Effects of pore-forming agents on microstructure and properties of biomedical porous Ti/16Mg composites
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摘要:
采用粉末冶金工艺结合微波烧结法制备了弹性模量接近于人体骨骼、强度符合人体植入物要求的医用多孔Ti/16Mg复合材料。通过扫描电镜、X射线衍射、金相显微镜、压缩试验以及耐腐蚀性测试等手段研究了造孔剂NH4HCO3粒径及添加量（质量分数）对复合材料的微观组织、力学性能和耐腐蚀性能的影响。结果表明：NH4HCO3对多孔Ti/16Mg复合材料的物相组成没有显著影响，试样孔隙随着NH4HCO3粒径的增大而增大，随着NH4HCO3添加量增加，试样孔隙率由16.64%增加到33.09%。当NH4HCO3粒径为165～198 μm、质量分数为18%时，多孔Ti/16Mg试样的弹性模量为6.49 GPa、抗压强度为115 MPa，满足人体植入物的力学性能要求。NH4HCO3粒径对复合材料的耐腐蚀性影响不大，在相同粒径条件下，随NH4HCO3质量分数由0增加至24%，复合材料的耐腐蚀性能略有下降，极化电阻由574.528 Ω·cm‒2下降到139.236 Ω·cm‒2。
Abstract:The biomedical porous Ti/16Mg composite materials with the elastic modulus close to that of human bone and the strength meeting the requirements of human implants were prepared by powder metallurgy combined with microwave sintering method in this paper. The effects of particle size and addition amount (mass fraction) of NH4HCO3 pore-forming agents on the microstructure, mechanical properties, and corrosion resistance of the composites were investigated by scanning electron microscopy, X-ray diffraction, metallography, compression test, and corrosion resistance test. The results show that NH4HCO3 has no significant effect on the phase composition of porous Ti/16Mg composites. The pore size increases with the increase of NH4HCO3 particle size, and the porosity increases from 16.64% to 33.09% with the increase of NH4HCO3 mass fraction. When the particle size of NH4HCO3 is 165~198 μm and the mass fraction is 18%, the elastic modulus of the porous Ti/16Mg composites is 6.49 GPa and the compressive strength is 115 MPa, which can meet the mechanical property requirements of human implants. Particle size of NH4HCO3 has little effect on the corrosion resistance of the porous Ti/16Mg composites. With the same particle size, the corrosion resistance of the porous Ti/16Mg composites decreases slightly and the polarization resistance decreases from 574.528Ω·cm‒2 to 139.236Ω·cm‒2 with the mass fraction of NH4HCO3 increasing from 0 to 24%.
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图 1 原始粉末微观形貌：（a）Ti粉；（b）Mg粉；（c）球磨8 h混合粉末
Figure 1. Microstructure of the original metal powders: (a) Ti powders; (b) Mg powders; (c) the mixed powders after ball milling for 8 h
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图 2 多孔Ti/Mg复合材料基体制备流程图
Figure 2. Preparationflow chart of the porous Ti/Mg composite matrix
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图 3 添加不同粒径18%NH4HCO3制备的Ti/16Mg复合材料X射线衍射图谱
Figure 3. XRD patterns of the Ti/16Mg composites added by 18%NH4HCO3 in different particle sizes
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图 4 添加不同粒径18%NH4HCO3制备的多孔Ti/16Mg复合材料显微形貌：（a）245～350 μm；（b）165～198 μm；（c）74～125 μm
Figure 4. SEM images of the porous Ti/16Mg composites added by 18%NH4HCO3 in different particle sizes: (a) 245~350 μm; (b) 165~198 μm; (c) 74~125 μm
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图 5 多孔Ti/16Mg复合材料孔隙周边部位能谱分析
Figure 5. EDS analysis around the pores of the porous Ti/16Mg composites
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图 6 多孔Ti/16Mg复合材料非孔隙部位分析
Figure 6. EDS analysis in the non-porous parts of the porous Ti/16Mg composites
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图 7 添加不同质量分数NH4HCO3制备的Ti/16Mg复合材料X射线衍射图谱
Figure 7. XRD patterns of the Ti/16Mg composites added by NH4HCO3 in different mass fraction
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图 8 添加不同质量分数NH4HCO3制备的多孔Ti/16Mg复合材料显微形貌：（a）6%；（b）12%；（c）18%；（d）24%
Figure 8. SEM images of the porous Ti/16Mg composites added by NH4HCO3 in different mass fraction: (a) 6%; (b) 12%; (c) 18%; (d) 24%
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图 9 添加不同质量分数NH4HCO3对多孔Ti/16Mg复合材料密度和孔隙率的影响
Figure 9. Effects of NH4HCO3 mass fraction on the density and porosity of the porous Ti/16Mg composites
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图 10 添加不同粒径18%NH4HCO3制备的多孔Ti/16Mg复合材料应力应变曲线
Figure 10. Stress-strain curves of the porous Ti/16Mg composites added by 18%NH4HCO3 in different particle sizes
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图 11 添加不同粒径18%NH4HCO3对多孔Ti/16Mg复合材料的力学性能影响
Figure 11. Effect of 18%NH4HCO3 with different particle sizes on the mechanical properties of the porous Ti/16Mg composites
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图 12 添加不同质量分数NH4HCO3制备的多孔Ti/16Mg复合材料的应力应变曲线
Figure 12. Stress‒strain curves of porous Ti/16Mg composites added by NH4HCO3 in different mass fraction
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图 13 添加不同质量分数NH4HCO3对多孔Ti/16Mg复合材料的力学性能影响
Figure 13. Effects of NH4HCO3 mass fraction on the mechanical properties of the porous Ti/16Mg composites
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图 14 添加不同粒径18%NH4HCO3制备的多孔Ti/16Mg复合材料动电位极化曲线
Figure 14. Potentiodynamic polarization curves of the porous Ti/16Mg composites added by 18%NH4HCO3 in different particle sizes
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图 15 添加不同质量分数NH4HCO3制备的多孔Ti/16Mg复合材料的动电位极化曲线
Figure 15. Potentiodynamic polarization curves of the porous Ti/16Mg composites added by NH4HCO3 in different mass fraction
表 1 钛、镁粉末中元素化学成分（质量分数）
Table 1 Chemical composition of the Ti and Mg powders
% 粉末 Fe Al C N Si V Mn Cu Cl Ni Pb Ti粉 ≤0.02 ≤0.01 ≤0.01 ≤0.01 ≤0.01 ≤0.02 ≤0.01 — — — — Mg粉 ≤0.02 ≤0.02 — — ≤0.01 — ≤0.01 ≤0.01 ≤0.01 ≤0.01 ≤0.01 
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表 2 人体模拟液配方
Table 2 Formula of the simulated body fluid
g·L‒1 NaCl NaHCO3 KCl K2HPO4·3H2O MgCl2·6H2O CaCl2 Na2SO4 (CH2OH)3CNH2 8.035 0.355 0.255 0.231 0.311 0.292 0.072 6.118
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表 3 添加不同粒径18%NH4HCO3制备的多孔Ti/16Mg复合材料动电位极化曲线计算结果
Table 3 Calculation results of potentiodynamic polarization curves for the porous Ti/16Mg composites added by 18%NH4HCO3 in different particle sizes
粒径 / μm Ecorr / mV Icorr /
(μA·cm‒2)βa / mV βc / mV Rp /
(Ω·cm‒2)74～125 ‒ 1239 57.754 35.906 278.525 239.125 165～198 ‒ 1214 84.073 67.081 162.996 245.445 245～350 ‒ 1200 110.922 89.081 208.516 244.333
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表 4 添加不同质量分数NH4HCO3制备的多孔Ti/16Mg复合材料动电位极化曲线计算结果
Table 4 Calculation results of potentiodynamic polarization curves for the porous Ti/16Mg composites added by NH4HCO3 in different mass fraction
NH4HCO3
质量分数 / %Ecorr / mV Icorr /
(μA·cm‒2)βa / mV βc / mV Rp /
(Ω·cm‒2)0 ‒ 1084 73.991 193.133 198.543 574.528 6 ‒ 1112 94.770 194.859 210.694 464.324 12 ‒ 1198 45.360 46.224 126.581 324.125 18 ‒ 1214 84.073 67.081 162.996 245.445 24 ‒ 1242 38.859 13.101 254.945 139.236
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