在钛基合金表面水热电化学沉积羟基磷灰石涂层

在Ca~(2+)、H_2PO_4~-和NO_3~–离子浓度分别为0.025 mol/L、0.015 mol/L和0.1 mol/L电解液中加入2.5×10~(-4)mol/L的柠檬酸钠,采用水热电化学方法在Ti6Al4V基体表面沉积羟基磷灰石涂层,研究了柠檬酸根对羟基磷灰石(HA)涂层的物相组成、形貌及结合强度的影响以及沉积时间对HA涂层物相、形貌、结晶度、涂层厚度及结合强度的影响。结果表明:在含柠檬酸根电解液中水热电化学沉积的仍为HA涂层,与不含柠檬酸根的电解液相比,HA晶体的尺寸显著减小,涂层表面更加均匀致密,涂层与基体之间的结合强度由15.39 MPa提高到24.31 MPa;HA(002)晶面的衍射峰随着水热电化学沉积时间的增加先增强后减弱,在沉积2 h时达到最大,HA晶粒尺寸较小,涂层更为均匀致密。随着沉积时间的增加,HA涂层厚度呈非线性增加,HA涂层的结晶度和结合强度均,先增大后减小,沉积时间为2 h时结晶度和结合强度分别达到最大值为75.7%和24.31 MPa。     

阳极氧化对钛合金表面HA-TiO2复合涂层的影响

对钛合金表面进行阳极氧化预处理,然后用水热电化学方法在其上沉积羟基磷灰石-二氧化钛(HA-TiO2)复合涂层,研究了阳极电压对基体表面的物相、形貌、润湿性和粗糙度的影响,以及对HA的物相、形貌及生物活性的影响。结果表明:阳极氧化电压高于110 V时在钛基体表面出现金红石型和锐钛矿型TiO2,孔径尺寸随阳极电压的增加而增大。在120 V预处理的钛合金试样表面具有好的润湿性,粗糙度Ra达到0.56μm。HA涂层沿c轴方向择优生长,并呈现分层生长,HA的结晶度随着阳极氧化电压的提高先增大后减小,在120 V取得最大值。在120 V氧化处理的试样具有较好的生物活性。     

喷砂酸蚀处理促进Ti6Al7Nb表面钙磷沉积

研究了Ti、Ti6Al4V和Ti6Al7Nb 3种钛基材料在喷砂酸蚀处理后成骨细胞在其表面生长的生物活性。通过Al2O3喷砂和盐酸、硫酸混合物酸蚀的表面改性方法,在Ti、Ti6Al4V和Ti6Al7Nb3种钛基材料表面进行喷砂酸蚀处理,通过SEM观察样品的表面形貌,样品的表面呈现出微米级多孔形貌;将样品浸入模拟体液(simulated body fluid,SBF)中浸泡7,14和21 d后通过SEM、X射线衍射仪(XRD)分析样品表面沉积物的形貌、物相,样品浸入SBF 14 d后,Ti6Al7Nb表面最先观察到表面覆盖的羟基磷灰石涂层;样品浸入SBF 21 d后,Ti、Ti6Al4V和Ti6Al7Nb表面都观察到羟基磷灰石涂层。羟基磷灰石涂层有利于促进钛基植入体与体内骨组织的骨结合,喷砂酸蚀处理的Ti6Al7Nb表现出良好的生物活性。     

电沉积镍-羟基磷灰石复合涂层的研究

在镀镍液中加人少量的Ca(NO3)2、NH4H2PO4，在钛基体上实现在电沉积过程中羟基磷灰石(HA)和Ni的共沉积，实验探讨了电流密度、钙、磷浓度对涂层表面形貌、HA含量及涂层结合强度的影响。实验结果表明：涂层中HA的含量随电流密度和钙、磷浓度的增加而提高，但涂层结合强度先增大后减小，Ni-HA复合涂层的结合强度明显高于纯HA涂层的结合强度。通过控制适当的电沉积条件，在[Ca^2 ]=0．01mol／L，电流密度jc=20—30mA/cm^2时，可以制得HA分散较为均匀、结合强度较高的Ni-HA复合涂层。     

阳极氧化电解质的组分对钛基体和表面涂层的影响

在浓度为0.15 mol/L的HF电解液中加入浓度为5 g/L的磷酸二氢钙(Ca(H_2PO_4)_2)进行阳极氧化,研究了Ca和P对阳极氧化后钛合金表面的物相组成和形貌的影响;进而用水热电化学方法在Ti6Al4V基体表面进行阴极沉积,研究了Ca、P元素对羟基磷灰石(HA)涂层物相、形貌、涂层结合强度的影响。进行细胞的粘附实验,测试了涂层的生物活性。结果表明:含有磷酸二氢钙的电解液阳极氧化后TiO_2纳米管的管径比未加磷酸二氢钙的管径大,表面的Ca、P含量提高,且Ca的含量明显变化。用水热电化学沉积生成的HA涂层表现为分层生长模式,下层为致密均匀的棒状,上层则为丰富度更大的团絮状。涂层与基体的结合强度由18.93 MPa提高到23.74 MPa。在粘附实验过程中细胞更易于依附团絮状HA涂层生长,加入磷酸二氢钙后团絮状羟基磷灰石增多,增大了细胞的依附生长空间,为细胞提供更大的生长接触面积,有利于植入体与人体结合。     

沉积电压对Hap-PAM生物涂层结构及性能的影响

为了提高生物惰性材料C/C的生物活性以及C/C基体与生物活性材料羟基磷灰石(HAp)的结合强度, 以丙烯酰胺单体(AM)和声化学制备的纳米HAp为原料, 异丙醇为分散介质, 采用水热电泳聚合沉积法在C/C复合材料表面制备了羟基磷灰石-聚丙烯酰胺(HAp-PAM)生物复合涂层。用XRD、 TEM、 SEM、 FTIR、 力学性能测试等手段对涂层的相组成、 官能团、 断面的微观形貌及结合强度进行了测试和表征, 研究了水热沉积电压对复合涂层结构和性能的影响。结果表明: 随着沉积电压的升高, 涂层中HAp的衍射峰呈现先增强后减小的趋势, PAM的衍射峰逐渐消失; 涂层的结合强度随着电压的升高先增强后减小。沉积电压为150 V时, 涂层的致密性和均匀性达到最佳, 涂层的厚度以及涂层与基体的结合强度分别达到最大值25 μm 和19 MPa。      

射频磁控溅射含氟羟基磷灰石涂层的研究

本文采用射频磁控溅射技术在钛合金(Ti6Al4V)基体上制备出含氟羟基磷灰石(FHA)生物涂层,探讨该涂层组织结构,不同氟含量和温度对涂层晶化程度的影响.利用扫描电镜(SEM)观察FHA生物涂层的表面形貌,采用X射线衍射仪(XRD)分析涂层相结构,利用能量分散谱仪(EDS)分析涂层的Ca/P比.结果表明,随着氟含量的增加可大大提高涂层的晶化程度,制备的FHA涂层致密、均匀.700℃晶化处理的涂层结晶度较高.     

镁合金表面电化学沉积制备羟基磷灰石涂层及耐腐蚀性能的研究

采用电化学沉积技术和水热合成技术在镁合金表面制备出均匀的羟基磷灰石(HA)涂层。运用扫描电镜(SEM)分析涂层的微观形貌、运用能谱(EDS)分析涂层的元素组成、和运用X射线衍射仪(XRD)分析涂层相的组成,并且在人体模拟液(SBF)中考察了其电化学性能。结果表明:与恒电流沉积制备出的HA相比,脉冲电流沉积制备出的涂层更加均匀致密;与镁合金基体的自腐蚀电流密度8.407×10~(-4) A/cm~2比较,恒电流和脉冲电流沉积的涂层自腐蚀电流密度分别为2.780×10~(-5)和5.582×10~(-7) A/cm~2,其耐蚀性明显得到提高。在镁合金表面用电化学沉积法制备的羟基磷灰石涂层可以有效的降低镁合金的降解率,从而使得镁合金进一步应用于生物材料。     

钛涂覆多孔羟基磷灰石涂层的制备及其生物活性

在纯钛基体表面通过电泳沉积的方法制得壳聚糖/羟基磷灰石(CS/HA)复合涂层, 然后将复合涂层烧结形成多孔HA涂层。采用SEM对多孔HA涂层的形貌进行观察, XRD分析涂层的物相组成, 粘结拉伸实验测定涂层与基体的结合强度, 1.5倍人体模拟体液(1.5SBF)浸泡测定涂层的生物活性。结果表明: 当悬浮液中CS与HA质量比为1∶1时, 制得的CS/HA复合涂层经过700℃烧结处理, 涂层中CS热分解致孔形成多孔HA涂层, 孔径在10~25 μm, 涂层与基体的结合强度可达19.5 MPa; 在1.5SBF中浸泡5天后, 多孔HA涂层表面完全碳磷灰石化, 呈现较好的生物活性。      

碳/碳复合材料表面的含氟磷灰石生物活性涂层

用超声电沉积与离子交换相结合的方法在碳/碳复合材料表面制备含氟磷灰石(FHA)生物活性涂层,研究了离子交换时间和氟化钠浓度对含氟磷灰石(FHA)生物活性涂层的形貌、结构和组成的影响.结果表明:离子交换后的涂层是羟基磷灰石(HA)和含氟磷灰石(FHA)混合物,离子交换前后其表面形貌均呈片状晶体.随着离子交换时间的延长或氟化钠浓度的增加,HA含量降低,FHA含量升高,涂层的晶粒尺寸和致密性均发生变化.离子交换后其涂层与基体的结合强度略有增强,其原因是FHA的热膨胀系数与碳/碳复合材料基体更为匹配,涂层的残余应力减小.     

Structure and properties of hydroxyapatite-bioactive glass composites plasma sprayed on Ti6Al4V

Hydroxyapatite (HA)-coated Ti6Al4V has recently been used as a bone substitute in orthopaedic and dental applications because of its favourable bioactivity and mechanical properties. Studies in the literature have shown that the bioactivity of calcium phosphate bioactive glass (BG) is higher than that of HA. In an attempt to increase the bioactivity of Ha-coated Ti6Al4V and enhance the bonding strength between coating and substrate, in the present study, HA/BG composites are applied onto Ti6Al4V using a plasma spraying technique. Microstructure and phase changes of the composite coating after plasma spraying are studied. The coating-substrate bonding strength is evaluated using an Instron, following the ASTM C633 method. Results indicate that the average bonding strengths of BG, HA/BG and HA coatings are 33.0±4.3, 39.1±5.0, and 52.0±11.7 MPa, respectively. Open pores with sizes up to 50 m are found in both BG and HA/BG coatings, which are probably advantageous in including mechanical interlocking with the surrounding bone structure, once implanted. These HA/BG composites could provide a coating system with sufficient bonding strength, higher bioactivity, and a significant reduction in cost in raw materials. The future of this HA/BG composite coating system seems pretty bright.     

Ti6Al4V钛合金表面Ta2O5/Ta2O5-Ti/Ti多涂层的制备与性能研究

采用磁控溅射技术在Ti6Al4V钛合金表面制备了Ta_2O_5/Ta_2O_5-Ti/Ti多层涂层;利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)和X射线光电子能谱仪 (XPS),分析了涂层的微观结构、物性组成和化学价态;通过划痕仪、纳米压痕仪、摩擦磨损试验机和电化学工作站,检测了涂层的结合强度、力学性能、摩擦系数和耐腐蚀性。研究结果表明,Ta_2O_5/Ta_2O_5-Ti/Ti多层涂层表面由峰型颗粒组成,粒径大小均匀,涂层结构致密。与Ti6Al4V相比,Ta_2O_5/Ta_2O_5-Ti/Ti多层涂层试样具有较小的摩擦系数,较高的腐蚀电位和较小的腐蚀电流密度,表现出良好的耐磨和耐腐蚀性能,能对Ti6Al4V合金植入材料起到较好的保护作用。     

等离子喷涂HA/Ti复合涂层研究 I.结构、组成和力学性能

采用等离子喷涂方法,在Ｔｉ－６Ａｌ－４Ｖ基体上成功地制备了ＨＡ／Ｔｉ复合涂层,并对复合涂层的微观结构,相组成和力学性能进行了研究。结果表明,ＨＡ和Ｔｉ两相均匀地分布于复合涂层中。ＨＡ／Ｔｉ复合涂层的结合强度明显高于纯ＨＡ涂层,这主要是由于ＨＡ／Ｔｉ的复合和了涂层与基体之间的热膨胀系数失配,ＨＡ／Ｔｉ复合涂层在模拟体液中浸泡一段时间后,结合强度没有明显降低,ＨＡ／Ｔｉ复合涂层的断裂韧性和硬度均高于Ｈ     

等离子喷涂HA/Ti复合涂层研究 I.结构、组成和力学性能

采用等离子喷涂方法,在Ｔｉ－６Ａｌ－４Ｖ基体上成功地制备了ＨＡ／Ｔｉ复合涂层,并对复合涂层的微观结构、相组成和力学性能进行了研究．结果表明,ＨＡ和Ｔｉ两相均匀地分布于复合涂层中．ＨＡ／Ｔｉ复合涂层的结合强度明显高于纯 ＨＡ涂层,这主要是由于 ＨＡ／Ｔｉ的复合缓和了涂层与基体之间的热膨胀系数失配．ＨＡ／Ｔｉ复合涂层在模拟体液中浸泡一段时间后,结合强度没有明显降低．ＨＡ／Ｔｉ复合涂层的断裂韧性和硬度均高于 ＨＡ涂层．     

Fabrication of nano-structured HA/CNT coatings on Ti6Al4V by electrophoretic deposition for biomedical applications

In order to improve the bone bioactivity and osteointegration of metallic implants, hydroxyapatite (HA) is often coated on their surface so that a real bond with the surrounding bone tissue can be formed. In the present study, cathodic electrophoretic deposition (EPD) has been attempted for depositing nanostructured HA coatings on titanium alloy Ti6Al4V followed by sintering at 800 degrees C. Nano-sized HA powder was used in the EPD process to produce dense coatings. Moreover, multiwalled carbon nanotubes (CNTs) were also used to reinforce the HA coating for enhancing its mechanical strength. The surface morphology, compositions and microstructure of the monolithic coating of HA and nanocomposite coatings of HA with different CNT contents (4 to 25%) on Ti6Al4V were investigated by scanning-electron microscopy, energy-dispersive X-ray spectroscopy and Xray diffractometry, respectively. Electrochemical corrosion behavior of the various coatings in Hanks' solution at 37 degrees C was investigated by means of open-circuit potential measurement and cyclic potentiodynamic polarization tests. Surface hardness, adhesion strength and bone bioactivity of the coatings were also studied. The HA and HA/CNT coatings had a thickness of about 10 microm, with corrosion resistance higher than that of the substrate and adhesion strength higher than that of plasma sprayed HA coating. The properties of the composite coatings were optimized by varying the CNT contents. The enhanced properties could be attributed to the use of nano-sized HA particles and CNTs. Compared with the monolithic HA coating, the CNT-reinforced HA coating markedly increased the coating hardness without deteriorating the corrosion resistance or adhesion strength.     

Hydroxyapatite-anatase-carbon nanotube nanocomposite coatings fabricated by electrophoretic codeposition for biomedical applications

In order to eliminate micro-cracks in the monolithic hydroxyapatite (HA) and composite hydroxyapatite/carbon nanotube (HA/CNT) coatings, novel HA/TiO₂/CNT nanocomposite coatings on Ti6Al4V were attempted to fabricate by a single-step electrophoretic codeposition process for biomedical applications. The electrophoretically deposited layers with difference contents of HA, TiO₂ (anatase) and CNT nanoparticles were sintered at 800°C for densification with thickness of about 7–10 μm. A dense and crack-free coating was achieved with constituents of 85 wt% HA, 10 wt% TiO₂ and 5 wt% CNT. Open-circuit potential measurements and cyclic potentiodynamic polarization tests were used to investigate the electrochemical corrosion behavior of the coatings in vitro conditions (Hanks’ solution at 37°C). The HA/TiO₂/CNT coatings possess higher corrosion resistance than that of the Ti6Al4V substrate as reflected by nobler open circuit potential and lower corrosion current density. In addition, the surface hardness and adhesion strength of the HA/TiO₂/CNT coatings are higher than that of the monolithic HA and HA/CNT coatings without compromising their apatite forming ability. The enhanced properties were attributed to the nanostructure of the coatings with the appropriate TiO₂ and CNT contents for eliminating micro-cracks and micro-pores.     

Influence of boron doping on mechanical and tribological properties in multilayer CVD-diamond coating systems

Titanium alloy (Ti6Al4V) substrates were deposited with smooth multilayer coatings, by hot filament chemical vapour deposition technique. The effect of boron doping on lattice parameter, residual stresses, hardness and coefficient of friction in multilayer-diamond coating system was studied. The frictional behaviour of the coatings was studied using a ball-on-disc micro-tribometer by sliding the coated samples of titanium alloy (Ti6Al4V) substrates against alumina (Al₂O₃) balls, and increasing normal load from 1 to 10 N. The average friction coefficient decreased from 0.36 to 0.29 for undoped multilayer-diamond coating system and from 0.33 to 0.18 for boron- doped (BD) multilayer-diamond coating system. The average indentation depths for undoped and BD multilayer- diamond coating systems were found to be equal to ～>58 and ～65 nm, respectively, and their hardness values were 60 and 55 GPa, respectively.     

Laser engineered multilayer coating of biphasic calcium phosphate/titanium nanocomposite on metal substrates

In this work, laser coating of biphasic calcium phosphate/titanium (BCP/Ti) nanocomposite on Ti-6Al-4 V substrates was developed. A continuous wave neodymium-doped yttrium aluminium garnet (Nd:YAG) laser was used to form a robust multilayer of BCP/Ti nanocomposite starting from hydroxyapatite and titanium nanoparticles. In this process, low power coating is realized because of the strong laser-nanoparticle interaction and good sinterability of nanosized titanium. To guide the optimization of laser processing conditions for the coating process, a multiphysics model coupling electromagnetic module with heat transfer module was developed. This model was validated by laser coating experiments. Important features of the coated samples, including microstructures, chemical compositions, and interfacial bonding strength, were characterized. We found that a multilayer of BCP, consisting of 72% hydroxyapatite (HA) and 28% beta-tricalcium phosphate (β-TCP), and titanium nanocomposite was formed on Ti-6Al-4 V substrates. Significantly, the coating/substrate interfacial bonding strength was found to be two times higher than that of the commercial plasma sprayed coatings. Preliminary cell culture studies showed that the resultant BCP/Ti nanocomposite coating supported the adhesion and proliferation of osteoblast-like UMR-106 cells.     

Surface characterization of colloidal-sol gel derived biphasic HA/FA coatings

Hydroxyapatite (HA) powders are ultrasonically dispersed in the precursor of fluoridated hydroxyapatite (FHA) or fluorapatite (FA) to form a “colloidal sol”. HA/FA biphasic coatings are prepared on Ti6Al4V substrate via dip coating, 150 °C drying and 600 °C firing. The coatings show homogenous distribution of HA particles in the FA matrix. The relative phase proportion can be tailored by the amount of HA in the colloidal sol. The surfaces of the coatings consist of two kinds of distinct domains: HA and FA, resulting in a compositionally heterogeneous surface. The biphasic coating surface becomes increasingly rougher with HA powders, from around 200 nm of pure FA to 400–600 nm in Ra of biphasic coatings. The rougher biphasic HA/FA surfaces with chemically controllable domains will favor cell attachment, apatite layer deposition and necessary dissolution in clinical applications.     

Ti-6Al-4V合金基体等离子喷涂生物活性羟基磷灰涂层的研究进展

系统阐述了在钛合金(Ti-6Al-4V)表面等离子喷涂羟基磷灰石(HA)涂层的研究进展.描述了等离子喷涂制备HA涂层的工艺过程、微观形貌和化学组成.综述几种综合性能较高的复合型涂层:HA/BG(生物活性玻璃)复合涂层,HA/ZrO2复合增强型涂层,HA/Ti涂层,HA/Ti-6Al-4V梯度涂层;并对HA涂层发展趋势进行了展望.