology of the samples were analyzed with scanning electron microscopy (SEM). Phase analysis was carried out using X-ray diffraction (XRD). The density, hardness, transverse rupture strength (TRS) and wear resistance were investigated for the effect of the sintering processes. The results showed that the coreeshell structure was not clearly observed for the TiC particles in microstructures and the high manganese steel matrix is BCC structure. Hot pressing, microwave sintering and SPS are useful processes for densiﬁcation of the cermet. Nearly full density and higher hardness can be reached by these three processes at a lower sintering temperature and in a shorter sintering time. However, higher TRS can be reached by means of alloying completely in a longer sintering time, for example vacuum sintering. Pre-sintering in a long sintering time at a lower sintering temperature is also useful for improving the TRS. Finally, vacuum sintering is an effective process for producing this composite with the lowest cost in the mass production. © 2015 Elsevier B.V. All rights reserved.
Keywords: Cermet Titanium carbide High manganese steel Sintering processes Microstructure and properties
1. Introduction Ceramic-metal composites e cermets, are widely used for high performance wear parts and cutting tools due to the good combination of hardness and toughness. Steel bonded carbide ﬁrst appeared in the early 1960s as a creative cermet integrating the characteristics of both steel and carbide. Steel bonded carbide has several advantages, including a wide range of process characteristics, good mechanical properties and excellent chemical stability . In this study, we focus on the processing and mechanical behavior of a special cermet: TiC reinforced high manganese steel composite. TiC, as one of the popular ceramic components in cermets, is especially suitable for steel or iron-based composites due to its high hardness, low density, good wettability and chemical stability with Fe-based matrices [2,3]. The high manganese austenite steel, on the other hand, has high toughness and wear resistance under high impact working conditions because of its high hardening capacity . Comparison with high manganese austenite
* Corresponding author. E-mail address: [email protected]
(T. Lin). http://dx.doi.org/10.1016/j.jallcom.2015.08.047 0925-8388/© 2015 Elsevier B.V. All rights reserved.
steels with Mn more than 14 wt.%, high manganese steels with Mn less than 14 wt.% perform better wear resistance under low stress abrasive wear condition. However, the wear resistance of high manganese steel with lower content of Mn under high stress abrasive conditions needs to be improved [5,6]. The production methods of such composites could be categorized into solid state and molten/casting state methods [7e9]. The main solid state process includes powder metallurgy, self-propagation high temperature synthesis, mechanical alloying and carbon-thermal reduction, and so on [10e18]. Compared with solid state process, molten/casting state methods have the advantage of easiness, ﬂexibility, low cost, automatic scale-up, and being able to make the big and the parts with complicated shapes. For production of TiCeFe composite, the reported processing methods include addition of TiC into FeeC, addition of ferrotitanium into molten FeeC, addition of C into FeeTi, addition of Ti into molten FeeC and inmould method have been reported so far [19e25]. TiC-based Cermet prepared by powder metallurgy facilitates the realization of complex components in near net shape and can effectively solve the difﬁcult of forming process, etc, which has been widely used. A lot of researchers have fabricated the steelbonded cermet by powder metallurgy. S.W. Hu et al.  reported the TiC reinforced quenched Mn13 steel composite via combustion
Z. Wang et al. / Journal of Alloys and Compounds 650 (2015) 918e924
synthesis during casting which has a hardness of 55 HRC with 40 wt.% TiC. F. Akhtar et al.  fabricated the TiC-465 stainless steel/ 465 stainless steel layer composites with 50, 60, 70 wt.% TiC and the hardness and TRS are 85.2, 87, 88.2 HRA and 1332, 1103, 782 MPa, respectively. F. Akhtar  reported TiB2 and TiC(30, 55, 70 wt.%) reinforced 465 stainless steel matrix composites, whose hardness are about 75, 88, 92 HRA and the wear loss with a sliding distance of 600 m at 200 N about 1.7e4.7 mg. B.H. Li et al.  prepared in situ TiC particles (>50 wt.%) reinforced Fe-based composites by use ferrotitanium and carbon black powders with the combination of in-situ and spark plasma sintering and the composite has a maximum hardness of 83.2 HRA. B.H. Li et al.  reported that TiB2eTiC(95 wt.%) reinforced steel matrix composites produced by spark plasma sintering. The maximum hardness of the composite is 83.8 HRA and the wear loss under the condition of dry sliding wear with loads of 196, 392 and 588 N are 9.66 18.80 55.83 mg, respectively. Y. Wu et al.  researched the effects of carbon content on the GT35 cermet produced by in-situ reduction of ilmenite and vacuum pressureless sintering. The average bending strength is over 1229 MPa after heat treatment and the hardness is 69.4 HRC. In this paper, the powder metallurgy method was used to make the TiC-50 wt.% high manganese steel cermet. Such processes as vacuum sintering, hot-pressing, spark plasma sintering and microwave sintering were used to investigate the effect of these processes on the microstructure and mechanical properties of the cermet. 2. Materials and experimental procedure 2.1. Powders In this study, the TiC-high manganese steel cermet was prepared with powder metallurgy process. Table 1 shows the initial composition of the cermet. The purity of TiC powder is 99.0% and its average particle size is 4.3 mm. Electrolytic iron powder (99.5% purity, 300 mesh), carbon black(99.5% purity, 500 mesh), as well as ferroalloys (99.0% purity, 300 mesh) with Cr and Mn were used to make the high manganese steel matrix. 2.2. Manufacture of the cermets The raw powder mixture of metal and ceramic was wet milled in ethanol for 4 h with a media ball to powder ratio of 4:1 in a planetary ball mill (XMQ-2L). The milled powders were dried in a vacuum drying oven (DZF-6020) at 70 C for 24 h, and then were sieved through a 100-mesh sieve. The milled powder was sintered with four different processes, which include vacuum sintering, hot pressing, microwave sintering, SPS. For vacuum sintering process, the powder was compacted with a steel mold at a pressure of 250 MPa and sintered in a vacuum sintering furnace at 1420 C for 1 h. For hot pressing, a vacuum hot pressing furnace (ZT-150) was used to hot-press the milled powder directly in a graphite mold with a pressure of 40 MPa. For microwave sintering process, the milled powder was compacted with a steel mold at a pressure of 250 MPa and was sintered in vacuum at 1200 C for 1 h and then was sintered in a microwave oven (MTS-20) with a 2.45 GHz frequency and a 1.4 kW power. For SPS process, the powder was
Table 1 The chemical composition of the TiC-steel cermet. Component
placed into a graphite die (30 mm in diameter) for sintering in vacuum with an SPS system (SPS-1030T). The applied uniaxial pressure was 40 MPa and maintained for 5 min at the ﬁnal sintering temperature. Fig. 1 shows the size distribution of the TiC powder and milled powder. The left peak corresponds to TiC particles and the right peak corresponds to metal matrix powders in Fig. 1b. Fig. 2 shows SEM micrograph of the TiC powder and milled powder. The TiC particles before milled have a irregular shape and have some accumulation (the average particle size 4.3 mm). After ball-milled, the particle size of TiC reduced to 3.0 mm (the left peak in Fig. 1b) and TiC particles still have the irregular shape. 2.3. Testing The average size of the TiC of the powder were analyzed by laser particle analyzer (JL-1177). The density of the sintered composites was determined using the Archimedes' immersion method in water. The porosity and the average size of the TiC of the cermets was measured by analyzing the polished surface of the cermets with an image tool software. Hardness was tested by a Rockwell hardness tester (HR-150A). A scanning electron microscope (SEM, Cambridge LEO-1450) together with an energy-dispersive spectrometer (EDS, Model Link-Isis) was used to evaluate powder morphology microstructure and the fracture morphology. The phases were identiﬁed by X-ray diffractometer (XRD, D8 ADVANCE). Electronic universal testing machine (WDW-100) was used to conduct the pressure to the samples of 35 mm 5 mm 5 mm in dimension for the TRS test. The wear resistance was evaluated using a pin-on-disk wear tester (MLS-225) with 60 mesh silicon carbide as an abrasive and a load of 196N. 3. Results and discussion 3.1. Densiﬁcation of various sintering processes Table 2 lists the properties of the as-sintered TiC-steel composites. Firstly, densiﬁcation was analyzed according to the density and porosity. The calculated density of the composite is 6.04 g/cm3. From Table 2 the density always increases with the increase of temperature and/or pressure. For vacuum sintering, the composite sintered at 1300 C has a lot of pores, but can be the nearly full density at 1420 C. For hot pressing, the sintering temperature of 1300 C isn't suitable for the densiﬁcation of the composite, and the samples sintered at 1400 C reaches the nearly full density. It seems that sintering at 1300 C is a solid sate sintering, and sintering above 1400 C is a liquid phase sintering. Compared with vacuum sintering and hot pressing, both the microwave sintering and SPS can produce the nearly full density with lower temperature and less sintering time. For both vacuum sintering and hot pressing, solid state sintering at 1300 C leads to a very low density. The densiﬁcation of solid state sintering depends on the relatively slow mutual diffusion between different components of particles and alloy homogenization process due to the fact that the relative motion of particles could not occur. For sintering above 1400 C, the liquid phase sintering becomes the main densiﬁcation mechanism. The liquid phase ﬂowing facilitated by the capillary force between the carbide particles makes it easier for the re-arrangement of the carbide particles, which accelerates the process of densiﬁcation. For both hot pressing and SPS, the pressure during sintering process can increase the plastic deformation of metal/carbide particles, improve the ﬂuidity of liquid phase, and facilitate the atomic diffusion between carbide particles. Table 2 shows that solid state
Z. Wang et al. / Journal of Alloys and Compounds 650 (2015) 918e924
Fig. 1. The size distribution of the TiC powder(a) and milled powder(b).
Fig. 2. SEM image of the TiC powder(a) and milled powder(b).
Table 2 The properties of the samples prepared by different sintering processes. No. 1 2 3
Sintering processes Vacuum sintering Hot pressing
4 5 6
1300 C, 1 h 1420 C, 1 h 1300 C, 40 MPa, 15 min 1400 C, 20 MPa, 15 min 1400 C, 40 MPa, 15 min 1350 C, 10 min 1300 C, 40 MPa, 5 min
4.50 5.96 5.41
25.41 0.58 10.50
68 86 78
227 1105 586
68.59 16.75 35.22
Note: * Before microwave sintering, vacuum sintering was carried out at 1200 C for 1 h.
hot pressing at 1300 C (process No. 3) can only yield a higher density than vacuum sintering at 1300 C (process No. 1), but this sample also has a low density. When the hot pressing temperature was increased to 1400 C, hot pressing can have nearly full density similar to the vacuum sintering at 1420 C. The hot pressing process can effectively reduce the sintering temperature and time compared with the vacuum sintering process. Due to the active interaction between metal-carbide powder and microwave ﬁeld, microwave sintering signiﬁcantly reduces the activation energy for sintering and subsequently reduces the whole sintering cycle to a relatively low temperature . Table 2 shows that microwave sintering at 1350 C for 10 min can have nearly full density.
SPS is a more efﬁcient sintering process compared with microwave sintering. It has both pressure and rapid heating mechanism with the localized spark-discharge process in the vicinity of contacting particles . Table 2 shows that SPS at 1300 C for 5 min can have the nearly full density. 3.2. Inﬂuence of sintering process on the microstructure of samples Fig. 3 shows SEM images of the microstructure of the samples sintered with different sintering processes corresponding to the Table 2. As shown in Fig. 3, all the microstructures present three different parts: the dark phase corresponds to pores in the binder,
Z. Wang et al. / Journal of Alloys and Compounds 650 (2015) 918e924
Fig. 3. Microstructures of the cermets sintered with different sintering process (SEM images a-g show the microstructures of the samples 1e7 in Table 2 respectively).
the grey corresponds to TiC particles, and the bright phase corresponds to the steel matrix. Since the high manganese steel matrix is an austenite structure, the main microstructure difference among different sintering processes include porosity, carbide particle size and particle spatial distribution. The porosity in the matrix has the most critical effect on the mechanical properties of sintered cermets. Besides porosity, the carbide particle size and spatial distribution have signiﬁcant inﬂuence on the mechanical properties of sintered cermets as well. Homogeneous distribution of the reinforcing particles ensures isotropic mechanical properties and uniform distribution of stresses in the sintered composite. As shown in Fig. 3, sintering processes including No.5, 6, 7 sintering processes (Fig. 3e, f, g), lead to the homogeneous distribution of TiC particles.
On the other hand, the sintering processes such as processes No.1, 2, 3, 4 (Fig. 3a, b, c, d), can have some cluster of TiC particles. The shape and size of TiC particles is closely related to the liquid sintering temperature and time. The carbide particle dissolution and re-deposition is the main mechanism for particle growth [31,32]. The average sizes of TiC particles are 4.1, 3.6, 3.8, 3.6, 4.7 mm respectively for the sintering processes No.2, 4, 5, 6, 7, as shown in Fig. 3b, d, e, f, g, in which the average size for SPS process is a little bigger than other processes. TiC particles in Fig. 3b, d, e, f, g. (No.2, 4, 5, 6, 7 sintering processes) is almost spherical. Generally, the particle size of TiC grew up and got spherically during sintering. For the TiC cermets, molybdenum was typically added to produce its carbide on the surface of TiC particles, which presents a coreeshell structure in the microstructure. However, molybdenum
Z. Wang et al. / Journal of Alloys and Compounds 650 (2015) 918e924 Table 3 The metal matrix composition of the samples prepared by different sintering processes. Process No.
1 2 3 4 5 6 7
Fig. 4. SEM image of line-scans for Ti, Cr, Mn and Fe elements.
Element content/wt.% Cr
2.11 2.12 2.18 2.21 2.19 2.23 2.16
12.56 12.48 12.94 12.88 13.06 12.86 13.16
2.35 2.56 2.14 2.18 2.55 2.76 2.23
bal. bal. bal. bal. bal. bal. bal.
sintered TiC-high manganese steel cermet does not show any reaction between TiC and binder metal phase. Interface debonding was not found in the sintered material in Fig. 3b, d, e, f, g, indicating the good wettability between high manganese steel and TiC particles. The samples were weighed after sintering and the weight loss is less than 0.2 wt.%. Furthermore, the metal matrix composition of the samples prepared by different sintering processes was shown in Table 3. Mn content for vacuum sintering is slightly lower than other processes because of the evaporation of Mn, and other elements contents are almost the same as each other. Titanium is also detected because of the dissolution of TiC. 3.3. Inﬂuence of sintering process on the hardness and TRS of samples
Fig. 5. XRD patterns of the blended powder (No.0) and cermets sintered by different sintering process (No.1e7 in Table 2).
was not added in this paper to decrease the production cost, and then the coreeshell structure was not clearly observed in Fig. 3 since the element number of Ti, Cr, Mn and Fe is very close. The line-scanning image is shown in Fig. 4, in which no elements was found to rich around the TiC particles to form coreeshell structure. The XRD patterns of blended powder and the sintered samples are shown in Fig. 5. It can be seen from Fig. 5 that TiC and a-Fe presents in the blended powders because the raw material is composed of TiC, iron and a small amount of ferroalloys of Cr and Mn. There are only TiC and Fe solution phases after sintered by different processes (the locations of Fe solution diffraction peaks are the same as that of a-Fe), and no other phase was observed in the XRD patterns. Generally, high manganese steel is austenite, but the diffraction peaks is the same as ferrite after sintered. Fe solution was used instead of a-Fe since alloying elements dissolved in the metal matrix. Gaard et al.  also found a large portion of BCC structure in the metal matrix of the TiC-(Fe,Ni) cermet since titanium is a strong stabilizer for BCC structure. During sintering, a part of TiC dissolved in the metal matrix (see Table 3) to stabilize the BCC structure. A very important factor inﬂuencing the structure and mechanical properties of the composite is the metal-ceramic interface. The
The hardness and TRS of the composites sintered by the various processes were shown in Table 2. It can be seen that for vacuum sintering process, the hardness of the composite increases with the heating temperature and for hot pressing, the hardness of the composite increases with the increases of both temperature and pressure. For vacuum sintering and hot pressing at 1300 C (Processes No.1, 3), both hardness and TRS have low values because big pores appear in these samples. For the other processes, the hardness and the TRS increased obviously because these samples have nearly full density. The hardness is almost the same, 86 or 87 HRA. Processes No.2, 4, 5, 6, 7 have more effects on the TRS. For hot pressing at 1400 C, the higher pressure can decrease the porosity as showed in Table 2, which increased the TRS of the cermet. Compared with the sample sintered by hot pressing at 1400 C/ 20 MPa/15 min, the sample sintered by vacuum sintering at 1420 C/1 h increased the TRS although it has a little more pores. Because the sintering time of vacuum sintering is longer than the sintering time of hot pressing, the degree of binder alloying for vacuum sintering could be higher than that for hot pressing. This is beneﬁt for improving the TRS of the cermet. Finally, the TRS of the sample sintered by the vacuum sintering is a little bit lower than hot pressing at 1400 C/40 MPa/15 min. Since there is sparkdischarge among particles, SPS can produce a high densiﬁcation in a short time at a low temperature, but didn't give a high TRS because of the short time for alloying. For microwave sintering, the sample had sintered at 1200 C for 1 h, so alloying was mostly completed before microwave sintering. With the lowest porosity in these processes, the TRS of the sample sintered by microwave sintering reaches the highest value. In addition, the cermet with the high manganese steel as matrix will be applied in as-sintered condition without heat treatment, which could simplify the production process. Molybdenum was not selected to decrease the production cost. Unfortunately, the TRS may not reach the high level value of the existing cermets at
Z. Wang et al. / Journal of Alloys and Compounds 650 (2015) 918e924
Fig. 6. SEM fractographs of the samples prepared by different sintering processes (aeg show the microstructures of the samples 1e7 in Table 2 respectively).
present. The composite in this paper are to be applied in some conditions having a low requirement to the properties with a lower cost of raw materials. Fig. 6 shows the SEM fractographs for all the sintering processes. As shown in Fig. 6, the brittle fracture of TiC particles is the dominant fracture feature for all the sintering processes. It is difﬁcult to see the ductile fracture of matrix. Both transcrystalline and intercrystalline fracture have been observed for TiC particle fracture with more transcrystalline fracture than intercrystalline fracture, indicating that there is good bonding between metal matrix and carbide particles. As mentioned before, the porosity is the most critical factor affecting the TRS of the composite. Besides porosity, the matrix strength, the TiC particle size, as well as the TiC particle spatial
distribution can have an important effect on the TRS. Certain sintering process, pre-sintering and microwave sintering in this study, can optimize these factors to have the best TRS. 3.4. Inﬂuence of sintering process on the wear of samples In order to examine the effects of the sintering process on the wear resistance of the composites, the wear test for different sintering processes were carried out by using a pin-on-disk wear testing machine with 60 mesh silicon carbide as the wear particles. The results are listed in Table 2, where ε is the weight loss on per square millimeter in 1 s. The lower the ε value, the higher the wear resistance of the sample. The sample sintered by microwave sintering has the best wear resistance. For this sample also has the
Z. Wang et al. / Journal of Alloys and Compounds 650 (2015) 918e924
highest hardness and TRS, the TiC-high manganese steel cermet prepared by pre-vacuum-sintering and microwave sintering (No.6 process) has the best comprehensive properties in this study. The wear resistance can have a higher value for vacuum sintering and hot pressing at 1400 C and SPS. The result also showed that the wear resistance can be related with the hardness and TRS. The high hardness and TRS can bring out the good wear resistance. Although the wear resistance for vacuum sintering at 1420 C is lower than that for hot pressing at 1400 C, microwave sintering and SPS, the vacuum sintering can be used to produce this composite with the lowest cost in the mass production . However, The hot pressing and SPS can get good comprehensive mechanical properties in a shorter time and at a lower sintering temperature, and also the microwave sintering with a lower pre-alloying sintering temperature .
In this study, the mechanical properties and wear resistance of TiC-50 wt.% high manganese steel cermet were investigated for several sintering processes, including vacuum sintering, hot pressing, microwave sintering and SPS. The coreeshell structure was not clearly observed for the TiC particles in microstructures and the high manganese steel matrix is BCC structure. Hot pressing, microwave sintering and SPS are useful processes for densiﬁcation of the cermet. Nearly full density and higher hardness can be reached by these three processes at a lower sintering temperature and in a shorter sintering time. However, higher TRS can be reached by means of sintering process with a longer sintering time, for example vacuum sintering. Pre-sintering in a long sintering time at a lower sintering temperature is also useful for improving the TRS. Finally, vacuum sintering is an effective process for producing this composite with the lowest cost in the mass production. The hot pressing and SPS can get good comprehensive mechanical properties in a shorter time and at a lower sintering temperature and also the microwave sintering with a lower pre-alloying sintering temperature.
  
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