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Properties of nanostructured TiC and TiC–TiAl3 hard materials rapidly sintered by the pulsed current activated heating
Int. Journal of Refractory Metals and Hard Materials 48 (2015) 187–193
Contents lists available at ScienceDirect
Int. Journal of Refractory Metals and Hard Materials journal homepage: www.elsevier.com/locate/IJRMHM
Short communication
Properties of nanostructured TiC and TiC–TiAl3 hard materials rapidly sintered by the pulsed current activated heating In-Jin Shon a,⁎, Hyoung-Gon Jo a, Hanjung Kwon b a b
Division of Advanced Materials Engineering, Research Center of Advanced Materials Development, Engineering College, Chonbuk National University, Republic of Korea Minerals and Materials Processing Division, Korea Institute of Geoscience, Mining and Materials Resources, Daejeon, Republic of Korea
a r t i c l e
i n f o
Article history: Received 1 May 2014 Received in revised form 25 August 2014 Accepted 5 September 2014 Available online 16 September 2014 Keywords: Nanomaterials Sintering Hardness Fracture toughness Hard materials
a b s t r a c t In the case of cemented TiC, Ni or Co is added as a binder for the formation of composite structures. However, the high cost of Ni or Co and the low corrosion resistance of the TiC–Ni and TiC–Co cermets have generated interest in recent years for alternative binder phases. In this study, TiAl3 was used as a novel binder and consolidated by the pulsed current activated sintering (PCAS) method. Highly dense TiC–TiAl3 with a relative density of up to 100% was obtained within 2 min by PCAS under a pressure of 80 MPa. The method was found to enable not only the rapid densification but also the inhibition of grain growth preserving the nano-scale microstructure. The average grain sizes of the sintered TiC and TiC–TiAl3 were lower than 100 nm. The addition of TiAl3 to TiC enhanced the toughness without great decrease of hardness due to crack deflection and increase of relative density. © 2014 Elsevier Ltd. All rights reserved.
1. Introduction The attractive properties of titanium carbide are high hardness, low density, relatively high thermal and electrical conductivities. TiC is also very stable, with a melting temperature of 2727 K, and does not undergo phase transformations. These properties have been used extensively in cutting tool and abrasive materials in composite with a binder metal, such as Ni or Co. The binder phase has inferior chemical characteristics compared to the carbide phase. Most notably, corrosion and oxidation occur preferentially in the binder phase [1]. Hence, the high cost of Ni or Co and the low corrosion resistance of the TiC–Ni or TiC–Co cermet have generated interest in recent years to find alternative binder phases [2,3]. It has been reported that aluminides show a higher oxidation resistance, a higher hardness and a cheaper materials compared to Ni or Co [4]. The improvement of mechanical properties and stability of cemented carbides could be achieved through microstructural changes such as grain size refinement [5,6]. Nanocrystalline materials have received much attention as advanced engineering materials with improved physical and mechanical properties [7,8]. Since they possess a high strength and hardness as well as excellent ductility and toughness, they have garnered more attention recently [9,10]. However, the use of conventional methods to consolidate nanopowders often leads to grain growth due to the extended time for sintering. Generally, the grain growth could be minimized by sintering at lower temperatures and for shorter times. In this regard, the pulsed current activated sintering (PCAS) technique has been ⁎ Corresponding author. E-mail address: [email protected] (I.-J. Shon).
http://dx.doi.org/10.1016/j.ijrmhm.2014.09.011 0263-4368/© 2014 Elsevier Ltd. All rights reserved.
shown to be effective in the sintering of nanostructured materials in a very short time (typically within 1 min) [11–14]. We present here the results of the sintering of TiC and TiC–TiAl3 composites by a pulsed current activated sintering with simultaneous application of pulsed current and high-pressure. The goal of this study was to produce dense and nanocrystalline TiC and TiCN–TiAl3 hard materials in very short sintering times (b 2 min). The effect of novel TiAl3 binder on the mechanical properties and relative density of TiC–TiAl3 composites was also examined. 2. Experimental procedures The TiC powder used in this research was supplied by Treibacher Industry AG (Germany). The average particle size was about 1.4 μm and the purity was 99%. TiAl3 (b45 μm, 99% pure, Sejong Co.) was used as binder material. Powders of three compositions corresponding to TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 were prepared by weighting and milled in a high-energy ball mill (Pulverisette-5 Planetary Mill) at 250 rpm for 10 h. WC balls (9 mm in diameter) were used in a sealed cylindrical stainless steel vial under an argon atmosphere. The weight ratio of balls-to-powder was 30:1. The grain size of the powders was calculated from the full width at half-maximum (FWHM) of the diffraction peak by Suryanarayana and Grant Norton's formula [15].
Br Bcrystalline þ Bstrain cos θ ¼ kλ=L þ η sinθ
ð1Þ
188
I.-J. Shon et al. / Int. Journal of Refractory Metals and Hard Materials 48 (2015) 187–193
where Br is the full width at half-maximum (FWHM) of the diffraction peak after instrumental correction; Bcrystalline and Bstrain are the FWHM caused by small grain size and internal stress, respectively; k is the constant (with a value of 0.9); λ is the wavelength of the X-ray radiation; L and η are the grain size and internal strain, respectively; and θ is the Bragg angle. The parameters B and Br follow Cauchy's form with the relationship: B = Br + Bs, where B and Bs are the FWHM of the broadened Bragg peaks and the standard sample's Bragg peaks, respectively. The milled powders were placed in a graphite die (outside diameter, 35 mm; inside diameter, 10 mm; height, 40 mm) and then introduced into the pulsed current activated sintering (PCAS) system made by Eltek Co. in the Republic of Korea. A schematic diagram of this system is shown in Fig. 1. The PCAS apparatus includes a 30 kW power supply and a uniaxial press with a maximum load of 50 kN. The system was first evacuated and a uniaxial pressure of 80 MPa was applied. A pulsed current (on time; 20 μs, off time; 10 μs) was then activated and maintained until the densification rate became negligible, as indicated by the observed shrinkage of the sample. Sample shrinkage was measured in real time by a linear gauge measuring the vertical displacement. Temperature was measured by a pyrometer focused on the surface of the graphite die. A temperature gradient from the surface to the center of the sample is dependent on the heating rate, the electrical and thermal conductivities of the compact, and its relative density. The heating rates were approximately 1200°K min−1 during the process. At the end of the process, the current was turned off and the sample was allowed to cool to room temperature. The entire process of densification using the PCAS technique consists of four major control stages: chamber evacuation, pressure application, power application, and cooling off. The process was carried out under a vacuum of 5.33 Pa. The relative densities of the sintered samples were measured by the Archimedes method. Microstructural information was obtained from the product samples, which had been polished and etched, using Murakami's reagent (10 g potassium ferricyanide, 10 g sodium hydroxide, and 100 ml water), for 1–2 min at room temperature. Compositional and microstructural analyses of the samples were carried out through X-ray diffraction (XRD), and field-emission scanning electron microscopy (FE-SEM). Vickers hardness was measured by performing indentations at a load of 30 kgf with a dwell time of 15 s.
Fig. 1. Schematic diagram of apparatus for pulsed current activated sintering.
3. Results and discussion FE-SEM images of TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 powders milled for 10 h are shown in Fig. 2. The powders are very fine and have a round shape. Fig. 3 shows X-ray diffraction pattern of the TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 powders after milling for 10 h. The broadening of TiC peaks due to crystallite refinement and strain is evident after milling for 10 h. The milling process is known to introduce impurities from the ball and/or container. However, in this study, peaks
Fig. 2. FE-SEM images of powders milled for 10 h; (a) TiC, (b) TiC–5 vol.%TiAl3, and (c) TiC–10 vol.%TiAl3.
I.-J. Shon et al. / Int. Journal of Refractory Metals and Hard Materials 48 (2015) 187–193
Fig. 3. XRD patterns of (a) TiC (b) TiC–5 vol.%TiAl3, (c) TiC–10 vol.%TiAl3 powders milled for 10 h.
other than TiC were not identified. Fig. 4 shows plot of Br (Bcrystalline + Bstrain) cosθ versus sinθ in Suryanarayana and Grant Norton's formula [15] to calculate particle size. The average grain sizes of the TiC in the TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 powders after milling for 10 h. calculated from the XRD data were about, 46, 39 and 33 nm, respectively. The shrinkage displacement–time (temperature) curve provides an important information on the consolidation behavior. Fig. 5 shows the shrinkage record of TiC, TiC–5 vol.%TiAl3, and TiC–
189
Fig. 4. Plot of Br (Bcrystalline + Bstrain) cosθ versus sinθ for TiC in (a) TiC (b) TiC–5 vol.%TiAl3, (c) TiC–10 vol.%TiAl3 powders milled for 10 h.
10 vol.%TiAl3 compacts under the applied pressure of 80 MPa. In all cases, the displacement abruptly increased with temperature and gradually increased up to the range of 800 and 1200 °C according to TiAl3 content and then rapidly increased above the temperatures. The application of the pulsed current resulted in shrinkage due to consolidation. The temperature of rapid shrinkage initiation was seen to reduce by the addition of TiAl3. It is considered that it is related to the melting of TiAl3 phase due to large Joule heat at contact of powders. Therefore, the main
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Fig. 5. Variations of temperature and shrinkage displacement with heating time during the sintering of TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 hard materials by PCAS.
densification mechanism could be the rearrangement of carbide particles, enhancement of the diffusion, and viscous flow of the binder [16]. Fig. 6 shows the XRD patterns of TiC, TiC–5 vol.%TiAl3, and TiC– 10 vol.%TiAl3 after sintering. In all cases, only TiC and TiAl3 peaks are detected. The average grain sizes of the TiC calculated from the XRD data using Suryanarayana and Grant Norton's formula are about 90, 98, and 105 nm for the samples with TiC, TiC–5 vol.%TiAl3, and TiC– 10 vol.%TiAl3. FE-SEM images of the samples after being sintered up to about 1340 °C are shown in Fig. 7. It is apparent that the TiC grains consist of nanocrystallites suggesting the absence of grain growth during sintering. This retention of the fine grain structure can be attributed to the high heating rate and the relatively short exposure to the high temperature. In comparison of microstructure of TiC and TiC-TiAl3, TiC is uniformly distributed in TiC-TiAl3. This is believed that TiC may easily rearrange in melted TiAl3 during the sintering. EDS of TiC and TiC– 10 vol.%TiAl3 was shown in Fig. 8. In EDS, Ti, C and Pt peaks in sintered TiC and Ti, C, Al and Pt in sintered TiC–10 vol.%TiAl3 were detected. Pt comes from surface coating that enables clear observation of the microstructure. And there are no other peaks, such as Fe or W, which can possibly happen during the milling process. Relative densities corresponding to TiC, TiC– vol.%TiAl3, and TiC– 10 vol.%TiAl3.were approximately 95, 99, and 100%, respectively. The role of the current in sintering and/or synthesis has been the focus of several attempts to provide an explanation for the observed sintering enhancement and the improved characteristics of the products. The role played by the current has been variously interpreted. The effect has been explained by fast heating due to Joule heating at contacts points, the presence of plasma in pores separating powder particles, and the intrinsic contribution of the current to mass transport [17–21].
Fig. 6. XRD patterns of (a) TiC (b) TiC–5 vol.%TiAl3, (c) TiC–10 vol.%TiAl3 hard materials produced by PCAS.
Vickers hardness measurements were performed on polished sections of the TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 samples using a 30 kg load and 15 s dwell time. Indentions with 30 kgf load produced median cracks around the indentation from which fracture toughness can be calculated. The lengths of these cracks permit estimation of the fracture toughness of the materials by means of the expression [22]: −3=2
KIC ¼ 0:203ðc=aÞ
1=2
Hv a
ð2Þ
I.-J. Shon et al. / Int. Journal of Refractory Metals and Hard Materials 48 (2015) 187–193
191
Fig. 8. EDS of (a) TiC, and (b) TiC–10 vol.%TiAl3 hard materials produced by PCAS.
without great decrease of hardness because the relative density of TiC increases with addition of TiAl3. The sintering method in this study was proven to be very effective to consolidate TiC–TiAl3 cermets. A comparison of the hardness and fracture toughness values obtained in this study with those reported by others is provided in Table 1 [23]. In one of the reported studies [23], WC–10Co and WC–10Ni were consolidated at 1250 °C by high-frequency induction heated sintering. Referring to Table 1, it is seen that the addition of TiAl3 to TiC significantly improves the fracture toughness of cemented TiC without greatly decreasing the hardness. Also comparing this investigation of TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 with a study of WC–10Co and WC–10Ni [23], there is a little difference in fracture toughness but hardness in this study is higher than that in the other study [23]. The use of TiAl3 binder instead of Co or Ni is very effective especially to maintain the high hardness of monolithic TiC without the expense of toughness reduction. In this regard, it would be worthwhile to consider TiAl3 as the possible replacement for Co or Ni especially for the applications requiring a high hardness. Vickers hardness indentations in the TiC, TiC–5 vol.%TiAl3, and TiC– 10 vol.%TiAl3 samples are shown in Fig. 9. They show typically one to three additional cracks propagating radially from the indentation. Fig. 10 shows a crack propagated in a deflective manner (↑) in TiC– Fig. 7. FEM images of (a) TiC, (b) TiC–5 vol.%TiAl3, and (c) TiC–10 vol.%TiAl3 hard materials produced by PCAS.
where c is the trace length of the crack measured from the center of the indentation, a is one half of the average length of the two indent diagonals, and Hv is the hardness. The Vickers hardness and the fracture toughness values of the TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 samples were 2518 kg/mm2, 6.3 MPa·m1/2, and 2465 kg/mm2, 8.2 MPa·m1/2 and 2315 kg/mm2, and 9.5 MPa·m1/2, respectively. These values represent the average of five measurements. The fracture toughness of TiC–5 vol.%TiAl3, and TiCN–10 vol.%TiAl3 samples are higher than that of monolithic TiC
Table 1 Comparison of mechanical properties of TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 in this study with the previously reported values. Ref.
Binder content (vol%)
Relative density (%)
Grain size (nm)
Hv (kg/mm2)
KIc (MPa∗m1/2)
[23] [23] [23] This study
10Co 10Ni 10Fe 0 5FeAl 10FeAl
98 98 99.9 98 99 100
61 44 80 98 63 120
1780 1822 1905 2518 2465 2315
8.3 8.6 8.5 6.3 8.2 9.5
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Fig. 10. Crack propagation in TiC–10 vol.%TiAl3 hard materials produced by PCAS.
successfully. Nearly full-dense nanostructured TiC–TiAl3 composites could be obtained within 2 min. The starting temperature of rapid densification and porosity of TiC were reduced remarkably by the addition of TiAl3. The average grain sizes of the TiC are about 90, 98, and 105 nm for the samples with TiC, TiC–5 vol.%TiAl 3 , and TiC–10 vol.%TiAl 3. The Vickers hardness and the fracture toughness values of the TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 samples were 2518 kg/mm2, 6.3 MPa·m1/2, and 2465 kg/mm2, 8.2 MPa·m1/2 and 2315 kg/mm2, 9.5 MPa·m1/2, respectively. The addition of TiAl3 to TiC improved the fracture toughness of cemented TiC without great reduction of hardness. It would be worthwhile to consider TiAl3 as the possible replacement for Co or Ni especially for the applications requiring a high hardness. Acknowledgments This study was supported by a grant from basic research project of the Korea Institute of Geoscience and Mineral Resources and are the results of a study on the “Leaders Industry-University Cooperation” Project, supported by the Ministry of Education, Science & Technology (MEST). References
Fig. 9. Vickers hardness indeatation in (a) TiC (b) TiC–5 vol.%TiAl3 (c) TiC–10 vol.%TiAl3 hard materials produced by PCAS.
10 vol.%TiAl3 composite. The enhanced fracture toughness of TiC– 10 vol.%TiAl3 composite is believed that TiC and TiAl3 in the composite may deter the propagation of cracks and TiC and TiAl3 have nanostructure phases. 4. Conclusions Using pulsed current activated sintering (PCAS), the rapid consolidation of the TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 was accomplished
[1] Imasato S, Tokumoto K, Kitada T, Sakaguchi S. Properties of ultra-fine grain binderless cemented carbide RCCFN. Int J Refract Met Hard Mater 1995;13:305–12. [2] Gille G, Bredthauer J, Gries B, Mende B. Advanced and new prades of WC and binder power—their properties and application. Int J Refract Met Hard Mater 2000;18(2–3): 87–102. [3] Lin Hua, Tao Bowan, Xiong Jie, Li Qing. Using a cobalt activator to synthesize titanium carbide (TiC) nanopowders. Int J Refract Met Hard Mater 2013;41:363–5. [4] Zhang ZG, Gesmundo F, Hou PY, Niu Y. Criteria for the formation of protective Al2O3 scales on Fe–Al and Fe–Cr–Al alloys. Corros Sci 2006;48:741–65. [5] Gleiter H. Nanocrystalline materials. Prog Mater Sci 1989;33(4):223–315. [6] Fougere GE, Weertman JR, Siegel RW, Kim S. Grain-size dependent hardening and softening of nanocrystalline Cu and Pd. Scr Metall Mater 1992;26(2):1879–83. [7] Sherif El-Eskandarany M. Structure and properties of nanocrystalline TiC full-density bulk alloy consolidated from mechanically reacted powders. J Alloys Compd 2000; 305:225–38. [8] Fu L, Cao LH, Fan YS. Two-step synthesis of nanostructured tungsten carbide–cobalt powders. Scr Mater 2001;44:1061–8. [9] Ni S, Wang YB, Liao XZ, Alhajeri SN, Li HQ, Zhao YH, Lavernia EJ, Ringer SP, Langdon TG, Zhu YT. Advanced structural inorganic composite. Mater Sci Eng A 2011;528: 3398–403. [10] Berger S, Porat R, Rosen R. Nanocrystalline materials: a study of WC-based hard metals. Prog Mater Sci 1997;42:311–20. [11] Kim Wonbaek, Lim Jae-Won, Oh Hyun-Su, Shon In-Jin. Mechanical properties of nanostructured TiN–AlN composites rapidly consolidated by pulsed current activated sintering. Ceram Int 2014;40:2511–7. [12] Lee Geon-Woo, Shon In-Jin. The effect of high-energy ball milling on sintering and the mechanical properties of Al2O3. Korean J Met Mater 2013;51(2):095–100. [13] Kwak Seung-Mi, Park Hyun-Kuk, Shon In-Jin. Mechanical properties and fabrication of nanostructured ZrO2 from ball milled powders by pulsed current activated sintering. Korean J Met Mater 2013;51(5):341–8.
I.-J. Shon et al. / Int. Journal of Refractory Metals and Hard Materials 48 (2015) 187–193 [14] Shon In-Jin, Na Kwon-Il, Doh Jung-Mann, Park Hyun-Kuk, Yoon Jin-Kook. Simultaneous synthesis and consolidation of nanocrystalline Fe2Al5 and Fe2Al5–Al2O3 by pulsed current activated sintering and their mechanical properties. Met Mater Int 2013;19(1):99–103. [15] Suryanarayana C, Grant Norton M. X-ray Diffraction: A Practical Approach. New York: Plenum Press; 1998. [16] Upadhyaya GS. Materials science of cemented carbides—an overview. Mater Des 2001;22(6):483–9. [17] Shen Z, Johnsson M, Zhao Z, Nygren M. Spark plasma sintering of alumina. J Am Ceram Soc 2002;85:1921–7. [18] Garay JE, Anselmi-Tamburini U, Munir ZA, Glade SC, Asoka- Kumar P. Electric current enhanced defect mobility in Ni3Ti intermetallic electric current enhanced defect mobility in Ni3Ti intermetallics. Appl Phys Lett 2004;85:573–5.
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Contents lists available at ScienceDirect
Int. Journal of Refractory Metals and Hard Materials journal homepage: www.elsevier.com/locate/IJRMHM
Short communication
Properties of nanostructured TiC and TiC–TiAl3 hard materials rapidly sintered by the pulsed current activated heating In-Jin Shon a,⁎, Hyoung-Gon Jo a, Hanjung Kwon b a b
Division of Advanced Materials Engineering, Research Center of Advanced Materials Development, Engineering College, Chonbuk National University, Republic of Korea Minerals and Materials Processing Division, Korea Institute of Geoscience, Mining and Materials Resources, Daejeon, Republic of Korea
a r t i c l e
i n f o
Article history: Received 1 May 2014 Received in revised form 25 August 2014 Accepted 5 September 2014 Available online 16 September 2014 Keywords: Nanomaterials Sintering Hardness Fracture toughness Hard materials
a b s t r a c t In the case of cemented TiC, Ni or Co is added as a binder for the formation of composite structures. However, the high cost of Ni or Co and the low corrosion resistance of the TiC–Ni and TiC–Co cermets have generated interest in recent years for alternative binder phases. In this study, TiAl3 was used as a novel binder and consolidated by the pulsed current activated sintering (PCAS) method. Highly dense TiC–TiAl3 with a relative density of up to 100% was obtained within 2 min by PCAS under a pressure of 80 MPa. The method was found to enable not only the rapid densification but also the inhibition of grain growth preserving the nano-scale microstructure. The average grain sizes of the sintered TiC and TiC–TiAl3 were lower than 100 nm. The addition of TiAl3 to TiC enhanced the toughness without great decrease of hardness due to crack deflection and increase of relative density. © 2014 Elsevier Ltd. All rights reserved.
1. Introduction The attractive properties of titanium carbide are high hardness, low density, relatively high thermal and electrical conductivities. TiC is also very stable, with a melting temperature of 2727 K, and does not undergo phase transformations. These properties have been used extensively in cutting tool and abrasive materials in composite with a binder metal, such as Ni or Co. The binder phase has inferior chemical characteristics compared to the carbide phase. Most notably, corrosion and oxidation occur preferentially in the binder phase [1]. Hence, the high cost of Ni or Co and the low corrosion resistance of the TiC–Ni or TiC–Co cermet have generated interest in recent years to find alternative binder phases [2,3]. It has been reported that aluminides show a higher oxidation resistance, a higher hardness and a cheaper materials compared to Ni or Co [4]. The improvement of mechanical properties and stability of cemented carbides could be achieved through microstructural changes such as grain size refinement [5,6]. Nanocrystalline materials have received much attention as advanced engineering materials with improved physical and mechanical properties [7,8]. Since they possess a high strength and hardness as well as excellent ductility and toughness, they have garnered more attention recently [9,10]. However, the use of conventional methods to consolidate nanopowders often leads to grain growth due to the extended time for sintering. Generally, the grain growth could be minimized by sintering at lower temperatures and for shorter times. In this regard, the pulsed current activated sintering (PCAS) technique has been ⁎ Corresponding author. E-mail address: [email protected] (I.-J. Shon).
http://dx.doi.org/10.1016/j.ijrmhm.2014.09.011 0263-4368/© 2014 Elsevier Ltd. All rights reserved.
shown to be effective in the sintering of nanostructured materials in a very short time (typically within 1 min) [11–14]. We present here the results of the sintering of TiC and TiC–TiAl3 composites by a pulsed current activated sintering with simultaneous application of pulsed current and high-pressure. The goal of this study was to produce dense and nanocrystalline TiC and TiCN–TiAl3 hard materials in very short sintering times (b 2 min). The effect of novel TiAl3 binder on the mechanical properties and relative density of TiC–TiAl3 composites was also examined. 2. Experimental procedures The TiC powder used in this research was supplied by Treibacher Industry AG (Germany). The average particle size was about 1.4 μm and the purity was 99%. TiAl3 (b45 μm, 99% pure, Sejong Co.) was used as binder material. Powders of three compositions corresponding to TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 were prepared by weighting and milled in a high-energy ball mill (Pulverisette-5 Planetary Mill) at 250 rpm for 10 h. WC balls (9 mm in diameter) were used in a sealed cylindrical stainless steel vial under an argon atmosphere. The weight ratio of balls-to-powder was 30:1. The grain size of the powders was calculated from the full width at half-maximum (FWHM) of the diffraction peak by Suryanarayana and Grant Norton's formula [15].
Br Bcrystalline þ Bstrain cos θ ¼ kλ=L þ η sinθ
ð1Þ
188
I.-J. Shon et al. / Int. Journal of Refractory Metals and Hard Materials 48 (2015) 187–193
where Br is the full width at half-maximum (FWHM) of the diffraction peak after instrumental correction; Bcrystalline and Bstrain are the FWHM caused by small grain size and internal stress, respectively; k is the constant (with a value of 0.9); λ is the wavelength of the X-ray radiation; L and η are the grain size and internal strain, respectively; and θ is the Bragg angle. The parameters B and Br follow Cauchy's form with the relationship: B = Br + Bs, where B and Bs are the FWHM of the broadened Bragg peaks and the standard sample's Bragg peaks, respectively. The milled powders were placed in a graphite die (outside diameter, 35 mm; inside diameter, 10 mm; height, 40 mm) and then introduced into the pulsed current activated sintering (PCAS) system made by Eltek Co. in the Republic of Korea. A schematic diagram of this system is shown in Fig. 1. The PCAS apparatus includes a 30 kW power supply and a uniaxial press with a maximum load of 50 kN. The system was first evacuated and a uniaxial pressure of 80 MPa was applied. A pulsed current (on time; 20 μs, off time; 10 μs) was then activated and maintained until the densification rate became negligible, as indicated by the observed shrinkage of the sample. Sample shrinkage was measured in real time by a linear gauge measuring the vertical displacement. Temperature was measured by a pyrometer focused on the surface of the graphite die. A temperature gradient from the surface to the center of the sample is dependent on the heating rate, the electrical and thermal conductivities of the compact, and its relative density. The heating rates were approximately 1200°K min−1 during the process. At the end of the process, the current was turned off and the sample was allowed to cool to room temperature. The entire process of densification using the PCAS technique consists of four major control stages: chamber evacuation, pressure application, power application, and cooling off. The process was carried out under a vacuum of 5.33 Pa. The relative densities of the sintered samples were measured by the Archimedes method. Microstructural information was obtained from the product samples, which had been polished and etched, using Murakami's reagent (10 g potassium ferricyanide, 10 g sodium hydroxide, and 100 ml water), for 1–2 min at room temperature. Compositional and microstructural analyses of the samples were carried out through X-ray diffraction (XRD), and field-emission scanning electron microscopy (FE-SEM). Vickers hardness was measured by performing indentations at a load of 30 kgf with a dwell time of 15 s.
Fig. 1. Schematic diagram of apparatus for pulsed current activated sintering.
3. Results and discussion FE-SEM images of TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 powders milled for 10 h are shown in Fig. 2. The powders are very fine and have a round shape. Fig. 3 shows X-ray diffraction pattern of the TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 powders after milling for 10 h. The broadening of TiC peaks due to crystallite refinement and strain is evident after milling for 10 h. The milling process is known to introduce impurities from the ball and/or container. However, in this study, peaks
Fig. 2. FE-SEM images of powders milled for 10 h; (a) TiC, (b) TiC–5 vol.%TiAl3, and (c) TiC–10 vol.%TiAl3.
I.-J. Shon et al. / Int. Journal of Refractory Metals and Hard Materials 48 (2015) 187–193
Fig. 3. XRD patterns of (a) TiC (b) TiC–5 vol.%TiAl3, (c) TiC–10 vol.%TiAl3 powders milled for 10 h.
other than TiC were not identified. Fig. 4 shows plot of Br (Bcrystalline + Bstrain) cosθ versus sinθ in Suryanarayana and Grant Norton's formula [15] to calculate particle size. The average grain sizes of the TiC in the TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 powders after milling for 10 h. calculated from the XRD data were about, 46, 39 and 33 nm, respectively. The shrinkage displacement–time (temperature) curve provides an important information on the consolidation behavior. Fig. 5 shows the shrinkage record of TiC, TiC–5 vol.%TiAl3, and TiC–
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Fig. 4. Plot of Br (Bcrystalline + Bstrain) cosθ versus sinθ for TiC in (a) TiC (b) TiC–5 vol.%TiAl3, (c) TiC–10 vol.%TiAl3 powders milled for 10 h.
10 vol.%TiAl3 compacts under the applied pressure of 80 MPa. In all cases, the displacement abruptly increased with temperature and gradually increased up to the range of 800 and 1200 °C according to TiAl3 content and then rapidly increased above the temperatures. The application of the pulsed current resulted in shrinkage due to consolidation. The temperature of rapid shrinkage initiation was seen to reduce by the addition of TiAl3. It is considered that it is related to the melting of TiAl3 phase due to large Joule heat at contact of powders. Therefore, the main
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Fig. 5. Variations of temperature and shrinkage displacement with heating time during the sintering of TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 hard materials by PCAS.
densification mechanism could be the rearrangement of carbide particles, enhancement of the diffusion, and viscous flow of the binder [16]. Fig. 6 shows the XRD patterns of TiC, TiC–5 vol.%TiAl3, and TiC– 10 vol.%TiAl3 after sintering. In all cases, only TiC and TiAl3 peaks are detected. The average grain sizes of the TiC calculated from the XRD data using Suryanarayana and Grant Norton's formula are about 90, 98, and 105 nm for the samples with TiC, TiC–5 vol.%TiAl3, and TiC– 10 vol.%TiAl3. FE-SEM images of the samples after being sintered up to about 1340 °C are shown in Fig. 7. It is apparent that the TiC grains consist of nanocrystallites suggesting the absence of grain growth during sintering. This retention of the fine grain structure can be attributed to the high heating rate and the relatively short exposure to the high temperature. In comparison of microstructure of TiC and TiC-TiAl3, TiC is uniformly distributed in TiC-TiAl3. This is believed that TiC may easily rearrange in melted TiAl3 during the sintering. EDS of TiC and TiC– 10 vol.%TiAl3 was shown in Fig. 8. In EDS, Ti, C and Pt peaks in sintered TiC and Ti, C, Al and Pt in sintered TiC–10 vol.%TiAl3 were detected. Pt comes from surface coating that enables clear observation of the microstructure. And there are no other peaks, such as Fe or W, which can possibly happen during the milling process. Relative densities corresponding to TiC, TiC– vol.%TiAl3, and TiC– 10 vol.%TiAl3.were approximately 95, 99, and 100%, respectively. The role of the current in sintering and/or synthesis has been the focus of several attempts to provide an explanation for the observed sintering enhancement and the improved characteristics of the products. The role played by the current has been variously interpreted. The effect has been explained by fast heating due to Joule heating at contacts points, the presence of plasma in pores separating powder particles, and the intrinsic contribution of the current to mass transport [17–21].
Fig. 6. XRD patterns of (a) TiC (b) TiC–5 vol.%TiAl3, (c) TiC–10 vol.%TiAl3 hard materials produced by PCAS.
Vickers hardness measurements were performed on polished sections of the TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 samples using a 30 kg load and 15 s dwell time. Indentions with 30 kgf load produced median cracks around the indentation from which fracture toughness can be calculated. The lengths of these cracks permit estimation of the fracture toughness of the materials by means of the expression [22]: −3=2
KIC ¼ 0:203ðc=aÞ
1=2
Hv a
ð2Þ
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Fig. 8. EDS of (a) TiC, and (b) TiC–10 vol.%TiAl3 hard materials produced by PCAS.
without great decrease of hardness because the relative density of TiC increases with addition of TiAl3. The sintering method in this study was proven to be very effective to consolidate TiC–TiAl3 cermets. A comparison of the hardness and fracture toughness values obtained in this study with those reported by others is provided in Table 1 [23]. In one of the reported studies [23], WC–10Co and WC–10Ni were consolidated at 1250 °C by high-frequency induction heated sintering. Referring to Table 1, it is seen that the addition of TiAl3 to TiC significantly improves the fracture toughness of cemented TiC without greatly decreasing the hardness. Also comparing this investigation of TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 with a study of WC–10Co and WC–10Ni [23], there is a little difference in fracture toughness but hardness in this study is higher than that in the other study [23]. The use of TiAl3 binder instead of Co or Ni is very effective especially to maintain the high hardness of monolithic TiC without the expense of toughness reduction. In this regard, it would be worthwhile to consider TiAl3 as the possible replacement for Co or Ni especially for the applications requiring a high hardness. Vickers hardness indentations in the TiC, TiC–5 vol.%TiAl3, and TiC– 10 vol.%TiAl3 samples are shown in Fig. 9. They show typically one to three additional cracks propagating radially from the indentation. Fig. 10 shows a crack propagated in a deflective manner (↑) in TiC– Fig. 7. FEM images of (a) TiC, (b) TiC–5 vol.%TiAl3, and (c) TiC–10 vol.%TiAl3 hard materials produced by PCAS.
where c is the trace length of the crack measured from the center of the indentation, a is one half of the average length of the two indent diagonals, and Hv is the hardness. The Vickers hardness and the fracture toughness values of the TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 samples were 2518 kg/mm2, 6.3 MPa·m1/2, and 2465 kg/mm2, 8.2 MPa·m1/2 and 2315 kg/mm2, and 9.5 MPa·m1/2, respectively. These values represent the average of five measurements. The fracture toughness of TiC–5 vol.%TiAl3, and TiCN–10 vol.%TiAl3 samples are higher than that of monolithic TiC
Table 1 Comparison of mechanical properties of TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 in this study with the previously reported values. Ref.
Binder content (vol%)
Relative density (%)
Grain size (nm)
Hv (kg/mm2)
KIc (MPa∗m1/2)
[23] [23] [23] This study
10Co 10Ni 10Fe 0 5FeAl 10FeAl
98 98 99.9 98 99 100
61 44 80 98 63 120
1780 1822 1905 2518 2465 2315
8.3 8.6 8.5 6.3 8.2 9.5
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Fig. 10. Crack propagation in TiC–10 vol.%TiAl3 hard materials produced by PCAS.
successfully. Nearly full-dense nanostructured TiC–TiAl3 composites could be obtained within 2 min. The starting temperature of rapid densification and porosity of TiC were reduced remarkably by the addition of TiAl3. The average grain sizes of the TiC are about 90, 98, and 105 nm for the samples with TiC, TiC–5 vol.%TiAl 3 , and TiC–10 vol.%TiAl 3. The Vickers hardness and the fracture toughness values of the TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 samples were 2518 kg/mm2, 6.3 MPa·m1/2, and 2465 kg/mm2, 8.2 MPa·m1/2 and 2315 kg/mm2, 9.5 MPa·m1/2, respectively. The addition of TiAl3 to TiC improved the fracture toughness of cemented TiC without great reduction of hardness. It would be worthwhile to consider TiAl3 as the possible replacement for Co or Ni especially for the applications requiring a high hardness. Acknowledgments This study was supported by a grant from basic research project of the Korea Institute of Geoscience and Mineral Resources and are the results of a study on the “Leaders Industry-University Cooperation” Project, supported by the Ministry of Education, Science & Technology (MEST). References
Fig. 9. Vickers hardness indeatation in (a) TiC (b) TiC–5 vol.%TiAl3 (c) TiC–10 vol.%TiAl3 hard materials produced by PCAS.
10 vol.%TiAl3 composite. The enhanced fracture toughness of TiC– 10 vol.%TiAl3 composite is believed that TiC and TiAl3 in the composite may deter the propagation of cracks and TiC and TiAl3 have nanostructure phases. 4. Conclusions Using pulsed current activated sintering (PCAS), the rapid consolidation of the TiC, TiC–5 vol.%TiAl3, and TiC–10 vol.%TiAl3 was accomplished
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