钛合金表面GO/HA/MAO复合膜层的制备及其性能

为了改善钛合金种植体在体液中的腐蚀及摩擦腐蚀行为,延长其在人体环境中的服役时间,在微弧氧化 (MAO)膜层上采用溶胶凝胶(Sol-gel)法于羟基磷灰石(HA)和氧化石墨烯(GO)的混合溶胶中浸渍提拉成膜,从而在 Ti6Al4V 合金表面成功地制备了 GO/ HA/ MAO 复合膜层。 结果表明,MAO 膜层表面的微孔及微球被 GO/ HA 薄膜有效的覆盖且较为致密;膜层的物相组成主要为金红石相及锐钛矿相的 TiO₂、HA、SiO₂ 和GO;根据电化学腐蚀和摩擦腐蚀结果分析知,GO/ HA/ MAO 复合膜层在模拟体液(SBF)中的耐蚀性及耐摩擦腐蚀性相比于 MAO 膜层和 Ti6Al4V 基体均得到了显著提高。     

钛合金微弧氧化生物活性陶瓷膜润湿性及耐腐蚀性能研究

通过微弧氧化技术(MAO)在Ti6Al4V合金表面获得了富含Ca、P的生物陶瓷膜,对陶瓷膜的物相组成、微观形貌及其在Hank's模拟体液中的阳极极化行为进行了研究,分析了不同微弧氧化电压对陶瓷膜润湿性能及耐腐蚀性能的影响.结果表明,所制备的陶瓷膜表面粗糙多孔,主要由锐钛矿、金红石以及少量羟基磷灰石和无定形相组成.随着微弧氧化电压升高陶瓷膜中的金红石和羟基磷灰石的含量增加,陶瓷膜中微孔数量减少,但尺寸增加,孔隙率变化不明显.微弧氧化膜的接触角随微弧氧化电压的升高不断减小,说明润湿性能逐渐改善,陶瓷膜的粗糙度和物相是主要影响因素.微弧氧化膜使合金在模拟体液中发生阳极电阻极化,氧化电压越高耐腐蚀性能越好.     

新型可降解Mg-1Ca合金微弧氧化工艺初探

采用微弧氧化(Micro-arc oxidation,MAO)在镁合金表面制备一层多孔陶瓷膜可以有效改善基体的耐蚀性和生物相容性。文章以新型Mg-1Ca为基体进行微弧氧化处理,研究了处理时间和电压对MAO膜层结构和成分及耐蚀性的影响,讨论了膜层的生长机理及其在SBF溶液中的腐蚀行为。     

碱热处理对TC4合金微弧氧化膜生物活性的影响

利用微弧氧化技术在Ti6Al4V合金表面制备含钙、磷的多孔TiO_2涂层(记为MAO),并对涂层进行碱热处理(记为MAONH).结果表明:MAONH膜层的相结构和MAO膜层的大有不同,它主要由TiO_2(金红石型和锐钛矿型)、钛酸钙相组成.钙和磷离子在MAONH膜层表面比在MAO膜层表面更容易沉积,其原因是钛酸钙在模拟体液浸泡时发生水解,生成大量的Ca~(2+)和OH~- 离子,Na~+和OH~-离子同模拟体液中的Ca~(2+)和PO_4~(3-)离子发生离子交换,导致磷灰石在MAONH膜层表面沉积.     

纯钛表面微弧氧化多孔陶瓷膜的结构特性

采用微弧氧化处理技术和电解液成分的优化设计,在纯钛表面制备了含钙磷的多孔复合陶瓷膜,并考察了陶瓷膜的表面形貌、截面形貌、化学成分、物相构成、生物活性及其与基体的结合强度等特性。研究结果表明:纯钛表面微弧氧化后形成了凹凸不平的多孔陶瓷膜,整个膜层分为表层疏松层、中间过渡层和内部致密层三个区域,总厚度为25～40μm,膜层与基体的界面呈"锯齿状"紧密结合。膜层主要由金红石相TiO2和锐钛矿相TiO2构成;膜层中含有Ca,P,O,Ti四种元素,其钙磷比ω(Ca)∶ω(P)为1.528;膜层中的Ti,Ca,P元素呈梯度分布,由表及里Ti含量逐渐增多,Ca和P含量逐渐减少,O元素分布比较均匀。含钙磷多孔复合陶瓷膜具有良好的生物活性,样品经碱液处理后再在快速钙化溶液(FCS)中浸泡4d即有羟基磷灰石(HA)形成;膜层与基体具有高的结合强度,在450V和600Hz时膜层的临界载荷值高达29.5N。     

TA2表面微弧氧化-水热合成复合陶瓷膜层结构及其表面能分析

采用微弧氧化-水热法在纯钛TA2表面制备了含有羟基磷灰石、金红石相Ti O2及锐钛矿相Ti O2的复合陶瓷膜层。观测与分析复合陶瓷膜层的微观形貌、元素成分、粗糙度及相组成,探讨水热时间对其结构及表面能的影响。结果表明,水热处理后膜层表面结晶形核出大量光滑且较规则的条柱状及针状HA颗粒,不同水热时间的膜层表面基本组成元素均为Ti、O、Ca、P。随着水热时间的延长,膜层表面HA晶粒增多,体积增大,表面粗糙度呈现先下降后上升的趋势。膜层表面与水的接触角在116.0o~140.2o之间,均大于纯钛TA2基材与水的接触角77.3o,疏水性能增强;膜层表面能为150.7~282.9 m J·m~(-2),较纯钛TA2基材的27.5m J·m~(-2)提高了4倍以上。粗糙度的改变是导致膜层表面能提高的主要因素。     

水热时间对钛合金微弧氧化膜合成羟基磷灰石的影响

目的研究水热时间对TC4钛合金微弧氧化膜合成羟基磷灰石(HA)的影响。方法对TC4钛合金微弧氧化膜进行不同时间的水热合成处理,分析其微观形貌、成分及相结构,观察其在模拟体液中浸泡5周后的形貌及结构变化。结果水热处理提高了微弧氧化膜的Ca/P摩尔比,使非晶态钙磷化合物转化为HA晶体,随着水热时间的延长,HA衍射峰数量增多且强度增加。在模拟体液中浸泡5周后,微弧氧化膜表面仅有微量磷酸钙形成,而如水热合成后再浸泡,氧化膜表面的HA几乎完全转化为磷酸钙。结论水热处理有助于钛合金微弧氧化膜表面合成HA晶体。在8 h内,水热时间越长,氧化膜表面的HA含量越高,模拟体液中浸泡后形成的磷酸钙也越多,与人体的相容性越好。     

纯钛表面载骨碎补提取物涂层的制备与性能

为了提高纯Ti的生物活性和抗感染性,采用微弧氧化(UMAO)制备多孔涂层,并以植酸(PA)偶联骨碎补提取物(ERD),并分析涂层结构、形貌及性能。结果表明,随着ERD浓度的提高,纳米颗粒增多,有PO43-,P2O74-和O=P-O-生成;载药12.5g/L的膜层摩擦磨损系数低,膜层结合力较高,为亲水涂层,膜层的电位提高了0.32V,自腐蚀电流降低一个数量级,模拟体液浸泡有羟基磷灰石(HA)生成。纯钛表面通过超声微弧氧化,植酸偶联载药的耐蚀性,结合力,生物活性均有提高。     

纯镁微弧氧化载葛根素膜层的耐蚀性和体外生物活性模拟

为了制备一种能提高医用纯Mg微弧氧化膜层的耐蚀性和生物活性的膜层,对纯Mg表面进行超声微弧氧化(Ultrasonic micro arc oxidation,UMAO),再将不同浓度的中药提取物葛根素添加到偶联剂硅烷水解液中,通过浸渍,获得载药膜层。通过SEM观察膜层表面形貌,傅里叶红外光谱分析官能团,并进行润湿角、电化学腐蚀及模拟体液浸泡试验。结果表明:载药膜层有Si-O-Si骨架和苯环官能团产生,起到了封孔的作用,复合膜层润湿角增加了48°,自腐蚀电流降低一个数量级,阻抗提高了约188 kΩ。模拟体液浸泡膜层表面有羟基磷灰石(Hydroxylapatite,HA)生成。纯Mg经UMAO,浸渍硅烷并载葛根素(1.2 mg/m L),阻抗是UMAO组的7倍,Ca/P比达到1.55,形成的复合生物膜层具有良好的耐蚀性和生物活性。     

纯钛材与大变形纯钛材微弧氧化-水热合成复合陶瓷膜层的细胞相容性研究

采用微弧氧化-水热法分别在纯钛材及大变形纯钛材表面制备了TiO_2/HA复合陶瓷膜层,从细胞毒性实验、细胞增殖实验、细胞黏附实验等方面评价膜层的细胞相容性。结果表明:纯钛材与大变形纯钛材微弧复合陶瓷膜层均无细胞毒性。与纯钛材微弧复合陶瓷膜层相比,大变形纯钛材微弧复合陶瓷膜层表面粗糙度更适宜,结晶形核的HA晶粒的形状及Ca/P比更接近人骨HA,更能有效促进成骨细胞的黏附和铺展,随着培养时间的延长,成骨细胞双层重叠生长结构更为明显。成骨细胞在大变形纯钛材微弧复合陶瓷膜层表面各时间点的吸光度值均更高,细胞相容性更好。     

AZ91镁合金表面含Ti生物复合涂层结构及腐蚀学性能

采用冷喷涂法在AZ91合金表面预置纯Ti涂层,再采用微弧氧化对Ti涂层进行仿生生物改性.用SEM、XRD、EDS等方法分析涂层的组织结构,用动电位法测试涂层的腐蚀学性能.结果表明:冷喷涂预置Ti层厚度约100 μm,外表面形貌粗糙.微弧氧化处理后在Ti层表面产生微弧放电孔.生物改性层主要由Ti_2O_3组成,还含有少量钙、磷等物质.微弧氧化层有利于提高冷喷涂Ti层的生物学活性和致密性.含Ti复合涂层显著提高AZ91合金在模拟体液(SBF)中的自腐蚀电位(提高了约0.3 V),表明含Ti生物复合涂层具有良好的抗腐蚀性能.     

Anti-corrosion microarc oxidation coatings on SiCP/AZ31 magnesium matrix composite

The corrosion-resistant ceramic coatings up to 80 μm thick were fabricated on SiC_P/AZ31 magnesium matrix composite by microarc oxidation (MAO) technique in Na₃PO₄ + KOH + NaF solution. The microstructure, composition and phase constituent of ceramic coatings were analyzed by SEM and XRD, and the electrochemical corrosion behaviour of coatings was evaluated by the electrochemical polarization method. The thicker coating is compact and displays a good adhesion to the composite substrate. The ceramic coatings consist of MgO, Mg₂SiO₄, MgF₂, Mg₃(PO₄)₂, furthermore, a few residual SiC phases were also found in the coatings by means of SEM observation and EDX analysis. Most of SiC reinforced particles in the oxidized composite substrate have transformed into the oxides under microarc discharge sintering, but a few residual SiC reinforcements in the MAO coatings have not disrupted the continuity of coatings. So the corrosion resistance of the SiC_P/AZ31 composite is greatly improved by MAO surface treatment, however, the corrosion resistance of coated composite also depends on the coating thickness.     

电压对AZ31镁合金微弧氧化涂层微观结构及腐蚀性能的影响

为研究过程参数对镁合金微弧氧化涂层的微观结构及耐腐蚀性能的影响,在AZ31镁合金基体上,采用不同电压,在电解液磷酸三钠(Na3PO4)中制备微弧氧化涂层.采用扫描电子显微镜(SEM)及光学显微镜,分析膜层腐蚀前后的微观组织结构;通过X射线衍射仪(XRD)分析涂层样品腐蚀前后的相组成.采用动电位极化曲线和电化学阻抗谱(EIS)测试对涂层的耐腐蚀性能进行评价.结果表明:AZ31镁合金微弧氧化涂层主要由Mg3(PO4)2,MgO,Mg和少量MgAl2O4组成,腐蚀产物由Mg(OH)2,quintinite和Ca10(PO4)6 (OH)2组成.在电压为325 V,频率3 000 Hz,氧化时间为5 min下制备的微弧氧化涂层具有最致密均匀的微观形貌和最小的腐蚀电流密度,因此表现出最强的耐腐蚀性能.     

α-Al2 O3微粒对铸造Al-Si合金微弧氧化膜耐蚀性的影响

目的通过共生沉积技术将α-Al2O3微粒引入到铸造Al-Si合金微弧氧化膜中,并研究其对膜层耐蚀性的影响。方法利用SEM和XRD分析α-Al2O3微粒对微弧氧化膜微观结构及成分的影响。通过极化曲线、交流阻抗谱及中性盐雾试验评价膜层的耐蚀性。结果α-Al2O3微粒复合改变了微弧氧化膜的组成及结构。微弧氧化膜呈双层结构,表面存在大量微孔,主要组成为γ-Al2O3;加入α-Al2O3微粒后,微弧氧化复合膜的表面微孔大幅减少,致密度提高,且膜层中α-Al2O3相增多。此外,α-Al2O3微粒复合改善了微弧氧化膜的耐蚀性。微弧氧化膜在质量分数为3.5%的Na Cl溶液中的自腐蚀电流密度约为1.476×10-5A/cm2,多孔层电阻Rp及阻挡层电阻Rb分别为0.259 kΩ·cm2及69.18 kΩ·cm2,耐盐雾试验时间为1200 h。加入α-Al2O3微粒后,微弧氧化复合膜的自腐蚀电流密度仅为微弧氧化膜层的28%,Rp大幅增加至274.5 kΩ·cm2,且Rb也上升了一个数量级,耐盐雾试验时间可达1440 h。结论α-Al2O3微粒的引入可以大幅提高铸造Al-Si合金微弧氧化膜的耐蚀性。     

Effect of hydroxyapatite‐titanium‐MWCNTs composite coating fabricated by electrophoretic deposition on corrosion and cellular behavior of NiTi alloy

In this study, the hydroxyapatite (HA)‐titanium (Ti, 20 wt.%) multiwalled carbon nanotubes (MWCNTs, 1 wt.%) composite coating was applied on the NiTi alloy by using the electrophoretic deposition (EPD) technique. The morphologies and the phase structures of the coatings were investigated by the FESEM and XRD analysis, respectively. The corrosion behaviors of the coated NiTi samples were investigated using the polarization and electrochemical impedance spectroscopy tests in a simulated body fluid (SBF). The amounts of the released Ni ions from the coated NiTi were studied in the SBF. The results of the electrochemical tests revealed the corrosion resistance of the NiTi coated with HA was further improved by the addition of the Ti and MWCNTs to the HA coating. The current density and corrosion resistance of the NiTi alloy changed from 2.52 μA.cm^?2 and 24.13 kΩ to 0.91 nA.cm^?2 and 5.92 MΩ after coated with the HA‐Ti‐MWCNTs composite coating. Also, the number of nickel ions released from the surface of the NiTi alloy to the SBF medium suppressed from 11.8 to 0.08 μgr.L^?1, after coating with HA‐Ti‐MWCNTs. Also, the cellular proliferation in the culture medium consisting of the NiTi alloy coated with the HA‐Ti‐MWCNTs improved significantly (compared with that of the NiTi alloy) as shown no toxicity in the cell culture medium.     

Effect of voltage on microstructure and corrosion resistance of microarc oxidation coatings on CP-Ti

The surface modification of commercially pure titanium (CP-Ti) by microarc oxidation (MAO) under different voltages was investigated using 1%H₃PO₄ solution as an electrolyte. The microstructure, phase composition and elemental distribution of ceramic coatings were investigated using scanning electron microscopy (SEM) and X-ray diffraction. The corrosion behaviour of the coating was also examined by potentiodynamic polarisation testing in a 3·5 wt-%NaCl solution. Micropore oxide films were formed on all the sample groups by MAO. The thickness and micropore size of the MAO coating increased with the increasing voltage. Energy dispersive X-ray spectroscopy results indicate that Ti, O and P became incorporated into the MAO coatings. At a low voltage of 250 V, the MAO coatings were composed of amorphous, P₂O₅, TiP₂O₇ and titania phases (rutile and anatase). Variation of treatment voltages increased the ceramic coatings from an amorphous structure to a phase structure, and the P₂O₅ phase disappeared. The corrosion potential Φ_corr of the MAO sample shifted towards nobler directions, and the corrosion density I_corr fell significantly compared with that of the bare CP-Ti. Corrosion testing showed that the sizes of the micropore of the MAO samples obviously decrease, and the MAO surface becomes smooth.     

脉冲频率对镁合金微弧氧化膜层在仿生液中耐蚀性的影响

研究了微弧氧化过程中不同电源脉冲频率下制备的膜层在仿生液中的电化学腐蚀行为。对膜层及腐蚀产物的微观组织,孔隙率,腐蚀形貌及相组成进行了分析。采用动电位极化曲线(Tafel)和电化学阻抗谱(EIS)法对膜层的耐腐蚀性能进行评价。结果表明,脉冲频率对AZ31镁合金微弧氧化膜层的耐蚀性有重要影响,随着频率的增加,腐蚀电流密度减小,而电化学阻抗增大。因此在本研究范围内,频率3000 Hz下制备的微弧氧化膜层具有最强的耐腐蚀性能。     

Structure of calcium titanate/titania bioceramic composite coatings on titanium alloy and apatite deposition on their surfaces in a simulated body fluid

In this study, TiO₂-based coatings containing Ca and P ions were prepared on titanium alloy surfaces by microarc oxidation (MAO). After soaking in aqueous NaOH solution and subsequent heat treatment at 700 and 800 °C, calcium titanate/titania bioceramic composite (CTBC) coatings were obtained. The results show that the outer layers (0–1.5 μm) of the CTBC coatings are mainly composed of Ca, Ti, O and Na constituents with a uniform distributions with increasing the depth near the surfaces. The surface phase compositions of the CTBC coating formed at 700 °C are anatase, rutile and CaTi₂₁O₃₈ phases, as well as a few CaTiO₃, while those of the CTBC coating formed at 800 °C are anatase, rutile and CaTiO₃. When incubated in a simulated body fluid (SBF), apatite was deposited on the CTBC coatings probably via formation of hydroxyl functionalized surface complexes on the CTBC coating surfaces by ionic exchanges between (Ca²⁺, Na⁺) ions of the CTBC coatings and H₃O⁺ ions in the SBF. The CTBC coating formed at 800 °C seems to facilitate the deposition of Ca and P probably due to the good crystallographic match between perovskite CaTiO₃ and HA on specific crystal planes.