粉末注射成形钛合金粘结剂体系的研究进展

尤力; 刘艳军; 潘宇; 孙健卓; 惠泰龙; 杨宇承; 于爱华; 刘博文; 李维斌; 路新

doi:10.19591/j.cnki.cn11-1974/tf.2020090009

粉末注射成形钛合金粘结剂体系的研究进展

doi: 10.19591/j.cnki.cn11-1974/tf.2020090009

尤力¹,
刘艳军^2, ,,
潘宇²,
孙健卓²,
惠泰龙²,
杨宇承²,
于爱华²,
刘博文²,
李维斌²,
路新^{1, 2, 3}

1.
北京科技大学新金属材料国家重点实验室，北京 100083
2.
北京科技大学新材料技术研究院，北京 100083
3.
北京科技大学北京材料基因工程高精尖创新中心，北京 100083

基金项目: 国家自然科学基金资助项目（51874037，51922004）；中央高校基本科研业务费专项资金资助项目（FRF-TP-19-054A2）；北京市自然科学基金资助项目（2212035）

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通讯作者:
E-mail: yanjunliu_123@163.com

中图分类号: TG146.2+3
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出版历程
- 收稿日期: 2020-09-11
- 刊出日期: 2021-12-10

Research progress of titanium alloy binder system for powder injection molding

1.
State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China
2.
Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China
3.
Beijing Advanced Innovation Center for Materials Genome Engineering, University of Science and Technology Beijing, Beijing 100083, China

More Information

Corresponding author: E-mail: yanjunliu_123@163.com

摘要

摘要: 钛及钛合金具有低比重、高比强度、优异的生物相容性以及良好的耐腐蚀性等特点，在航空航天、生物医疗、化工、船舶、汽车等领域极具应用潜力。钛合金粉末注射成形技术（powder injection molding，PIM）提高了材料的利用率，实现了中小型复杂形状钛产品的大批量、低成本制备，显著地推动了钛及钛合金产品的生产及应用。目前关于粉末注射成形钛合金粘结剂体系的相关文献报道十分有限，新型粉末注射成形钛合金粘结剂体系的开发处于停滞不前的状态。本文分析总结了不同粉末注射成形钛合金粘结剂体系的研究现状，并针对目前存在的问题提出改进措施。
- 钛合金 /
- 粉末注射成形 /
- 粘结剂 /
- 脱脂
Abstract: Titanium and titanium alloys have the low specific gravity, high specific strength, excellent biocompatibility, and good corrosion resistance, showing the great application potential in the aerospace, biomedicine, chemical engineering, shipbuilding, automobile, and other fields. The powder injection molding (PIM) technology used for titanium alloys increases the utilization rate of materials, realizes the large-scale and low-cost preparation of small and medium-sized titanium products with complex shape, and significantly promotes the development of titanium and its alloys. At present, there are few reports about the titanium alloy binder system for powder injection molding, and the development of new type titanium alloy binder system for powder injection molding is in a stagnating state. The research status of the different titanium alloy binder systems for powder injection molding was introduced in this paper, and some improvements for the existing problems were suggested as the reference for researchers.
- titanium alloys /
- powder injection molding /
- binders /
- debinding

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图 1 波音民航客机钛制品用量占比与研发时间关系

Figure 1. Relationship between the usage amount (mass fraction) and the development time of titanium products in Boeing commercial passenger aircraft

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图 2 部分粉末注射成形钛合金产品：（a）德国TiJet公司制备的工程应用零部件；（b）德国TiJet公司制备生物医用零部件；（c）Ti‒6Al‒7Nb合金骨螺钉；（d）CP-Ti人工镫骨；（e）钛合金眼镜架；（f）Ti‒6Al‒4V表壳实物

Figure 2. Parts of titanium alloy products by powder injection molding: (a) parts of engineering applications prepared by TiJet; (b) parts of biomedical applications prepared by TiJet; (c) Ti‒6Al‒7Nb bone screws; (d) CP-Ti artificial stapes; (e) titanium alloy spectacle frames; (f) Ti‒6Al‒4V watchcase

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图 3 氧质量分数对钛合金力学性能的影响^[12]

Figure 3. Effect of oxygen mass fraction on the mechanical properties of titanium alloys^[12]

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图 4 改进型以及传统型粘结剂喂料的热重分析曲线^[17]

Figure 4. TGA curves of the improved and traditional feedstocks^[17]

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图 5 不同粘结剂混合物的热重分析曲线^[34]

Figure 5. TGA curves of the different binder blends^[34]

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图 6 两组元粘结剂脱除模型^[37]：（a）初始阶段；（b）连通孔隙形成；（c）低熔点组元脱除；（d）高熔点组元脱除

Figure 6. Two-component binder removal model^[37]: (a) initial stage; (b) formation of connected pores; (c) removal of low melting point components; (d) removal of high melting point components

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图 7 催化脱脂模型示意图^[39]：（a）脱脂催化反应；（b）催化脱脂动力学

Figure 7. Schematic diagram of the solvent debinding mode^[39]: (a) catalytic debinding reaction; (b) catalytic debinding kinetics

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图 8 溶剂脱脂模型示意图^[40]

Figure 8. Schematic diagram of the solvent debinding model^[40]

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表 1 粉末注射成形钛合金常用粘结剂骨架剂组元的热力学性质

Table 1. Thermodynamic properties of the skeleton components of titanium alloys by powder injection molding

聚合物组元	结构	热分解行为
聚合物组元	结构	热分解起始温度 / ℃	热分解结束温度 / ℃	分解原理	产物类型
高密度聚乙烯（HDPE）		368	498	随机断链	烷烃、烯烃、少量单体
低密度聚乙烯（LDPE）		355	467	随机断链	烷烃、烯烃、少量单体
聚丙烯（PP）		304	420	随机断链	烷烃、烯烃、少量单体
聚苯乙烯（PS）		236	426	随机断链	苯乙烯单体、二聚体及三聚体
聚甲基丙烯酸甲酯（PMMA）		278	428	端链断裂	单体（约90%～100%）
乙烯—醋酸乙烯共聚物（EVA）		306	491	链式剥离	乙酸、1-丁烯、CO₂、 CO、乙烯、甲烷
聚甲醛（POM）		180	395	端链断裂	甲醛单体
注：以上各聚合物的热分解温度都是通过热分析曲线获得。

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表 2 粉末注射成形钛粉杂质元素含量（质量分数）及力学性能^[21]

Table 2. Impurity element content (mass fraction) and the mechanical properties of Ti powders used in PIM^[21]

成分	O / %	N / %	C / %	H / %	相对密度 / %	屈服强度 / MPa	极限抗拉强度 / MPa	延伸率 / %
粉末注射成形钛粉	0.30	0.27	0.065	0.013	97.1	519	666	15
ASTM 四级纯钛	0.40	0.05	0.080	0.015	100.0	480	550	15

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表 3 喂料配方（体积分数）^[32‒33]

Table 3. Feedstock formulations^[32‒33] %

喂料编号	粉末含量	PEG	PVB	SA	粘结剂组元比例 PEG:PVB:SA
1	55	33.8	9.0	2.2	75:20:5
2	60	30.0	8.0	2.0	75:20:5
3	55	36.0	6.8	2.2	80:15:5
4	60	32.0	6.0	2.0	80:15:5

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