生物医用超细晶钛合金及其表面改性
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摘要
高强度、低弹性模量且不含有害元素的医用钛材的成分、组织结构优化及其表面改性成为当前生物医用植入材料领域的研究热点之一。超细晶/纳米晶结构钛和钛合金由于其优良的力学相容性和生物相容性,在硬组织修复材料领域具有广阔的应用前景。植入体表面的活化处理和多孔结构设计可诱导骨组织向内生长,增加界面结合强度、加快骨修复进程,从而改善治疗效果。超细晶/纳米晶结构钛和钛合金的制备工艺、微观结构、细化机制和化学/电化学反应特性等值得深入研究。
为了研发兼备优良力学性能和表面性能的硬组织替代材料,本文在超细晶钛合金的制备、表征、表面改性及其理论探讨等方面做了如下工作：
1.制备了3种超细晶钛材,对材料的微观结构、形成机理、力学性能、热稳定性及其在模拟体液中的耐蚀性能进行研究,分析其用于硬组织替代材料的可行性。钛表面高能喷丸(HESP)处理工艺制备了表面粗糙度(Ra)-4.8μm、厚度>40μm、晶粒直径(D)-100nm的超细晶层。由OM、XRD、TEM和HRTEM逐层分析变形层微观结构和应力分布的结果表明：高能喷丸处理中,钛表层剧烈塑性变形,首先产生一定量位错,随后变形以孪生为主,产生多系孪晶且发生强烈交割作用,使晶粒不断细化,最终在大的应变量、高应变速率和多方向重复载荷作用下,形成等轴状、随机取向的纳米-亚微米晶粒。经450℃退火处理的样品晶粒尺寸增加不明显,晶体缺陷减少。由于HESP样品表面粗糙度增加、存在宏观缺陷,表面层(0-40μm)在模拟体液中的耐蚀性能有所下降；次表层(40-70μm)内部存在大量非平衡态的界面和位错等,易形成钝化膜,耐蚀抗力改善,但钝态稳定性较差。通过等径角挤压(ECAP)工艺制备了在横截面方向晶粒直径约为200nm、强度增加到1050 MPa的大块超细晶纯钛。经热轧及后续冷轧制备的纳米α+β双相Ti2448钛合金板材达到高强度(～1150 MPa)和低弹性模量(～65 GPa)的最佳结合,且不引入有害合金元素。
2.采用在(CH3COO)2Ca·H2O和NaH2PO4·2H2O混合电解液中的微弧氧化处理工艺,在超细晶ECAP Ti上制备含羟基磷灰石(HA)的多孔结构生物活性氧化层。通过SEM、EDX、XRD、XPS、TEM和EELS等测试手段,对比研究经不同反应时间超细晶钛和粗晶钛表面氧化层的相组成、成份、表面形貌、厚度及微观结构等,分析多孔活性氧化层的形成机理,揭示晶粒细化对微弧氧化行为的影响：含有大量非平衡态的缺陷和晶界的超细晶结构提高了氧、钙、磷等元素的扩散能力,加速了晶态钙磷化合物的生成。相同条件下,超细晶钛表面氧化层的钙、磷含量和钙磷比明显高于粗晶钛上的。经20 min反应的细晶钛表面氧化层中形成纳米晶HA和α-Ca3(PO4)2相,在模拟体液中浸泡2天即可形成类骨磷灰石层,表明其具有优良的生物活性。通过纳米压痕仪和EBSD研究超细晶钛在微弧氧化过程中的热稳定性：对比原始ECAP Ti,20 min反应后的钛基体硬度下降8%到～2.9 GPa,但仍远高于粗晶钛的～1.5 GPa。超细晶ECAP Ti经过合适的微弧氧化处理可获得力学性能和表面生物学性能俱佳的硬组织植入材料。
3.在100℃的5 mol/L NaOH溶液中处理的HESP Ti与CP Ti表面均形成颗粒状的钛酸钠。HESP工艺提高钛表面在碱液中的反应活性,表面颗粒大且多,加速了碱热处理钛表面HA的沉积速度；较大的表面粗糙度提高了矿化层与基体的结合力；在90℃下经5 mol/L NaOH溶液处理的两类钛表面均形成纳米网状结构。两类样品改性层的表面形貌及矿化能力差异不明显：在模拟体液中浸泡14天,样品表面均形成半球状的HA颗粒；HESP Ti表面的HA颗粒较大,某些区域已扩展成层。
由Ca(NO3)2·4H2O和P2O5制备前驱溶液,采用溶胶-凝胶法制备高结晶度的晶粒尺寸为5-10 nm的高纯HA粉末。在HESP Ti表面涂覆的HA层与基体的拉伸强度可达18.0MPa,拉伸时于HA层内部断裂,可见基层结合力大于18.0 MPa。CP Ti基体与HA层的结合力为9.0 MPa,断口在基层的界面处。HESP Ti表面涂层由于其细小的针状组织而具良好的抗凝血性能；
高能喷丸超细晶预处理促进晶态α-Ca3(PO4)2在微弧氧化过程中在钛表面的形成,有效改善表面生物活性；粗糙钛表面上形成的氧化层与基体具有微机械咬合作用,可提高基体和氧化层的结合力。
4.在Ti2448钛合金表面采用微弧氧化法制备含钙、磷元素的多孔氧化层,材料的腐蚀性能、血液相容性等得到改善,基体的力学性能保持稳定(硬度下降3%、弹性模量基本不变),但其生物活性改善不明显。为进一步提高钛合金表面氧化层的生物活性,通过后续浓碱处理在其上制备纳米结构的钛酸钠层(孔径～100 nm),氧化层中磷元素溶解。通过SEM、EDX、XRD和XPS等分析碱处理对氧化层组织、成分和形貌等的影响。在模拟体液中的矿化试验表明,表层Na+和溶液中H3O+交换,形成了Ti-OH,表面带负电,促进了Ca2+和PO43-交替吸附,依次形成钛酸钙、磷酸钙和磷灰石。在矿化过程中,微弧氧化层中的高含量的Ca2+易扩散到模拟体液中,保持体液中Ca2+的过饱和度,从而增加磷灰石生长动力。经20 min氧化及碱处理样品在模拟体液中浸泡10天即可产生类骨磷灰石层,体现出良好生物活性。建立了微弧氧化及后续碱处理工艺的生物活化机制和在模拟体液中的矿化模型。
The improvement of chemical composition and microstructure, surface modification of titanium alloys with high strength and low elastic elastic modulus without the addition of harmful alloying elements have been widely investigated recently for biomedical implants applications. Ultrafine-grained titanium and titanium alloys, owing to their superior bio-conductibility and biocompatiblity, are usually frequently used for orthopedic and dental implants. The preparation process, microstructure, mechanism of grain refinement and response characteristics of ultrafine-grained/nano-crystaline titanium alloys during chemical and electrochemical reaction for surface modification were investigated:
1. Three kinds of ultrafine-grained titanium materials were preduced by severe plastic deformation and alloying processes. An ultrafine-grained surface layer up to 40μm thick was formed on commercially pure (CP) titanium by means of the High energy shot peening (HESP) process. The microstructural features of the HESP Ti surface layer were systematically characterized by cross-sectional optical microscopy observations, transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) investigations. The grain refinement mechanism of the surface layer during the HESP will be analyzed:Firstly, a great deal of dislocations and twin crystals were formed in due order, while severe plastic deformation of the Ti surface layer; After that, the grain size of Ti decreased owing to the interwoven twin crystals cross each other; Finally grains further refined and equiaxed nano-crystaline or sub-micro grains were producted under high-frequency and multi-directional loading. The grain size stability can be maintained up to 450℃, crystal defects decrease after annaling at 450℃. Corrosion resistance of the HESP Ti surface layer with depth within 40μm in SBF was decreased because surface roughness increase and macroscopic defect exist. Accordingly, passive film forming ability and corrosion resistance of subsurface (depth within 40～70μm) enhanced evidently due to their high defect density and a large number of high-energy grain and sub-grain boundaries, which stored a large excess enery as extra driving force. Equal channel angular pressing (ECAP) results in ultrafine-grained (200～500 nm) Ti with superior mechanical properties without harmful alloying elements, which benefits medical implants.
2. To further improve the bioactivity of Ti surfaces, Ca/P-containing porous titania coatings were prepared on ultrafine-grained and coarse-grained Ti by micro-arc oxidation (MAO) in electrolyte mixed with (CH3COO)2Ca·H2O and NaH2PO4·2H2O. The phase identification, composition, morphology and microstructure of the coatings and the thermal stability of ultrafine-grained Ti during MAO were investigated subsequently. The enhanced diffusivity of O, Ca, P and the improvement of the chemical reactivity of Ti may originate from a large volume fraction of non-equilibrium grain boundaries (GBs)/sub-GBs and a considerable amount of defects density (dislocation) in the present ultrafine-grained Ti sample processed by means of the ECAP technique.The amounts of Ca, P and the Ca/P ratio of the coatings formed on ultrafine-grained Ti were higher than those on coarse-grained Ti. Nanocrystalline hydroxyapatite (HA) and a-Ca3(PO4)2 phases appeared in the MAO coating formed on ultrafine-grained Ti for 20 min (E20). Incubated in a simulated body fluid, bone-like apatite was completely formed on the surface of E20 for 2 days, as evidence of preferable bioactivity. Compared with initial ultrafine-grained Ti, the microhardness of the E20 substrate was reduced by 8% to 2.9 GPa, which is considerably higher than that of coarse-grained Ti (～1.5 GPa). Therefore, the reuslts clearly demonstrate that the MAO coating formed on the ECAP-treated Ti exhibits an optimum combination of mechanical and bioactivity.
3. The CP Ti and HESP Ti specimens were soaked in 5 mol/L solution of NaOH at temperatures of 100℃and 90℃. Lots of granular sodium titanate was formed on their surfaces at 100℃. The HESP process enhanced the chemical reactivity of the Ti, the sodium titanate particles become larger in size and amount. The acceleration in the rate of apatite formation is significant, as it should allow for earlier load bearing of prostheses following implantation. Surface roughness increasement narrowed the coating cracks, and enhanced the cohesion between the substrate and coating. A thin nano-porous network structural sodium titanate layer formed on the two kinds of substrate by the NaOH treatment at 90℃. Hemispherical HA deposition formed on the treated Ti surface when immersed in SBF for 14 days. The larger HA particles formed on the HESP Ti, which have already spread out and become layer on some areas.
Nano-crystaline HA powders with grain size of 5-10 nm and HA coatings on HESP Ti and CP Ti were prepared by the sol-gel technique using Ca(NO3)2·4H2O and P2O5 as calcium and phosphorus precursors, respectively. The coating layer formed on HESP Ti was porous, and adhered to HESP Ti substrate strongly with adhesion strength of about 18.0 MPa. Adhesion strength between HA coating and CP Ti was 9.0 MPa. The coating on HESP Ti has better anticoagulant property, because of their small acicular structrue.
To improve the bioactivity of Ti surfaces, porous titania coating were prepared on HESP and CP Ti by MAO. The phase identification, thickness, composition and morphology of the coating were analyzed. The amounts of Ca, P and Ca/P ratio of the MAO coating formed on the HESP-treated Ti were higher than those of CP Ti obviously. The a-Ca3(PO4)2 phase appeared in H10 MAO coating. Due to roughness of HESP Ti increased, the oxidation rate is different in different locations, which leads the micro-mechanical occlusion and cohesion improvement between substrate and coating.
4. Nanostructured Ti2448 alloy (Ti-24Nb-4Zr-7.9Nb), which contains no harmful elements and has an elastic modulus close to human bone and high strength, the alloy has been processed by MAO in a solution containing Ca/P. The corrosion resistance, hemocompatibility of Ti2448 alloy with composite coatings was superior evidently to that with merely MAO film, but the influence of MAO process on the bioactivity improvment of the Ti2448 alloy substrate is not quite obvious. To further improve bioactivity of Ti2448 alloys, a surface layer containing porous titania and sodium titanate is successfully formed by subsequent Alkline treatment. The phase identification, composition and morphology of the MAO coatings before and after alkaline treatment (MAO-A) were analyzed by XRD, SEM equipped with EDX and XPS. The amounts of Ca, P in MAO coating increased with increasing oxidation time, but the P element dissolved into the NaOH solution after alkaline treatment. It was demonstrated that alkaline treatment significantly improves the bioactivity of coatings as compared with MAO alone. Soaking in the SBF, Na+ ions in the MAO-A samples were release via exchange with the H3O+ ions in the fluid to form Ti-OH (Nb-OH) groups, which accelerated the nucleation of hydroxyapatite in SBF. Compared with sample T05A, which contains 3.6% Ca, incubated in SBF within 7 days, bone-like apatite was formed on sample T20A (contains 12% Ca), together with improved bioactivity. Mineralization experiments show that a high concentration of Ca in the MAO coating leads to a preferred release into SBF to keep its high consistency of Ca2+ and leads to accelerated growth of hydroxyapatite.
为了研发兼备优良力学性能和表面性能的硬组织替代材料,本文在超细晶钛合金的制备、表征、表面改性及其理论探讨等方面做了如下工作：
1.制备了3种超细晶钛材,对材料的微观结构、形成机理、力学性能、热稳定性及其在模拟体液中的耐蚀性能进行研究,分析其用于硬组织替代材料的可行性。钛表面高能喷丸(HESP)处理工艺制备了表面粗糙度(Ra)-4.8μm、厚度>40μm、晶粒直径(D)-100nm的超细晶层。由OM、XRD、TEM和HRTEM逐层分析变形层微观结构和应力分布的结果表明：高能喷丸处理中,钛表层剧烈塑性变形,首先产生一定量位错,随后变形以孪生为主,产生多系孪晶且发生强烈交割作用,使晶粒不断细化,最终在大的应变量、高应变速率和多方向重复载荷作用下,形成等轴状、随机取向的纳米-亚微米晶粒。经450℃退火处理的样品晶粒尺寸增加不明显,晶体缺陷减少。由于HESP样品表面粗糙度增加、存在宏观缺陷,表面层(0-40μm)在模拟体液中的耐蚀性能有所下降；次表层(40-70μm)内部存在大量非平衡态的界面和位错等,易形成钝化膜,耐蚀抗力改善,但钝态稳定性较差。通过等径角挤压(ECAP)工艺制备了在横截面方向晶粒直径约为200nm、强度增加到1050 MPa的大块超细晶纯钛。经热轧及后续冷轧制备的纳米α+β双相Ti2448钛合金板材达到高强度(～1150 MPa)和低弹性模量(～65 GPa)的最佳结合,且不引入有害合金元素。
2.采用在(CH3COO)2Ca·H2O和NaH2PO4·2H2O混合电解液中的微弧氧化处理工艺,在超细晶ECAP Ti上制备含羟基磷灰石(HA)的多孔结构生物活性氧化层。通过SEM、EDX、XRD、XPS、TEM和EELS等测试手段,对比研究经不同反应时间超细晶钛和粗晶钛表面氧化层的相组成、成份、表面形貌、厚度及微观结构等,分析多孔活性氧化层的形成机理,揭示晶粒细化对微弧氧化行为的影响：含有大量非平衡态的缺陷和晶界的超细晶结构提高了氧、钙、磷等元素的扩散能力,加速了晶态钙磷化合物的生成。相同条件下,超细晶钛表面氧化层的钙、磷含量和钙磷比明显高于粗晶钛上的。经20 min反应的细晶钛表面氧化层中形成纳米晶HA和α-Ca3(PO4)2相,在模拟体液中浸泡2天即可形成类骨磷灰石层,表明其具有优良的生物活性。通过纳米压痕仪和EBSD研究超细晶钛在微弧氧化过程中的热稳定性：对比原始ECAP Ti,20 min反应后的钛基体硬度下降8%到～2.9 GPa,但仍远高于粗晶钛的～1.5 GPa。超细晶ECAP Ti经过合适的微弧氧化处理可获得力学性能和表面生物学性能俱佳的硬组织植入材料。
3.在100℃的5 mol/L NaOH溶液中处理的HESP Ti与CP Ti表面均形成颗粒状的钛酸钠。HESP工艺提高钛表面在碱液中的反应活性,表面颗粒大且多,加速了碱热处理钛表面HA的沉积速度；较大的表面粗糙度提高了矿化层与基体的结合力；在90℃下经5 mol/L NaOH溶液处理的两类钛表面均形成纳米网状结构。两类样品改性层的表面形貌及矿化能力差异不明显：在模拟体液中浸泡14天,样品表面均形成半球状的HA颗粒；HESP Ti表面的HA颗粒较大,某些区域已扩展成层。
由Ca(NO3)2·4H2O和P2O5制备前驱溶液,采用溶胶-凝胶法制备高结晶度的晶粒尺寸为5-10 nm的高纯HA粉末。在HESP Ti表面涂覆的HA层与基体的拉伸强度可达18.0MPa,拉伸时于HA层内部断裂,可见基层结合力大于18.0 MPa。CP Ti基体与HA层的结合力为9.0 MPa,断口在基层的界面处。HESP Ti表面涂层由于其细小的针状组织而具良好的抗凝血性能；
高能喷丸超细晶预处理促进晶态α-Ca3(PO4)2在微弧氧化过程中在钛表面的形成,有效改善表面生物活性；粗糙钛表面上形成的氧化层与基体具有微机械咬合作用,可提高基体和氧化层的结合力。
4.在Ti2448钛合金表面采用微弧氧化法制备含钙、磷元素的多孔氧化层,材料的腐蚀性能、血液相容性等得到改善,基体的力学性能保持稳定(硬度下降3%、弹性模量基本不变),但其生物活性改善不明显。为进一步提高钛合金表面氧化层的生物活性,通过后续浓碱处理在其上制备纳米结构的钛酸钠层(孔径～100 nm),氧化层中磷元素溶解。通过SEM、EDX、XRD和XPS等分析碱处理对氧化层组织、成分和形貌等的影响。在模拟体液中的矿化试验表明,表层Na+和溶液中H3O+交换,形成了Ti-OH,表面带负电,促进了Ca2+和PO43-交替吸附,依次形成钛酸钙、磷酸钙和磷灰石。在矿化过程中,微弧氧化层中的高含量的Ca2+易扩散到模拟体液中,保持体液中Ca2+的过饱和度,从而增加磷灰石生长动力。经20 min氧化及碱处理样品在模拟体液中浸泡10天即可产生类骨磷灰石层,体现出良好生物活性。建立了微弧氧化及后续碱处理工艺的生物活化机制和在模拟体液中的矿化模型。
The improvement of chemical composition and microstructure, surface modification of titanium alloys with high strength and low elastic elastic modulus without the addition of harmful alloying elements have been widely investigated recently for biomedical implants applications. Ultrafine-grained titanium and titanium alloys, owing to their superior bio-conductibility and biocompatiblity, are usually frequently used for orthopedic and dental implants. The preparation process, microstructure, mechanism of grain refinement and response characteristics of ultrafine-grained/nano-crystaline titanium alloys during chemical and electrochemical reaction for surface modification were investigated:
1. Three kinds of ultrafine-grained titanium materials were preduced by severe plastic deformation and alloying processes. An ultrafine-grained surface layer up to 40μm thick was formed on commercially pure (CP) titanium by means of the High energy shot peening (HESP) process. The microstructural features of the HESP Ti surface layer were systematically characterized by cross-sectional optical microscopy observations, transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) investigations. The grain refinement mechanism of the surface layer during the HESP will be analyzed:Firstly, a great deal of dislocations and twin crystals were formed in due order, while severe plastic deformation of the Ti surface layer; After that, the grain size of Ti decreased owing to the interwoven twin crystals cross each other; Finally grains further refined and equiaxed nano-crystaline or sub-micro grains were producted under high-frequency and multi-directional loading. The grain size stability can be maintained up to 450℃, crystal defects decrease after annaling at 450℃. Corrosion resistance of the HESP Ti surface layer with depth within 40μm in SBF was decreased because surface roughness increase and macroscopic defect exist. Accordingly, passive film forming ability and corrosion resistance of subsurface (depth within 40～70μm) enhanced evidently due to their high defect density and a large number of high-energy grain and sub-grain boundaries, which stored a large excess enery as extra driving force. Equal channel angular pressing (ECAP) results in ultrafine-grained (200～500 nm) Ti with superior mechanical properties without harmful alloying elements, which benefits medical implants.
2. To further improve the bioactivity of Ti surfaces, Ca/P-containing porous titania coatings were prepared on ultrafine-grained and coarse-grained Ti by micro-arc oxidation (MAO) in electrolyte mixed with (CH3COO)2Ca·H2O and NaH2PO4·2H2O. The phase identification, composition, morphology and microstructure of the coatings and the thermal stability of ultrafine-grained Ti during MAO were investigated subsequently. The enhanced diffusivity of O, Ca, P and the improvement of the chemical reactivity of Ti may originate from a large volume fraction of non-equilibrium grain boundaries (GBs)/sub-GBs and a considerable amount of defects density (dislocation) in the present ultrafine-grained Ti sample processed by means of the ECAP technique.The amounts of Ca, P and the Ca/P ratio of the coatings formed on ultrafine-grained Ti were higher than those on coarse-grained Ti. Nanocrystalline hydroxyapatite (HA) and a-Ca3(PO4)2 phases appeared in the MAO coating formed on ultrafine-grained Ti for 20 min (E20). Incubated in a simulated body fluid, bone-like apatite was completely formed on the surface of E20 for 2 days, as evidence of preferable bioactivity. Compared with initial ultrafine-grained Ti, the microhardness of the E20 substrate was reduced by 8% to 2.9 GPa, which is considerably higher than that of coarse-grained Ti (～1.5 GPa). Therefore, the reuslts clearly demonstrate that the MAO coating formed on the ECAP-treated Ti exhibits an optimum combination of mechanical and bioactivity.
3. The CP Ti and HESP Ti specimens were soaked in 5 mol/L solution of NaOH at temperatures of 100℃and 90℃. Lots of granular sodium titanate was formed on their surfaces at 100℃. The HESP process enhanced the chemical reactivity of the Ti, the sodium titanate particles become larger in size and amount. The acceleration in the rate of apatite formation is significant, as it should allow for earlier load bearing of prostheses following implantation. Surface roughness increasement narrowed the coating cracks, and enhanced the cohesion between the substrate and coating. A thin nano-porous network structural sodium titanate layer formed on the two kinds of substrate by the NaOH treatment at 90℃. Hemispherical HA deposition formed on the treated Ti surface when immersed in SBF for 14 days. The larger HA particles formed on the HESP Ti, which have already spread out and become layer on some areas.
Nano-crystaline HA powders with grain size of 5-10 nm and HA coatings on HESP Ti and CP Ti were prepared by the sol-gel technique using Ca(NO3)2·4H2O and P2O5 as calcium and phosphorus precursors, respectively. The coating layer formed on HESP Ti was porous, and adhered to HESP Ti substrate strongly with adhesion strength of about 18.0 MPa. Adhesion strength between HA coating and CP Ti was 9.0 MPa. The coating on HESP Ti has better anticoagulant property, because of their small acicular structrue.
To improve the bioactivity of Ti surfaces, porous titania coating were prepared on HESP and CP Ti by MAO. The phase identification, thickness, composition and morphology of the coating were analyzed. The amounts of Ca, P and Ca/P ratio of the MAO coating formed on the HESP-treated Ti were higher than those of CP Ti obviously. The a-Ca3(PO4)2 phase appeared in H10 MAO coating. Due to roughness of HESP Ti increased, the oxidation rate is different in different locations, which leads the micro-mechanical occlusion and cohesion improvement between substrate and coating.
4. Nanostructured Ti2448 alloy (Ti-24Nb-4Zr-7.9Nb), which contains no harmful elements and has an elastic modulus close to human bone and high strength, the alloy has been processed by MAO in a solution containing Ca/P. The corrosion resistance, hemocompatibility of Ti2448 alloy with composite coatings was superior evidently to that with merely MAO film, but the influence of MAO process on the bioactivity improvment of the Ti2448 alloy substrate is not quite obvious. To further improve bioactivity of Ti2448 alloys, a surface layer containing porous titania and sodium titanate is successfully formed by subsequent Alkline treatment. The phase identification, composition and morphology of the MAO coatings before and after alkaline treatment (MAO-A) were analyzed by XRD, SEM equipped with EDX and XPS. The amounts of Ca, P in MAO coating increased with increasing oxidation time, but the P element dissolved into the NaOH solution after alkaline treatment. It was demonstrated that alkaline treatment significantly improves the bioactivity of coatings as compared with MAO alone. Soaking in the SBF, Na+ ions in the MAO-A samples were release via exchange with the H3O+ ions in the fluid to form Ti-OH (Nb-OH) groups, which accelerated the nucleation of hydroxyapatite in SBF. Compared with sample T05A, which contains 3.6% Ca, incubated in SBF within 7 days, bone-like apatite was formed on sample T20A (contains 12% Ca), together with improved bioactivity. Mineralization experiments show that a high concentration of Ca in the MAO coating leads to a preferred release into SBF to keep its high consistency of Ca2+ and leads to accelerated growth of hydroxyapatite.
引文
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