Study on powder metallurgical properties of molten salt electrolytic titanium powder
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摘要: 以电解钛粉为原料，采用模压-烧结的方法制备多孔钛，对电解钛粉的成型和烧结特性进行了研究，最后针对制备的多孔钛的力学性能、孔结构、孔径分布及透气率等性能进行了表征。结果表明：随压制压力的增加，具有二次颗粒特征的电解钛粉颗粒间搭桥空间逐渐消失，可通过成型压力和烧结温度的调节获得不同孔隙率和力学强度的多孔钛。电解钛粉与氢化脱氢钛粉相比具有成型性能良好、更易发生烧结致密化、制件孔隙率高、透气率高、杨氏模量高等特点。使用粒径74～104 μm的电解钛粉在70～110 MPa成型、
1110 ℃烧结后的多孔钛，杨氏模量与人体松质骨接近，透气率和最大孔径满足烧结金属过滤元件（GBT6887-2019）TG035、TG020要求，在人体松质骨植入件以及过滤材料领域有应用前景。Abstract: Electrolytic titanium powder was utilized as the raw material for fabricating porous titanium through press-sintering technique. The forming and sintering characteristics were investigated. Then the mechanical properties, pore structure, pore size distribution and permeability of the prepared porous titanium were characterized. The results show that with the increase of pressing pressure, the bridging space between the particles of electrolytic titanium powder with secondary particle characteristics gradually disappears. Porous titanium powder with different porosity and mechanical strength can be obtained by adjusting the molding pressure and sintering temperature. Compared to HDH titanium powder, electrolytic titanium powder exhibits better molding performance, easier sintering densification, higher porosity, greater permeability, and a higher Young’s modulus. A porous titanium was obtained by using electrolytic titanium powder with a particle size of 74~104 μm at 70~110 MPa and then sintering it at1110 ℃, whose Young’s modulus is similar to that of human cancellous bone. The permeability and maximum pore diameter meet the requirements of TG035 and TG020 in the standard for sintered metal filtration elements (GBT6887-2019), indicating promising applications in the fields of human cancellous bone implants and filtration materials.-
Key words:
- porous titanium /
- electrolytic titanium powder /
- molding /
- sinter /
- mechanical property
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图 1 钛粉的形貌
(a)(b)(c) 电解钛粉（粒径365～833 μm）；(d)(e)(f) 电解钛粉（粒径74～104 μm）；(g)(h)(i) HDH钛粉（粒径74～104 μm）
Figure 1. Morphology of titanium powder
图 2 不同成型压力获得的料坯密度
(a)电解钛粉料坯；(b) HDH钛粉料坯
Figure 2. Compact density under different forming pressures
图 3 不同成型压力及温度烧结多孔钛的孔隙率及收缩率
(a)孔隙率；(b)收缩率
Figure 3. Porosity and shrinkage of sintered porous titanium at different molding pressures and temperatures
图 4 不同烧结温度下保温2 h获得的多孔钛孔形貌
(a)(b)(c)电解钛粉；(d)(e)(f) HDH钛粉；烧结温度分别为(a)(d)1 000 ℃；(b)(e)1 110 ℃；(c)(f)1 200 ℃
Figure 4. Pore morphology at different sintering temperatures（sintering holding time 2 h）
图 5 电解钛粉不同成型压力获得的多孔钛形貌
钛粉粒径74～104 μm；烧结条件
1110 ℃，2 hFigure 5. The morphology of porous titanium obtained by electrolytic titanium powder under different forming pressures
(a) 50 MPa; (b) 70 MPa; (c) 110 MPa; (d) 130 MPa; (e) 170 MPa; (f) 190 MPa
图 6 不同类型钛粉制备多孔钛孔结构
(a)(d) 365～833 μm电解粉；(b)(e) 74～104 μm 电解粉；(c)(f) 74～104 μm HDH 粉
Figure 6. The structures of the porous titanium prepared using different titanium powder
图 7 不同成型压力制备多孔钛压缩力学强度
(a)压缩曲线；(b)电解粉多孔钛成型压力与抗压强度关系；钛粉粒径74～104 μm，烧结条件1 100 ℃，2 h
Figure 7. Compressive mechanical strength of porous titanium prepared by different forming pressures
图 8 多孔钛孔径分布
(a)和(b)为原料分别为365～833 μm和74～104 μm的电解粉；(c)为粒径74～104 μm的HDH粉；制备条件为110 MPa成型，1 110 ℃烧结2 h
Figure 8. Pore size distribution of porous titanium
表 1 钛粉化学成分
Table 1. Chemical compositions of titanium powder
钛粉种类 粒径/μm 杂质含量/% Ni Cr Mn Na Ca Fe C N H O 电解粉 74～104 0.04 0.02 <0.01 0.02 0.02 0.04 <0.01 0.010 0.032 0.89 电解粉 365～833 <0.01 0.01 <0.01 0.02 0.01 <0.01 <0.01 0.007 0.005 0.78 HDH粉 74～104 0.02 0.01 <0.01 0.01 0.01 0.05 <0.01 0.010 0.022 0.12 
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表 2 不同成型压力的料坯
1100 ℃烧结后力学强度Table 2. Mechanical strength of billets sintered at
1100 ℃ under different forming pressures原料类型 成型压力/MPa 最大压缩力/kN 抗压强度/MPa 杨氏模量/GPa 电解
钛粉70 5.264 73.7 0.84 110 11.043 157 2.79 150 17.507 245 4.07 190 27.103 378 5.17 230 34.459 488 6.11 HDH
钛粉110 174.2 1.51 150 216.4 3.51
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表 3 不同制备条件的钛粉孔隙率及孔径
Table 3. Porosity and pore size of titanium powder under different preparation conditions
原料
类型钛粉粒径/μm 制备条件 孔隙率
(质量-
体积)/%孔隙率
(压汞法)/%体积中值孔径
（压汞法）/μm成型压力/MPa 烧结温度/℃ 烧结时间/h 电解
钛粉365～833 110 1110 2 54.2 44.60 26.4 74～104 150 1110 2 40.1 25.91 11.2 74～104 110 1110 2 43.9 43.30 21.6 74～104 110 1200 2 42.1 9.75 10.7 74～104 190 1200 2 36.6 6.66 5.06 74～104 50 1200 2 55.8 68.82 172.5 HDH
钛粉74～104 110 1110 2 39.5 17.31 11.1
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表 4 多孔钛的透气率及最大孔径
Table 4. Permeability and maximum pore size of porous titanium
样品
编号原料
类型粒径/μm 制备条件 透气率/
（m3·h−1·m−2·kPa−1）气泡最大孔径/μm 成型
压力/
MPa烧结
温度/
℃烧结
时间/
h1 电解粉 365～833 110 1110 2 292 68 2 电解粉 365～833 70 1110 2 472 92 3 电解粉 74～104 110 1110 2 207 44 4 HDH粉 74～104 110 1110 2 100 32
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