添加Ti+Al或Ti_3Al对TiB_2-Fe金属陶瓷结构和性能的影响
摘要
金属间化合物Ti_3Al、Ni_3Al，NiAl，FeAl等，尤其是钛合金—Ti_3Al，由于具有与TiB_2陶瓷基体一致的晶格结构和相近的晶格参数，均为密排六方晶格，有望改善TiB_2陶瓷材料的高温性能。
本文通过运用扫描电子显微镜(SEM)、能谱分析和X-衍射等方法系统研究了采用气氛保护烧结的加入了金属Ti和Al或金属间化合物Ti_3Al的TiB_2-Fe系金属陶瓷的组织结构、元素的分布以及相组成，分析了它们在TiB_2-Fe系金属陶瓷中的作用及反应机理。在加入一定量的金属3Ti+Al或金属间化合物Ti_3Al的TiB_2-Fe金属陶瓷中均形成了TiB_2+TiC双硬质相结构，与TiB_2-Fe金属陶瓷比较，TiB_2晶粒略大，并形成了多种元素组成的合金粘接相。在TiB_2-Fe金属陶瓷加入3Ti+Al，没有反应合成Ti_3Al化合物，Ti_3Al与TiB_2没发现固溶现象，Ti_3Al有一部分在烧结过程中分解了。加入的金属3Ti+Al较少时，在TiB_2-Fe金属陶瓷中没有发现TiC相，更没有TiB_2+TiC双硬质相，而添加少量的金属间化合物Ti_3Al，依然有TiC相，以及TiB_2+TiC双硬质相。与TiB_2-Fe金属陶瓷比较，添加较少量3Ti+Al或Ti_3Al的TiB_2-Fe金属陶瓷中TiB_2晶粒尺寸略小，这是由于Ti溶入液相Fe中的量大大增加而导致TiB_2晶粒析出时数量多且细所造成的。TiB_2-Fe-Ti_3Al系金属陶瓷在1550℃烧结生成了TiAl_3相。制备了加入较少量的金属3Ti+Al，或金属间化合物Ti_3Al的TiB_2-Fe基金属陶瓷，以及TiB_2-Fe金属陶瓷，比较了他们的力学性能。
添加少量的Ti_3Al或(3Ti+Al)的TiB_2-Fe系金属陶瓷有较好的强度-硬度性能组合，有潜在的应用前景。
Intermetallic compouds. such as Ti3Al, Ni3Al, NiAl, FeAl, especially Ti3Al, which are of same crystalline structure and proximate lattice parameters, are expected to improve properties at elevated temperature of TiB2 ceramic.
By means of SEM, EDXA and XRD, the sturcture, components and phases of the TiB2-Fe, TiB2-Fe-(3Ti+Al), and TiB2-Fe-Ti3Al cermet sintered in protective atomosphere were studied. The effects of adding 3Ti+AI or Ti3Al on the structure and properties of TiB2-Fe cermet were also dealed with. If the amount of additives being enough, whether no matter w hether in the form of 3Ti+AI or Ti3Al added, two hard phases structure of TiB2+TiC are formed in these cermets. The size of TiB2 crystallines in TiB2-Fe-(3Ti+Al) and TiB2-Fe-Ti3Al cermets are little larger than that in TiB2-Fe cermet No Ti3Al compoud is formed in TiB2-Fe- (3Ti+Al) cermet TiB2 and Ti3Al are not combined together in TiB2-Fe-Ti3Al cermet, and some Ti3Al is decompoed during sintering process. The binders in the above cermets are alloys composed of several elements. During the process, the TijAl compound in TiB2-Fe-Ti3Al mixture are decomposed and formed TiAl3 compound. If the amount of additives is not enough, no TiC, even less two hard phases structure of TiB2+TiC is found in TiB2-Fe-(3Ti+Al) cermet, but TiC and two hard phases structure of TiB2+TiC are still formed in TiB2-Fe-Ti3Al cermetthe size of TiB2 crystallines in TiB2-Fe-(3Ti+Al) and TiB2-Fe-Ti3Al cermet are little smaller than that in TiB2-Fe since that a large amount of Ti disolving into Fe liquid cause precipitating a large
amount of fine TiB2 crystallines. Some TiB2-Fe, TiB2-Fe-(3Ti+Al) and TiB2-Fe-Ti3Al cermets were manufactured, and the physical and mechanical properties were compared.
TiB2-Fe cermet added alittle amount of Ti3Al or Ti and Al with nice combination of strenth and hardness, is of potential applications in future.
本文通过运用扫描电子显微镜(SEM)、能谱分析和X-衍射等方法系统研究了采用气氛保护烧结的加入了金属Ti和Al或金属间化合物Ti_3Al的TiB_2-Fe系金属陶瓷的组织结构、元素的分布以及相组成，分析了它们在TiB_2-Fe系金属陶瓷中的作用及反应机理。在加入一定量的金属3Ti+Al或金属间化合物Ti_3Al的TiB_2-Fe金属陶瓷中均形成了TiB_2+TiC双硬质相结构，与TiB_2-Fe金属陶瓷比较，TiB_2晶粒略大，并形成了多种元素组成的合金粘接相。在TiB_2-Fe金属陶瓷加入3Ti+Al，没有反应合成Ti_3Al化合物，Ti_3Al与TiB_2没发现固溶现象，Ti_3Al有一部分在烧结过程中分解了。加入的金属3Ti+Al较少时，在TiB_2-Fe金属陶瓷中没有发现TiC相，更没有TiB_2+TiC双硬质相，而添加少量的金属间化合物Ti_3Al，依然有TiC相，以及TiB_2+TiC双硬质相。与TiB_2-Fe金属陶瓷比较，添加较少量3Ti+Al或Ti_3Al的TiB_2-Fe金属陶瓷中TiB_2晶粒尺寸略小，这是由于Ti溶入液相Fe中的量大大增加而导致TiB_2晶粒析出时数量多且细所造成的。TiB_2-Fe-Ti_3Al系金属陶瓷在1550℃烧结生成了TiAl_3相。制备了加入较少量的金属3Ti+Al，或金属间化合物Ti_3Al的TiB_2-Fe基金属陶瓷，以及TiB_2-Fe金属陶瓷，比较了他们的力学性能。
添加少量的Ti_3Al或(3Ti+Al)的TiB_2-Fe系金属陶瓷有较好的强度-硬度性能组合，有潜在的应用前景。
Intermetallic compouds. such as Ti3Al, Ni3Al, NiAl, FeAl, especially Ti3Al, which are of same crystalline structure and proximate lattice parameters, are expected to improve properties at elevated temperature of TiB2 ceramic.
By means of SEM, EDXA and XRD, the sturcture, components and phases of the TiB2-Fe, TiB2-Fe-(3Ti+Al), and TiB2-Fe-Ti3Al cermet sintered in protective atomosphere were studied. The effects of adding 3Ti+AI or Ti3Al on the structure and properties of TiB2-Fe cermet were also dealed with. If the amount of additives being enough, whether no matter w hether in the form of 3Ti+AI or Ti3Al added, two hard phases structure of TiB2+TiC are formed in these cermets. The size of TiB2 crystallines in TiB2-Fe-(3Ti+Al) and TiB2-Fe-Ti3Al cermets are little larger than that in TiB2-Fe cermet No Ti3Al compoud is formed in TiB2-Fe- (3Ti+Al) cermet TiB2 and Ti3Al are not combined together in TiB2-Fe-Ti3Al cermet, and some Ti3Al is decompoed during sintering process. The binders in the above cermets are alloys composed of several elements. During the process, the TijAl compound in TiB2-Fe-Ti3Al mixture are decomposed and formed TiAl3 compound. If the amount of additives is not enough, no TiC, even less two hard phases structure of TiB2+TiC is found in TiB2-Fe-(3Ti+Al) cermet, but TiC and two hard phases structure of TiB2+TiC are still formed in TiB2-Fe-Ti3Al cermetthe size of TiB2 crystallines in TiB2-Fe-(3Ti+Al) and TiB2-Fe-Ti3Al cermet are little smaller than that in TiB2-Fe since that a large amount of Ti disolving into Fe liquid cause precipitating a large
amount of fine TiB2 crystallines. Some TiB2-Fe, TiB2-Fe-(3Ti+Al) and TiB2-Fe-Ti3Al cermets were manufactured, and the physical and mechanical properties were compared.
TiB2-Fe cermet added alittle amount of Ti3Al or Ti and Al with nice combination of strenth and hardness, is of potential applications in future.
引文
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2.李良福，硬质合金 1999, Vol. 16 No.2: 65-70.
3.L.G.Boxall, A.V.Cooke,H.W.Hayden, TiB_2 Cathod Material:Application in Conventional VSS Cell, Journal of Metals, November 1984,35-37.
4.E.S.KANG, C.H.Kim, Improvements in mechanical properties of TiB_2 by the dispersion of B_4C particles, Journal of Materials Science 1990,25,580-584.
5.L.S.Sigl, K.A.Schwetz, U.Dworak, Continuous Turning with TiB_2 Cermet:Preliminary Cutting Test,Int.J.of Refractory Metals & Hard Materials 12(1993-1994) 95-99.
6.宫本钦生，Y.C.Hyun,山田 修等，粉体和粉末冶金，1988, Vol 35, No. 7,651-654。
7、松下纯一，长岛秀夫，齐藤 肇，粉体和粉末冶金，(1990)Vol 37, No.7,1017-1020。
8.T.J.Davis,A.A.Ogwu, Characterisation of composite of TiC+TiB_2 bonded with nickel based binder alloy: mechanical and microstructural properties,Powder Metallurgy, 1995,Vol, 38 No.1,39-44.
9.T. Watanabe, H. Yamamoto, K. Shobu, Factors affecting the Porosity and Bending Strength of Ti (CN)-TiB_2 Materials, J.AM.Ceram. Soc., 1988, 71[4] C-202-C-204.
10.S.K.Lee, D.H.Kim, C.H.Kim, Fabrication of TiB_2/TiC composites by the directional reaction of Titanium with Boron Carbide,Journal of Materials Science 1994,29,4125-4130.
11．张国军，反应热压法制备 TiB_2-Ti(C，N)复相陶瓷研究，硅酸盐学报，1993，Vol21，NO．2，182-187。
12.M.Moriyama, H.Aoki, Fabrication and Mechanical Properties ofTiB_2-TiNxCy Composites by Reaction Sintering of B_4C and TiN Powders,Journal of the Ceramic Society of Japan, 1996,104[4],333-339.
13.R.Tomoshige, A.Murayama, Production of TiB_2-TiN Composites by Combustion Synthesis and their Properties, J.Am. Ceram. Soc., 1997, 80[3], 761-64.
14.M.Ouabdesselam, Z.Amunr, The sintering of Combustion synthesized Titanium Diboride,Journal of Materials Science 1987,22,1799-1807.
15.L.J.Kecskes, A.niiler, T. Kottke, Precursor Morphology Effects in Combustion-synthesized and Dynamically Consolidated Titanium Carbide and Titanium Boride, J.Am.Ceram. Soc., 1993, 76[12], 2961-70.
16.L.Wang, M.R. Wixom, Structural and mechanical properties of TiB_2 and TiC prepared by self-propergating high-temperature sythesis/dynamic, Journal of Materials Science 1994,29,534-543.
17.H.Taimatsu, T. Atsumi, T. Okaniwa, Synthesis of TiB_2-TiC Composites by the Solid-state Reaction between B_4C and Ti Powder, Journal of the Ceramic Society of Japan 1999,107[11], 1041-1045.
18.C.C.O 1987, No.5,32-34.
19.S.Torizuki, K.Sato, H.Nishio, Effect of SiC On Interfacial Reaction and Sintering Mechanism of TiB_2, J.Am. Ceram. Soc., 1995, 78 [6], 1606-10.
20.D.A.Hoke, D.K.Kim, J.C.LaSalvia, Combustion Synthesis/Dynamic Densification ofa TiB_2-SiC Composite, J.Am. Ceram. Soc., 1996, 79 [1] 177-82.
21．日本专利，特开平5-139834，岛冢史郎等，1993。
22、三上哲郎，日本专利，平4-14496834．1992．5．19。
23. T. Watanabe, K. Shoubu, Mechanical Properties of Hot Pressed TiB_2-ZrO_2 Composites, J.Am. Ceram. Soc., 1985, 68[2], C-34-C36.
24. Y. Muraoka, M.Yoshinaka, K.Hirota, Hot Isostatic Pressing of(2mol%Y2O3) Composite Powders, Material Reasearch Bulletin, 1996,Vol31, No.7, 787-79.
25．岛冢史郎，西尾浩明，粉体和粉末冶金1989，Vol36，No．2，100-104。
26．岛冢史郎，西尾浩明，粉体和粉末冶金，1991，Vol38，No．6，723-728。
27．松下纯一，长岛秀夫，齐藤肇，粉体和粉末冶金，1990，Vol37，No．4，551-555。
28. W.A.zdaniewski, Stereoscopic Fractography of Crack Propagation Phenomena in a TiB_2-AlN Composite, J.Am.Ceram. Soc., 1989, 72[1], 116-21.
29. Jongin Jung, Swwon, United state patent, 5,061,662, 1991.10.29.
30. E.S.Kang, C.W.Jang, C.H.Kim, Effect of Iron and Boron Carbide on the Densification and Mechanical Properties of Titanium Diboride Ceramics, J.Am. Ceram. Soc., 1989, 72[10], 1868-72.
31. J.H. Park, Y.H.Koh, HE.Kim, Densification and mechanical Properties of Titanium Diboride with Silicon Nitride as a Sintering Aid, J.Am.Ceram. Soc., 1999, 82[11], 3037-42.
32. J.H. Park, Y.H.Lee, Y.H. Koh, Effect of Hot-Pressing Temperature on Densification and Mechnical Properties of Titanium Diboride with Silicon Nitride as a Sintering Aid, J.Am. Ceram. Soc., 2000, 83[6], 1542-44.
33．山崎义照，日本公开特许公报，特开平5-306177，1993．11．19。
34、高容根．硬质合金1998，Vol．15 No．4：235-240。
35. Th.Jungling, L.S.Sigl, R. Oberacker et al., New Hardmetals Based on TiB_2, Refractory Metals Hard Meterials, 1993-1994, Vol. 12, 71-88
36. I.Smid,E.Kny, Refractory & Hard Metal, September 1988,Vol7, 135-139
37．西藤 广等。粉体与粉末冶金(日刊)，Vol．30(1989)，90-94。
38. B.Yuriditsky, TiB_2-Based Cermets,RM & HM, March 1990, 32-35.
39. J.K.Yang, A.griffo,R.M.German, Full Density Processing of Titanium Diboride Cermet,Advances in Powder Metallurgy & Particulate Materials, New Jersey, U.S.A, Metal Powder Industries Federation, 1997, 95-105.
40. J.Azcona, J.M.Sanchez, F. Castro, Hipping after Sintering of titanium Diboride Cermets, Powder Metallurgy 2001 Vol 44, No.2, 133-138.
41. Walker, J.K & Saha, C.K, J.Am. Ceram. Soc., 71(4)(1988)C-207-C209.
42．国外难熔金属与硬质材料，1996，Vol12，No．2．
43. M.W. Barsoum, B.Houng , Transient Plastic Phase Precessing of Titanium-Boron-Carbon Composites, J.Am.Ceram. Soc., 1993,76[6], 1445-51.
44. H.Holleck, H.Leiste, W. Schneider, R & HM September 1987, 149-154.
45. 1987, No.5,40-42.
46. Z.Y. Ma, J.H.Li, M.Lou, In-situ Formed Al_2O_3 and TiB_2 Particlulates Mixture reinforced Aluminum Composite, Scripta Metallurgica et Materialia, 1994, Vol.31, No.5,635-639.
47．齐藤 肇，长岛秀夫，松下纯一，日本公开特许公报，平 3-146473，1993年6月21日。
48．加藤英喜，松原 优，日本公开特许公报，特开平9-208322，1997年8月12日。
49. T. Graziani, A.Bellosi, D.D.Fabbriche, Effects of some Iron—group Metals on Densification and Characteristics of TiB_2, Refractory Metals & Hard Materials, 1992.11, 105-112.
2.李良福，硬质合金 1999, Vol. 16 No.2: 65-70.
3.L.G.Boxall, A.V.Cooke,H.W.Hayden, TiB_2 Cathod Material:Application in Conventional VSS Cell, Journal of Metals, November 1984,35-37.
4.E.S.KANG, C.H.Kim, Improvements in mechanical properties of TiB_2 by the dispersion of B_4C particles, Journal of Materials Science 1990,25,580-584.
5.L.S.Sigl, K.A.Schwetz, U.Dworak, Continuous Turning with TiB_2 Cermet:Preliminary Cutting Test,Int.J.of Refractory Metals & Hard Materials 12(1993-1994) 95-99.
6.宫本钦生，Y.C.Hyun,山田 修等，粉体和粉末冶金，1988, Vol 35, No. 7,651-654。
7、松下纯一，长岛秀夫，齐藤 肇，粉体和粉末冶金，(1990)Vol 37, No.7,1017-1020。
8.T.J.Davis,A.A.Ogwu, Characterisation of composite of TiC+TiB_2 bonded with nickel based binder alloy: mechanical and microstructural properties,Powder Metallurgy, 1995,Vol, 38 No.1,39-44.
9.T. Watanabe, H. Yamamoto, K. Shobu, Factors affecting the Porosity and Bending Strength of Ti (CN)-TiB_2 Materials, J.AM.Ceram. Soc., 1988, 71[4] C-202-C-204.
10.S.K.Lee, D.H.Kim, C.H.Kim, Fabrication of TiB_2/TiC composites by the directional reaction of Titanium with Boron Carbide,Journal of Materials Science 1994,29,4125-4130.
11．张国军，反应热压法制备 TiB_2-Ti(C，N)复相陶瓷研究，硅酸盐学报，1993，Vol21，NO．2，182-187。
12.M.Moriyama, H.Aoki, Fabrication and Mechanical Properties ofTiB_2-TiNxCy Composites by Reaction Sintering of B_4C and TiN Powders,Journal of the Ceramic Society of Japan, 1996,104[4],333-339.
13.R.Tomoshige, A.Murayama, Production of TiB_2-TiN Composites by Combustion Synthesis and their Properties, J.Am. Ceram. Soc., 1997, 80[3], 761-64.
14.M.Ouabdesselam, Z.Amunr, The sintering of Combustion synthesized Titanium Diboride,Journal of Materials Science 1987,22,1799-1807.
15.L.J.Kecskes, A.niiler, T. Kottke, Precursor Morphology Effects in Combustion-synthesized and Dynamically Consolidated Titanium Carbide and Titanium Boride, J.Am.Ceram. Soc., 1993, 76[12], 2961-70.
16.L.Wang, M.R. Wixom, Structural and mechanical properties of TiB_2 and TiC prepared by self-propergating high-temperature sythesis/dynamic, Journal of Materials Science 1994,29,534-543.
17.H.Taimatsu, T. Atsumi, T. Okaniwa, Synthesis of TiB_2-TiC Composites by the Solid-state Reaction between B_4C and Ti Powder, Journal of the Ceramic Society of Japan 1999,107[11], 1041-1045.
18.C.C.O 1987, No.5,32-34.
19.S.Torizuki, K.Sato, H.Nishio, Effect of SiC On Interfacial Reaction and Sintering Mechanism of TiB_2, J.Am. Ceram. Soc., 1995, 78 [6], 1606-10.
20.D.A.Hoke, D.K.Kim, J.C.LaSalvia, Combustion Synthesis/Dynamic Densification ofa TiB_2-SiC Composite, J.Am. Ceram. Soc., 1996, 79 [1] 177-82.
21．日本专利，特开平5-139834，岛冢史郎等，1993。
22、三上哲郎，日本专利，平4-14496834．1992．5．19。
23. T. Watanabe, K. Shoubu, Mechanical Properties of Hot Pressed TiB_2-ZrO_2 Composites, J.Am. Ceram. Soc., 1985, 68[2], C-34-C36.
24. Y. Muraoka, M.Yoshinaka, K.Hirota, Hot Isostatic Pressing of(2mol%Y2O3) Composite Powders, Material Reasearch Bulletin, 1996,Vol31, No.7, 787-79.
25．岛冢史郎，西尾浩明，粉体和粉末冶金1989，Vol36，No．2，100-104。
26．岛冢史郎，西尾浩明，粉体和粉末冶金，1991，Vol38，No．6，723-728。
27．松下纯一，长岛秀夫，齐藤肇，粉体和粉末冶金，1990，Vol37，No．4，551-555。
28. W.A.zdaniewski, Stereoscopic Fractography of Crack Propagation Phenomena in a TiB_2-AlN Composite, J.Am.Ceram. Soc., 1989, 72[1], 116-21.
29. Jongin Jung, Swwon, United state patent, 5,061,662, 1991.10.29.
30. E.S.Kang, C.W.Jang, C.H.Kim, Effect of Iron and Boron Carbide on the Densification and Mechanical Properties of Titanium Diboride Ceramics, J.Am. Ceram. Soc., 1989, 72[10], 1868-72.
31. J.H. Park, Y.H.Koh, HE.Kim, Densification and mechanical Properties of Titanium Diboride with Silicon Nitride as a Sintering Aid, J.Am.Ceram. Soc., 1999, 82[11], 3037-42.
32. J.H. Park, Y.H.Lee, Y.H. Koh, Effect of Hot-Pressing Temperature on Densification and Mechnical Properties of Titanium Diboride with Silicon Nitride as a Sintering Aid, J.Am. Ceram. Soc., 2000, 83[6], 1542-44.
33．山崎义照，日本公开特许公报，特开平5-306177，1993．11．19。
34、高容根．硬质合金1998，Vol．15 No．4：235-240。
35. Th.Jungling, L.S.Sigl, R. Oberacker et al., New Hardmetals Based on TiB_2, Refractory Metals Hard Meterials, 1993-1994, Vol. 12, 71-88
36. I.Smid,E.Kny, Refractory & Hard Metal, September 1988,Vol7, 135-139
37．西藤 广等。粉体与粉末冶金(日刊)，Vol．30(1989)，90-94。
38. B.Yuriditsky, TiB_2-Based Cermets,RM & HM, March 1990, 32-35.
39. J.K.Yang, A.griffo,R.M.German, Full Density Processing of Titanium Diboride Cermet,Advances in Powder Metallurgy & Particulate Materials, New Jersey, U.S.A, Metal Powder Industries Federation, 1997, 95-105.
40. J.Azcona, J.M.Sanchez, F. Castro, Hipping after Sintering of titanium Diboride Cermets, Powder Metallurgy 2001 Vol 44, No.2, 133-138.
41. Walker, J.K & Saha, C.K, J.Am. Ceram. Soc., 71(4)(1988)C-207-C209.
42．国外难熔金属与硬质材料，1996，Vol12，No．2．
43. M.W. Barsoum, B.Houng , Transient Plastic Phase Precessing of Titanium-Boron-Carbon Composites, J.Am.Ceram. Soc., 1993,76[6], 1445-51.
44. H.Holleck, H.Leiste, W. Schneider, R & HM September 1987, 149-154.
45. 1987, No.5,40-42.
46. Z.Y. Ma, J.H.Li, M.Lou, In-situ Formed Al_2O_3 and TiB_2 Particlulates Mixture reinforced Aluminum Composite, Scripta Metallurgica et Materialia, 1994, Vol.31, No.5,635-639.
47．齐藤 肇，长岛秀夫，松下纯一，日本公开特许公报，平 3-146473，1993年6月21日。
48．加藤英喜，松原 优，日本公开特许公报，特开平9-208322，1997年8月12日。
49. T. Graziani, A.Bellosi, D.D.Fabbriche, Effects of some Iron—group Metals on Densification and Characteristics of TiB_2, Refractory Metals & Hard Materials, 1992.11, 105-112.