高性能Ti（C，N）基金属陶瓷材料及其刀具切削性能研究
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摘要
本文应用粉末冶金、材料科学和固体经验电子理论(EET理论)研究了Nj对Ti(C,N)基金属陶瓷中不同碳化物的润湿性、润湿性与陶瓷相价电子结构的关系以及细晶粒的Ti(C,N)基金属陶瓷材料和切削刀具的性能。
首先,介绍了Ti(C,N)基金属陶瓷的发展过程、组织性能、研究现状、存在的问题及其在切削刀具领域的应用。重点概述了加入晶粒长大抑制剂对金属陶瓷组织和性能的影响、纳米增强和超细晶粒Ti(C,N)基金属陶瓷的研究现状,指出了Ti(C,N)基金属陶瓷的发展趋势;同时也概述了EET理论在金属陶瓷领域的应用;指出了本文研究的目的与意义。简要讨论了润湿性测试用陶瓷基板的制备工艺,发现采用热压烧结(HP)工艺(Ar保护、压力为30MPa、在1800℃下保温1h)可以制备出致密度达97%以上的陶瓷基板。详细研究了金属陶瓷中不同碳化物对Ni的润湿性,指出在Ti(C,N)固溶体中添加Mo_2C、TaC、WC、VC和NbC等碳化物都能降低金属Ni/(Ti,Me)(C,N)体系的接触角(θ),添加一元碳化物对改善润湿性能力大小依次为:Mo_2C>TaC>WC>VC>NbC。添加多元碳化物能够使Ni对Ti(C,N)固溶体的接触角持续降低。研究发现,Ni/(Ti,Me)(C,N)体系的润湿机理是存在元素扩散与金属/陶瓷互溶的反应性润湿。而在研究润湿性与陶瓷相价电子结构的关系时发现,多元陶瓷相的价电子结构参数(n_A)随碳化物添加量的增加而增加,碳化物对n_A影响大小依次为VC>Mo_2C>NbC>WC>TaC;建立了陶瓷相最强键上共价电子数(n_A)、润湿性(接触角θ)以及陶瓷相成份(x)之间的关系;发现了添加Mo_2C可使陶瓷相与金属相的界面电子密度增大,润湿性得到改善,界面得到强化,金属陶瓷的强韧性也得以提高。
其次,研究了纳米TiN改性TiC基金属陶瓷的组织与性能。发现添加纳米TiN或复合添加纳米—微米TiN可以增强TiC基金属陶瓷材料;随纳米TiN的添加量的增加,金属陶瓷材料的组织都得到了细化,材料力学性能得到提高;当添加6～8wt%的纳米TiN时可以获得最优的力学性能;组织细化和力学性能提高的原因与在基体(TiC)晶界处分布的纳米TiN颗粒可以有效钉扎TiC晶粒的运动有关。而Mo含量对5Co-5Ni和10Co-10Ni纳米改性金属陶瓷的组织的影响不尽相同。研究发现,随Mo添加量的增大,材料的断裂韧性和抗弯强度下降;当Mo添加量为4wt%时,材料的断裂韧性和抗弯强度都达到最大值。纳米TiN增强金属陶瓷的机制有细晶强化、弥散强化和固溶强化。
本文还研究了纳米改性金属陶瓷刀具的切削性能和磨损机理。结果表明,在切削正火态45#钢、灰铸铁、淬硬钢利不锈钢时,与YT15硬质合金刀具和YG8刀具相比,纳米改性金属陶瓷刀具寿命明显较高。而与未进行纳米改性的金属陶瓷刀具相比,纳米改性金属陶瓷刀具的切削性能与耐磨性有了较大的提高。纳米改性金属陶瓷刀具在v_c=200 m/min～400m/min下切
In order to improve the strength and toughness of Ti(C,N) cermets efficiently and make cermets win more and more wide applications, wettability of nickel on various carbides in cermets, relationship between valence electron structure (VES) and wettability, the microstructures and mechanical properties of Ti(C,N)-based cermets materials with nano-TiN modifications and cutting properties of cermets cutters are investigated systematically in this dissertation by means of powder metallurgy, materials science and empirical electron theory of solids (EET theory).In the first part, the development process, microstructures and properties, present research situation, problems presently existing and application areas as cutters have been outlined and a special attention is paid to the role and effect of grain growth inhibitors on the microstructures and properties of cermets and research status in the nano reinforcing Ti(C,N)-based cermets and ultra-fine grained Ti(C,N)-based cermets. Simultaneously, the present research progress of EET theory is also outlined and the development trends of cermets pointed out. Grounded on the above work, the purposes and significance of this dissertation have also been pointed out. Preparation techniques for wetting test samples was briefly given and results have shown that ceramic substrates with high density (above 97 %) can be prepared by using hot press technology (pressure being 30MPa, temperature being 1800℃ for 1 h at an argon atmosphere).Furthermore, wettability of nickel on various carbides in cermets was investigated and wetting tests reveal that contact angle (θ) reduces continuously and wettability of Ni/(Ti,Me)(C,N) are improved efficiently with the addition of various carbides such as Mo_2C, TaC, WC, VC as well as NbC and contact angle ( 9) decreases definitely with the increase of carbides content, the impact order of the carbides on θis Mo_2C>TaC>WC>VC >NbC. It is also found that wetting mechanism of Ni/(Ti,Me)(C,N) system is virtually a process in which diffusion and dissolution of elements are characterized. On the other hand, it can be deduced from EET calculations that the covalent electrons on the strongest bond (n_a) in ceramic phases increase with the content of carbides, and the impact order is VC>Mo_2C>NbC>WC>TaC. The author have also posed the regression relationship among the chemical composition (x), contact angle (θ) and valence electron structure (n_A). In this section, the author have also found that addition of M02C can efficiently improve the wettability between (Ti,Me)(C,N) and Ni and the interfacial binding and strength are therefore
improved, and cermets with high strength and toughness can be obtained.In the second part, microstructures and mechanical properties of TiC based cermets with nano-TiN modifications are presented. Results reveal that addition of nano-TiN particles or compound addition of nano-TiN and micro-TiN can to some extent strengthen the cermets and a finer microstructure and higher mechanical properties have been obtained with the increase of content of nano-TiN. Investigations have also shown that optimally comprehensive properties are achieved when the content of nano-TiN reaches 6~8wt%.TEM characterizations reveal that dispersive distribution of residual nano-TiN particles at/among TiC interfaces results in the fining effect and improvements of mechanical properties of cermets. On the other hand, the effects of Mo on the microstructures of 5Co-5Ni cermets and lOCo-lONi cermets are not identical. Mechanical tests show that bending strength and fracture toughness decline definitely with addition of Mo and reach a maximum value when Mo content is about 4 wt%. In general, the reinforcing mechanism of nano-particles on cermets can be summarized as grain fining strengthening, dispersion strengthening and solid solution strengthening.Next, the cutting characteristics and wearing mechanism of cermets cutters with nano-TiN modifications are discussed in detail. Results show that in machining normalized medium carbon steel, gray cast iron, quenched steel and stainless steel cermets cutters with nano-TiN modifications definitely exhibit better cutting properties and longer tool life in comparison with cemented carbide cutters (YT15 and YG8) and conventional cermets cutter. Grain wear, diffusion wear and oxidation wear are predominant wear mechanism when the cutter is cutting at a higher speed (200 m/min ~ 400m/min). Comparably, the main wear mechanism changes to adhesion wear, diffusion wear and oxidation wear when the cutter is utilized in cutting gray cast iron. Investigations also show that in cutting quenched steel cermets cutter readily fails in the form of "chipping".Finally, thermal shock resistance of cermets with nano-modifications is investigated. Results reveal that the quantity and size of the voids plus the size of micro-cracks in cermets increases with thermal shock cycles (N) and cermets with nano-modifications possesses a better thermal shock resistance in comparison with conventional cermets materials.
首先,介绍了Ti(C,N)基金属陶瓷的发展过程、组织性能、研究现状、存在的问题及其在切削刀具领域的应用。重点概述了加入晶粒长大抑制剂对金属陶瓷组织和性能的影响、纳米增强和超细晶粒Ti(C,N)基金属陶瓷的研究现状,指出了Ti(C,N)基金属陶瓷的发展趋势;同时也概述了EET理论在金属陶瓷领域的应用;指出了本文研究的目的与意义。简要讨论了润湿性测试用陶瓷基板的制备工艺,发现采用热压烧结(HP)工艺(Ar保护、压力为30MPa、在1800℃下保温1h)可以制备出致密度达97%以上的陶瓷基板。详细研究了金属陶瓷中不同碳化物对Ni的润湿性,指出在Ti(C,N)固溶体中添加Mo_2C、TaC、WC、VC和NbC等碳化物都能降低金属Ni/(Ti,Me)(C,N)体系的接触角(θ),添加一元碳化物对改善润湿性能力大小依次为:Mo_2C>TaC>WC>VC>NbC。添加多元碳化物能够使Ni对Ti(C,N)固溶体的接触角持续降低。研究发现,Ni/(Ti,Me)(C,N)体系的润湿机理是存在元素扩散与金属/陶瓷互溶的反应性润湿。而在研究润湿性与陶瓷相价电子结构的关系时发现,多元陶瓷相的价电子结构参数(n_A)随碳化物添加量的增加而增加,碳化物对n_A影响大小依次为VC>Mo_2C>NbC>WC>TaC;建立了陶瓷相最强键上共价电子数(n_A)、润湿性(接触角θ)以及陶瓷相成份(x)之间的关系;发现了添加Mo_2C可使陶瓷相与金属相的界面电子密度增大,润湿性得到改善,界面得到强化,金属陶瓷的强韧性也得以提高。
其次,研究了纳米TiN改性TiC基金属陶瓷的组织与性能。发现添加纳米TiN或复合添加纳米—微米TiN可以增强TiC基金属陶瓷材料;随纳米TiN的添加量的增加,金属陶瓷材料的组织都得到了细化,材料力学性能得到提高;当添加6～8wt%的纳米TiN时可以获得最优的力学性能;组织细化和力学性能提高的原因与在基体(TiC)晶界处分布的纳米TiN颗粒可以有效钉扎TiC晶粒的运动有关。而Mo含量对5Co-5Ni和10Co-10Ni纳米改性金属陶瓷的组织的影响不尽相同。研究发现,随Mo添加量的增大,材料的断裂韧性和抗弯强度下降;当Mo添加量为4wt%时,材料的断裂韧性和抗弯强度都达到最大值。纳米TiN增强金属陶瓷的机制有细晶强化、弥散强化和固溶强化。
本文还研究了纳米改性金属陶瓷刀具的切削性能和磨损机理。结果表明,在切削正火态45#钢、灰铸铁、淬硬钢利不锈钢时,与YT15硬质合金刀具和YG8刀具相比,纳米改性金属陶瓷刀具寿命明显较高。而与未进行纳米改性的金属陶瓷刀具相比,纳米改性金属陶瓷刀具的切削性能与耐磨性有了较大的提高。纳米改性金属陶瓷刀具在v_c=200 m/min～400m/min下切
In order to improve the strength and toughness of Ti(C,N) cermets efficiently and make cermets win more and more wide applications, wettability of nickel on various carbides in cermets, relationship between valence electron structure (VES) and wettability, the microstructures and mechanical properties of Ti(C,N)-based cermets materials with nano-TiN modifications and cutting properties of cermets cutters are investigated systematically in this dissertation by means of powder metallurgy, materials science and empirical electron theory of solids (EET theory).In the first part, the development process, microstructures and properties, present research situation, problems presently existing and application areas as cutters have been outlined and a special attention is paid to the role and effect of grain growth inhibitors on the microstructures and properties of cermets and research status in the nano reinforcing Ti(C,N)-based cermets and ultra-fine grained Ti(C,N)-based cermets. Simultaneously, the present research progress of EET theory is also outlined and the development trends of cermets pointed out. Grounded on the above work, the purposes and significance of this dissertation have also been pointed out. Preparation techniques for wetting test samples was briefly given and results have shown that ceramic substrates with high density (above 97 %) can be prepared by using hot press technology (pressure being 30MPa, temperature being 1800℃ for 1 h at an argon atmosphere).Furthermore, wettability of nickel on various carbides in cermets was investigated and wetting tests reveal that contact angle (θ) reduces continuously and wettability of Ni/(Ti,Me)(C,N) are improved efficiently with the addition of various carbides such as Mo_2C, TaC, WC, VC as well as NbC and contact angle ( 9) decreases definitely with the increase of carbides content, the impact order of the carbides on θis Mo_2C>TaC>WC>VC >NbC. It is also found that wetting mechanism of Ni/(Ti,Me)(C,N) system is virtually a process in which diffusion and dissolution of elements are characterized. On the other hand, it can be deduced from EET calculations that the covalent electrons on the strongest bond (n_a) in ceramic phases increase with the content of carbides, and the impact order is VC>Mo_2C>NbC>WC>TaC. The author have also posed the regression relationship among the chemical composition (x), contact angle (θ) and valence electron structure (n_A). In this section, the author have also found that addition of M02C can efficiently improve the wettability between (Ti,Me)(C,N) and Ni and the interfacial binding and strength are therefore
improved, and cermets with high strength and toughness can be obtained.In the second part, microstructures and mechanical properties of TiC based cermets with nano-TiN modifications are presented. Results reveal that addition of nano-TiN particles or compound addition of nano-TiN and micro-TiN can to some extent strengthen the cermets and a finer microstructure and higher mechanical properties have been obtained with the increase of content of nano-TiN. Investigations have also shown that optimally comprehensive properties are achieved when the content of nano-TiN reaches 6~8wt%.TEM characterizations reveal that dispersive distribution of residual nano-TiN particles at/among TiC interfaces results in the fining effect and improvements of mechanical properties of cermets. On the other hand, the effects of Mo on the microstructures of 5Co-5Ni cermets and lOCo-lONi cermets are not identical. Mechanical tests show that bending strength and fracture toughness decline definitely with addition of Mo and reach a maximum value when Mo content is about 4 wt%. In general, the reinforcing mechanism of nano-particles on cermets can be summarized as grain fining strengthening, dispersion strengthening and solid solution strengthening.Next, the cutting characteristics and wearing mechanism of cermets cutters with nano-TiN modifications are discussed in detail. Results show that in machining normalized medium carbon steel, gray cast iron, quenched steel and stainless steel cermets cutters with nano-TiN modifications definitely exhibit better cutting properties and longer tool life in comparison with cemented carbide cutters (YT15 and YG8) and conventional cermets cutter. Grain wear, diffusion wear and oxidation wear are predominant wear mechanism when the cutter is cutting at a higher speed (200 m/min ~ 400m/min). Comparably, the main wear mechanism changes to adhesion wear, diffusion wear and oxidation wear when the cutter is utilized in cutting gray cast iron. Investigations also show that in cutting quenched steel cermets cutter readily fails in the form of "chipping".Finally, thermal shock resistance of cermets with nano-modifications is investigated. Results reveal that the quantity and size of the voids plus the size of micro-cracks in cermets increases with thermal shock cycles (N) and cermets with nano-modifications possesses a better thermal shock resistance in comparison with conventional cermets materials.
引文
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