超细Ti（C，N）粉体表面包覆及其金属陶瓷的制备
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摘要
本研究首次将非均相沉淀—热还原法应用于制备金属包覆碳氮化钛复合粉末。本文设计了两种非均相沉淀—热还原法,分别制备了Ni包覆Ti(C,N)复合粉末及Ni、Mo包覆Ti(C,N)复合粉末,然后以包覆粉末为原料,采用真空烧结制备了Ti(C,N)基金属陶瓷。运用SEM、EDS、XRD、TG-DSC等分析技术对包覆工艺进行了研究,并对金属陶瓷的显微组织、微区成分及性能进行了表征和分析。
以碳酸氢铵、硝酸镍、Ti(C,N)粉末为主要原料,采用非均相沉淀—热还原法制备Ni/Ti(C,N)包覆粉,实验确定了制备过程优化的工艺参数:使用0.5μm的Ti(C,N)粉末,Ti(C,N)颗粒含量为15g/L,碳酸氢铵溶液的滴加速度为3mL/min,搅拌速度为800r/min,添加表面活性剂PEG6000为5～10g/L,最终的pH值控制在8.0～8.5范围内,然后将获得的前驱体在550℃氢气气氛中煅烧及还原。将合成的Ni/Ti(C,N)包覆粉经压制与真空烧结制得金属陶瓷,结果表明: Ti(C,N)-Ni金属陶瓷的硬质相和粘结相分布均匀,但仍然存在晶粒长大现象;金属陶瓷的断裂方式为沿晶和穿晶混合型断裂;相成分为纯净的Ti(C,N)与Ni两相;该金属陶瓷的综合性能优于传统工艺制得的金属陶瓷。
以氨水、硝酸镍、钼酸铵、Ti(C,N)粉末为主要原料,结合配位沉淀的原理与非均相成核的机理,采用非均相沉淀—热还原法制备制备Ni-Mo-C/Ti(C,N)包覆粉,制备过程的优化的工艺参数为:Ti(C,N)颗粒含量为15g/L,搅拌速度为800r/min,PEG6000的加入量为8g/L,1～1.5倍的释水量,反应温度为55～60℃,然后将获得的前驱体在850℃氢气气氛中煅烧及还原。进一步的实验表明:采用包覆粉为原料制得了晶粒细小、显微结构均匀的(Ti,Mo)(C,N)-Ni金属陶瓷,但金属陶瓷的显微组织中看不到明显的环形结构;金属陶瓷的断裂方式为沿晶和韧窝混合型断裂;增韧机理主要为裂纹偏转和裂纹桥接;金属陶瓷中出现Ni3Ti相;除断裂韧性外,金属陶瓷的力学性能优于传统工艺制得的金属陶瓷;由于包覆粉在烧结过程中使得Ti、Mo原子在金属粘结相中固溶过多,检测不到金属陶瓷的磁性能。
The heterogeneous precipitation-thermal reduction process was applied to preparation of metal coated titanium carbonitride composite powders for the first time in this paper. Two new technologies of heterogeneous precipitation-thermal reduction process for synthesizing Ni coated Ti(C,N) composite powders and Ni&Mo coated Ti(C,N) composite powders had been developed,then the Ti(C,N) based cermets were prepared from the as-prepared composite powders after vacuum sintering. The preparation technologies of the coated powders were studied by applying various analysis techniques such as SEM, EDS, XRD, TG-DSC. The microstructure, micro-area chemical composition and properties of the as-prepared cermets were also analyzed.
Ni/Ti(C,N) coated powders were synthesized by heterogeneous precipitation-thermal reduction process using nickel nitrate, ammonium bicarbonate and Ti(C,N) powders as the main materials, The optimum process parameters were determined through our experiments, i.e., 0.5μm of particle size of Ti(C,N), 15g/L of Ti(C,N) powders, 3mL/min of feeding rate of ammonium bicarbonate solution, 800r/min of stirring rate, 5~10g/L of PEG6000, 8.0~8.5 of final pH value, then calcing and reducing at 550℃in H2 atmosphere. The Ni/Ti(C,N) coated powders were pressed and vacuum sintered,finally the cermet was obtained. The results show that the distribution of hard phase and binder phase in the cermet is uniform, but the phenomenon of growth of grain still occurs; fracture micrographs show that main failure mode of the cermet is a mixed one, i.e., trans-granular and inter-granular fractures are both exist; the phase constituents of the cermet are pure Ti(C,N) phase and Ni phase; the cermet show better comprehensive properties compared to the cermet which prepared by traditional process.
Combing the theory of coordinated precipitation with the mechanism of heterogeneous nucleation,Ni-Mo-C/Ti(C,N) coated powders were also synthesized by heterogeneous precipitation-thermal reduction process using nickel nitrate, ammonium molybdate, ammonium hydroxide and Ti(C,N) powders as the main materials, The optimum process parameters are as follows: 15g/L of Ti(C,N) powders, 800r/min of stirring rate, 8 g/L PEG6000, 1~1.5 times dilution with water, 55~60℃reaction temperature, then calcing and reducing at 850℃in H2 atmosphere. The futher experiments show that an ultrafine and uniform microstructure of (Ti,Mo)(C,N)-Ni cermet was obtained and there is no obvious surrounding structure can be found in the microstructure of the cermet; The fracture micrographs of the cermet show that the fracture is mainly characterized by inter-granular fractures and dimple fractures; the main toughening mechanisms of the cermet are crack deflection and crack bridge; the Ni3Ti phase is founded in the cermet; with the exception of fracture toughness, the mechanical properties of the cermet are better than cermet which perpared by traditional process; because excessive Ti&Mo atoms dissolved in binder phase, the magnetic properties of the cermets are not detected.
以碳酸氢铵、硝酸镍、Ti(C,N)粉末为主要原料,采用非均相沉淀—热还原法制备Ni/Ti(C,N)包覆粉,实验确定了制备过程优化的工艺参数:使用0.5μm的Ti(C,N)粉末,Ti(C,N)颗粒含量为15g/L,碳酸氢铵溶液的滴加速度为3mL/min,搅拌速度为800r/min,添加表面活性剂PEG6000为5～10g/L,最终的pH值控制在8.0～8.5范围内,然后将获得的前驱体在550℃氢气气氛中煅烧及还原。将合成的Ni/Ti(C,N)包覆粉经压制与真空烧结制得金属陶瓷,结果表明: Ti(C,N)-Ni金属陶瓷的硬质相和粘结相分布均匀,但仍然存在晶粒长大现象;金属陶瓷的断裂方式为沿晶和穿晶混合型断裂;相成分为纯净的Ti(C,N)与Ni两相;该金属陶瓷的综合性能优于传统工艺制得的金属陶瓷。
以氨水、硝酸镍、钼酸铵、Ti(C,N)粉末为主要原料,结合配位沉淀的原理与非均相成核的机理,采用非均相沉淀—热还原法制备制备Ni-Mo-C/Ti(C,N)包覆粉,制备过程的优化的工艺参数为:Ti(C,N)颗粒含量为15g/L,搅拌速度为800r/min,PEG6000的加入量为8g/L,1～1.5倍的释水量,反应温度为55～60℃,然后将获得的前驱体在850℃氢气气氛中煅烧及还原。进一步的实验表明:采用包覆粉为原料制得了晶粒细小、显微结构均匀的(Ti,Mo)(C,N)-Ni金属陶瓷,但金属陶瓷的显微组织中看不到明显的环形结构;金属陶瓷的断裂方式为沿晶和韧窝混合型断裂;增韧机理主要为裂纹偏转和裂纹桥接;金属陶瓷中出现Ni3Ti相;除断裂韧性外,金属陶瓷的力学性能优于传统工艺制得的金属陶瓷;由于包覆粉在烧结过程中使得Ti、Mo原子在金属粘结相中固溶过多,检测不到金属陶瓷的磁性能。
The heterogeneous precipitation-thermal reduction process was applied to preparation of metal coated titanium carbonitride composite powders for the first time in this paper. Two new technologies of heterogeneous precipitation-thermal reduction process for synthesizing Ni coated Ti(C,N) composite powders and Ni&Mo coated Ti(C,N) composite powders had been developed,then the Ti(C,N) based cermets were prepared from the as-prepared composite powders after vacuum sintering. The preparation technologies of the coated powders were studied by applying various analysis techniques such as SEM, EDS, XRD, TG-DSC. The microstructure, micro-area chemical composition and properties of the as-prepared cermets were also analyzed.
Ni/Ti(C,N) coated powders were synthesized by heterogeneous precipitation-thermal reduction process using nickel nitrate, ammonium bicarbonate and Ti(C,N) powders as the main materials, The optimum process parameters were determined through our experiments, i.e., 0.5μm of particle size of Ti(C,N), 15g/L of Ti(C,N) powders, 3mL/min of feeding rate of ammonium bicarbonate solution, 800r/min of stirring rate, 5~10g/L of PEG6000, 8.0~8.5 of final pH value, then calcing and reducing at 550℃in H2 atmosphere. The Ni/Ti(C,N) coated powders were pressed and vacuum sintered,finally the cermet was obtained. The results show that the distribution of hard phase and binder phase in the cermet is uniform, but the phenomenon of growth of grain still occurs; fracture micrographs show that main failure mode of the cermet is a mixed one, i.e., trans-granular and inter-granular fractures are both exist; the phase constituents of the cermet are pure Ti(C,N) phase and Ni phase; the cermet show better comprehensive properties compared to the cermet which prepared by traditional process.
Combing the theory of coordinated precipitation with the mechanism of heterogeneous nucleation,Ni-Mo-C/Ti(C,N) coated powders were also synthesized by heterogeneous precipitation-thermal reduction process using nickel nitrate, ammonium molybdate, ammonium hydroxide and Ti(C,N) powders as the main materials, The optimum process parameters are as follows: 15g/L of Ti(C,N) powders, 800r/min of stirring rate, 8 g/L PEG6000, 1~1.5 times dilution with water, 55~60℃reaction temperature, then calcing and reducing at 850℃in H2 atmosphere. The futher experiments show that an ultrafine and uniform microstructure of (Ti,Mo)(C,N)-Ni cermet was obtained and there is no obvious surrounding structure can be found in the microstructure of the cermet; The fracture micrographs of the cermet show that the fracture is mainly characterized by inter-granular fractures and dimple fractures; the main toughening mechanisms of the cermet are crack deflection and crack bridge; the Ni3Ti phase is founded in the cermet; with the exception of fracture toughness, the mechanical properties of the cermet are better than cermet which perpared by traditional process; because excessive Ti&Mo atoms dissolved in binder phase, the magnetic properties of the cermets are not detected.
引文
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