Fabrication of Mesoporous Hydroxycarbonate Apatite/Polyaniline Composite Coatings on Ti6Al4V Substrates

采用电泳沉积法在 Ti6Al4V 基体上形成碳酸钙/聚苯胺复合涂层,然后经磷酸缓冲溶液 37 ℃下浸泡处理得到介孔碳酸根型羟基磷灰石/聚苯胺复合涂层。无裂纹的碳酸钙/聚苯胺复合涂层通过溶解-沉积反应转化成具有片状结构的碳酸根型羟基磷灰石/聚苯胺复合涂层,介孔和大孔分别存在于片状磷灰石内部和之间。模拟体液浸泡实验表明,多孔结构可以提高涂层的体外磷灰石形成活性,类骨型磷灰石首先沉积在介孔上,然后随着浸泡时间的延长逐渐覆盖所有大孔。此外,碳酸根型羟基磷灰石/聚苯胺复合涂层的体外磷灰石形成活性与聚苯胺纳米线有关,聚苯胺上的官能团(H2PO4-)不仅可以提高局部过饱和度,而且可以促进类骨型磷灰石的形核和生长。     

低温制备片状磷灰石生物陶瓷

采用磷酸缓冲溶液浸泡法在37℃制备了碳酸根型磷灰石,借助XRD,FTIR,SEM,DSC-TG等分析手段研究了磷灰石的形貌、结构、热稳定性以及形成机理.结果表明,碳酸钙浸泡到磷酸缓冲溶液后,碳酸钙表面部分溶解,然后沉积上一层具有低结晶度的片状磷灰石;磷灰石的转化率,随磷酸缓冲溶液浸泡时间的延长而提高,但转化速率随之下降磷灰石降低了残留碳酸钙的热稳定性,DSC的吸热峰从810℃迁移到755℃.预计制备的磷灰石可应用于骨支架材料或填充材料.     

贝壳表面沉积片状磷灰石及其体外生物活性

采用溶液浸泡法将贝壳在37 ℃转化成磷灰石,借助XRD、FTIR、SEM、TEM等分析手段研究磷灰石的形貌、结构和体外生物活性.贝壳在磷酸缓冲溶液中浸泡24 h后,通过溶解-再结晶反应在其表面沉积上一层具有片状形貌的缺钙型磷灰石,其Ca/P比为(1.35±0.05).低温下制备的磷灰石结晶度较低,而且晶格内含有碳酸根和磷酸氢根离子.SBF实验表明,以贝壳为原料制备的磷灰石具有优良的体外生物活性,试样在SBF溶液中浸泡12 h后表面就沉积上一层类骨型磷灰石.预计溶液浸泡法制备的磷灰石可应用于骨支架材料或者填充材料.     

等离子喷涂TiO2-CaF2复合涂层的结构及体外生物矿化能力

目的等离子喷涂TiO_2涂层是生物惰性材料,不能与骨组织很好地结合,制备TiO_2-CaF_2复合涂层以提高氧化钛涂层的体外生物矿化能力。方法利用等离子喷涂技术在医用Ti合金表面制备TiO_2-CaF_2复合涂层。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和拉曼光谱仪(Raman)对复合涂层的微观结构进行表征,利用接触角仪、三维轮廓仪和电化学工作站考察复合涂层的接触角、表面粗糙度和耐腐蚀性能。采用模拟体液(SBF)浸泡实验考察复合涂层的体外矿化能力。结果 TiO_2和TiO_2-20%CaF_2涂层主要由金红石型TiO_2构成,其中含有少量的锐钛矿型TiO_2成分。20%CaF_2的掺杂会促进金红石型TiO_2的形成。CaF_2的加入可改变TiO_2涂层的表面形貌,表面粗糙度Ra从4.96μm降低至0.94μm,亲水性也得到增强。TiO_2-CaF_2复合涂层在SBF中的耐腐蚀性能也较TiO_2涂层有所提高。经SBF浸泡28 d后,TiO_2-CaF_2复合涂层表面可沉积类骨磷灰石,显示了较好的体外矿化能力,而TiO_2涂层则无此能力。结论 CaF_2的掺杂可使TiO_2涂层的表面粗糙度下降,亲水性增强,耐腐蚀性增强。体外矿化实验结果表明,TiO_2-CaF_2复合涂层表面可沉积类骨磷灰石,显示了较好的生物活性。     

微弧氧化镁表面钙磷生物涂层的制备及性能

为改善镁合金的骨植性能,采用微弧氧化处理和电沉积钙磷涂层相结合的方法在纯镁表面制备具有生物活性的复合涂层,研究了复合涂层在模拟体液和细胞培养液中的组织结构演化、腐蚀行为、骨形成能力和细胞粘附行为。 微弧氧化镁表面沉积的钙磷相为二水合磷酸氢钙(DCPD)。 电沉积过程中 DCPD 优先在微弧氧化层的通孔和放电通道处形核、随后长大并覆盖微弧氧化层而起到封孔作用。 涂覆后镁的低频阻抗模值在浸泡初期超过了 10⁵ Ω·cm² ,且在 120 h 内基本保持稳定;腐蚀电流密度与纯镁相比下降了约 3 个数量级,复合涂层显著地提高了镁的耐蚀性。 复合涂层在模拟体液和细胞培养液中均表现出了诱导羟基磷灰石(HA)沉积的能力,在细胞培养液中浸泡 14 d 后涂层表面出现球状类骨 HA 组织;细胞黏附试验中,活细胞几乎黏附在整个涂层表面,表现出良好的骨形成能力和细胞活性。     

微束等离子喷涂氧化锆增韧羟基磷灰石复合涂层

采用微束等离子喷涂方法,在Ti-6Al-4V基体上制备了羟基磷灰石 氧化锆(70HA-30ZrO2,质量分数,%)复合涂层.将复合涂层置于模拟体液中分别浸泡了3,7,14,28 d并观察表面磷灰石的生长情况以评价涂层生物活性.采用扫描电镜(SEM)和X射线衍射(XRD)分析技术对涂层浸泡前后的表面形貌和相组成进行了研究.结果表明,涂层中ZrO2主要以立方相存在;喷涂过程中羟基磷灰石(HA)出现了一定的分解,产生大量的α-Ca3(PO4)2杂质相.HA涂层熔化效果很好,但涂层中有未熔化的ZrO2颗粒.涂层在模拟体液中浸泡28 d后表面可以形成磷灰石,说明涂层具有很好的生物活性.     

溶胶凝胶法制备TiO_2/HA复合生物活性涂层及其体外活性

通过溶胶凝胶法在纯钛基体上制备了羟基磷灰石(HA)/TiO2复合生物活性涂层。HA和TiO2溶胶由前驱体制得,按不同摩尔比直接混合两种溶胶来制备混合溶胶。HA可以提高钛基的生物活性,TiO2可以提高涂层与基体的物理、化学相容性和结合强度。粘结拉伸结果表明,复合涂层与基体结合良好,比纯HA涂层与基体的结合强度提高约47%。复合涂层试样于SBF中浸泡4、7和14d的SEM分析结果表明,复合涂层表面的类骨磷灰石生成量较高。成骨细胞实验结果表明,复合涂层上细胞铺展良好。     

可降解镁合金骨螺钉表面微弧电泳水热复合涂层的制备与性能

目的在医用镁合金骨螺钉表面构建羟基磷灰石涂层,有效控制其降解速率。方法利用微弧电泳/水热复合方法,在形貌复杂的骨螺钉表面制备涂层。该方法首先利用电解抛光对骨螺钉表面进行表面预处理,采用微弧电泳技术在其表面制备羟基磷灰石涂层,再利用水热合成对微弧电泳涂层进行封孔。利用XRD、SEM、AFM等分析手段对涂层显微结构进行分析,利用体外浸泡实验和电化学实验对涂层耐腐蚀性能及其对钙磷盐的诱导特性进行了评价。结果在电解抛光电流0.14 A、抛光时间2 min的工艺条件下进行电解抛光预处理,可以提高基体和涂层的结合性能。由于骨螺钉的特殊形状,在微弧电泳电解液中添加丙三醇,并通过调整电解液中丙三醇含量优化微弧电泳工艺(电压155 V,反应时间20 min),能有效抑制尖端放电现象,防止膜层组织疏松和大量的氧化物堆积,以及涂层剥落甚至基体烧蚀的现象。再优化水热合成工艺参数(处理液p H值8.5,反应时间1.5 h,反应温度393 K)对微弧电泳涂层进行封孔,得到微弧电泳/水热复合涂层。结论微弧电泳/水热复合涂层表面形貌为菜花状结构,由纳米棒状羟基磷灰石组装而成,均匀致密,结晶性好。电化学腐蚀测试表明,制备复合涂层后,骨螺钉的腐蚀电流密度降低了一个数量级。在模拟体液中浸泡6天,骨螺钉的形貌依然完整,说明水热复合涂层在改善生物相容性的同时,提高了骨螺钉的耐腐蚀性能。但微动摩擦磨损测试显示,水热复合封孔处理后磨损性能下降。     

悬浮液等离子喷涂制备FHA/CS复合涂层

目的 采用悬浮液等离子喷涂技术（SPS）在纯钛表面制备氟代羟基磷灰石/硅酸钙（FHA/CS）生物复合涂层。方法 利用X射线衍射仪（XRD）、傅里叶红外光谱仪（FT-IR）、扫描电子显微镜（SEM）及能谱仪（EDS）对复合涂层的物相组成、组织结构和显微形貌进行分析。通过动电位极化测试和体外生物活性测试,分析复合涂层在模拟体液（SBF）中的腐蚀行为和类骨磷灰石形成能力。通过电感耦合等离子体光谱仪（ICP）分析涂层中Ca2+的释放行为,评估复合涂层的化学稳定性。采用划痕法表征涂层的结合强度。结果 SPS制备的复合涂层具有粗糙的表面和层片堆叠结构。涂层中FHA和CS两相分布均匀,结晶性良好。复合涂层临界载荷达到111.43 N,比单一FHA涂层提高62.5%。与纯钛相比,涂层样品具有较高的腐蚀电位（Ecorr）和较低的腐蚀电流密度（Jcorr）。在SBF溶液中浸泡3天,涂层样品表面被类骨磷灰石完全覆盖。ICP结果表明,复合涂层中Ca2+释放速率低于单一CS涂层。结论 通过SPS在纯钛表面制备的FHA/CS复合涂层具有良好的生物活性、耐腐蚀性能和与基体的结合强度,复合涂层中FHA组分的存在有利于提高涂层的化学稳定性。     

空心玻璃微球表面仿生沉积羟基磷灰石涂层

用NaOH和生物活性玻璃依次对空心玻璃微球进行预处理.将处理过的空心玻璃微球浸泡在1.5 SBF溶液中,仿生沉积得到羟基磷灰石涂层.利用X射线衍射仪、扫描电镜以及热场发射扫描电镜对空心玻璃微球和涂层进行表征.结果表明,浸泡15天后在空心玻璃微球表面形成一层均匀致密的羟基磷灰石涂层,随时间延长涂层厚度增加.     

Bone-like apatite formation on HA/316L stainless steel composite surface in simulated body fluid

HA/316L stainless steel(316L SS) biocomposites were prepared by hot-pressing technique. The formation of bone-like apatite on the biocomposite surfaces in simulated body fluid(SBF) was analyzed by digital pH meter, plasma emission spectrometer, scanning electron microscope(SEM) and energy dispersive X-ray energy spectrometer(EDX). The results indicate that the pH value in SBF varies slightly during the immersion. It is a dynamic process of dissolution-precipitation for the formation of apatite on the surface. With prolonging immersion time, Ca and P ion concentrations increase gradually, and then approach equilibrium. The bone-like apatite layer forms on the composites surface, which possesses benign bioactivity and favorable biocompatibility and achieves osseointegration, and can provide firm fixation between HA60/316L SS composite implants and human body bone.     

Effects of plasma treatment on bioactivity of TiO2 coatings

In this work, nano-TiO₂ powders were deposited on titanium alloy substrates by atmospheric plasma spraying, followed by plasma immersion ion implantation (PIII) using hydrogen, oxygen and ammonia gases. The bioactivities of PIII-treated TiO₂ coatings were evaluated by the formation of apatite on their surface after soaked in simulated body fluids (SBF) for a period of time. As-sprayed TiO₂ coating is composed of rutile, anatase and TiO_2−x (most of them is Ti₃O₅). After immersion in SBF for two weeks, the hydrogen PIII-treated TiO₂ coating can induce bone-like apatite formation on its surface but apatite cannot be formed on the surface of as-sprayed and oxygen, ammonia PIII-treated TiO₂ coatings. The results obtained indicated that a hydrogenated surface plays a very important role to induce bioactivity of TiO₂ coatings.     

Effect of Applied Stresses on the Microstructure and Dissolution Behavior of Plasma Sprayed Wollastonite Coatings

Wollastonite coatings were deposited on the U-shape titanium alloy coupons by atmospheric plasma spraying.The effect of applied stresses on the microstructure and dissolution behavior of wollastonite coatings was investigated.The microstructure and composition of coatings were examined by scanning electron microscope(SEM)and electron diffraction spectroscopy(EDS).In addition,the dissolution behavior of coatings was evaluated by immersion in simulated body fluid(SBF).More apatite is observed on the surface of coatings under a tensile stress and a stress-free condition after immersion in the SBF solution,whereas almost no apatite can be found for the coatings under a compressive stress.The dissolution rate of coatings characterized by the pH changes and the ion concentration of Ca,Si and P in the SBF solution is lower under the compressive stress than those under a tensile stress or a stress-free condition.It can be concluded from the experimental results that the compressive stress inhibits the dissolution of wollastonite coatings and the formation of apatite,whereas a tensile stress enhances the two processes.     

Preparation and in vitro characterization of crack-free mesoporous titania films

Crack-free mesoporous titania films (MTFs) on Ti6Al4V demonstrated potential application for implanting and bone regeneration materials in the future. The MTFs were prepared on Ti6Al4V substrate by an evaporation-induced self-assembly (EISA) process. The BET surface area, pore volume, and pore size of the MTFs samples were calculated to be 190 m²/g, 0.31 cm³/g, and 4.8 nm, respectively. The apatite-forming ability of the MTFs was evaluated by immersing them in simulated body fluid (SBF). After immersion in SBF for 5 days, bone-like apatite was induced on the surface of the MTFs. With increasing immersion time, the apatite would continue to grow and cover the surface of the MTFs. The apatite induced by MTFs contains Mg and Na ions, carbonated moieties and nano-network structure. In this work, preliminary investigation of the MG63 cell proliferation on the surface of the MTFs was also conducted. The cell experiment indicated that the MTFs possessed good biocompatibility and can thus provide a surface suitable for MG63 cell proliferation. The effects of surface properties and mesostructure on inducing apatite and cell proliferation were also discussed.     

聚苯胺微乳液及其对水性防腐涂料防腐性能的影响

目的用不同酸掺杂的聚苯胺微乳液制备水性防腐涂料,提高马口铁表面涂层的耐腐蚀性能。方法采用扫描电子显微镜、傅立叶变换红外光谱和热重分析表征聚苯胺性能,通过动电位极化法及耐水性、耐盐雾和耐盐水实验检测聚苯胺微乳液水性防腐涂层的防腐性能,用铅笔硬度和划格法表征涂层的硬度和附着力。结果磷酸掺杂聚苯胺微乳液、本征态聚苯胺微乳液制备的水性防腐涂层都对马口铁起到良好保护作用。含有盐酸掺杂聚苯胺微乳液和不含聚苯胺微乳液的水性防腐涂层在浸泡过程中很快失去保护作用。掺杂态聚苯胺使马口铁表面钝化和屏蔽,本征态聚苯胺起机械屏蔽作用。通过把聚苯胺微乳液添加到水性防腐涂料中,发现涂层的硬度和附着力均没有发生明显下降,表明聚苯胺微乳液在水性防腐涂料中分散均匀,对涂层的性能影响较小。结论当水性防腐涂料中的聚苯胺质量分数为0.3%时,磷酸掺杂的聚苯胺微乳液具有最佳的耐腐蚀性能,其腐蚀电流密度Jcorr=7.359×10-7 A/cm2,腐蚀电位Ecorr=-0.527 V。     

Bioactivity and cytocompatibility of plasma-sprayed titania coating treated by sulfuric acid treatment

Titania coatings were fabricated on titanium alloy substrate using atmospheric plasma spraying technology, and treated by sulfuric acid (H₂SO₄) at room temperature for 24 h. The as-sprayed and acid-treated titania coatings were soaked in simulated body fluid (SBF) to investigate the formation of apatite on their surfaces. Human mesenchymal stem cells (MSCs) were used to evaluate the cytocompatibility of titania coatings. The results indicated that bone-like apatite was formed on the surfaces of acid-treated titania coatings after soaked in SBF for a period of time. The concentration of sulfuric acid had an effected on the bioactivities of titania coatings. The bioactivity of titania coating could not be improved by 0.01 M sulfuric acid treatment. The MSCs could attach, grow and proliferate well on the surface of titania coatings. The results showed that plasma-sprayed titania coating after acid treatment exhibited favorable bioactivity and cytocompatibility.