镁合金表面层层组装PSS/PAH膜诱导钙磷涂层

目的镁合金具有良好的生物相容性和可降解性,作为生物医用材料具有广泛的应用前景。有效地提高镁合金的耐蚀性能,对镁合金作为医用材料具有重要意义。方法利用浸泡法在AZ31镁合金基体表面层层组装制备聚苯乙烯磺酸钠(PSS)、聚丙烯胺盐酸盐(PAH)多层膜,并将获得的样品采用水热法在Ca(NO)_3、NaH_2PO_4、Na_2CO_3溶液中诱导钙磷涂层(羟基磷灰石)的形成。利用高分辨扫描电子显微镜、傅里叶红外光谱、X射线光电子能谱对Ca-P/(PAH/PSS)5/Mg复合膜层的表面形貌、化学成分进行了表征,通过析氢和电化学实验(包括极化曲线及阻抗谱)研究了Ca-P/(PAH/PSS)5/Mg涂层的耐腐蚀性能。结果Ca-P/(PAH/PSS)5/Mg膜层厚度约为7.67μm,表现为立体叶草状,在镁合金表面紧密排列。Ca-P/(PAH/PSS)5/Mg涂层耐蚀性提高一个数量级,其腐蚀电流密度从镁合金AZ31的3.69×10–5 A/cm2降低到1.61×10–6 A/cm~2,同时析氢速率降低。结论该涂层可以有效地提高镁合金的耐蚀性能,其成因则主要归功于组装的两种聚电解质的类生物矿化作用。这种诱导所得钙磷膜层对镁合金在生物医用领域的应用提供了新的思路。     

In vitro degradation resistance of glucose and L-cysteine-bioinspired Schiff-base anodic Ca–P coating on AZ31 magnesium alloy

A Schiff base (a compound containing a C=N bond) induced anodic Ca–P coating was prepared on AZ31 Mg alloy in a mixed solution of CaCl₂ and KH₂PO₄ at 60 °C in the presence of glucose and L-cysteine. The microstructure and chemical composition of the coatings were characterized using FE-SEM, FT-IR, XRD, and XPS. The in vitro degradation resistance of the coated samples was evaluated via potentiodynamic polarization (PDP), electrochemical impedance spectroscopy (EIS), and hydrogen evolution test. The experimental results show that the Ca–P_{Schiff base} coating is composed of CaHPO₄ (DCPA) and hydroxyapatite (HA), whereas HA is not present in the Ca–P coating. The Ca?P_{Schiff base} coating thickness is about 2 times that of Ca–P coating (Ca?P coating: (9.13±4.20) μm and Ca–P_{Schiff base}: (18.13±5.78) μm). The corrosion current density of the Ca–P_{Schiff base} coating is two orders of magnitude lower than that of the Ca–P coating. The formation mechanism of the Ca–P_{Schiff base} is proposed.     

溶液温度对医用Mg-Li—Ca合金表面锌钙系磷酸盐转化膜耐蚀性能的影响

考察不同磷化液温度对Mg-Li-Ca合金表面锌钙磷酸盐转化膜质量和耐蚀性能的影响。利用扫描电子显微镜、电子探针、能谱仪、X射线衍射和傅里叶红外光谱研究转化膜的表面形貌、化学成分和物相,采用析氢腐蚀实验和动电位电化学技术以及电化学阻抗研究磷化液温度对 Mg-Li-Ca 合金表面磷酸盐转化膜耐蚀性能的影响。结果表明：当溶液温度低于45℃时,膜层主要由Zn和ZnO组成,而当温度高于50℃时,膜层的主要相为Zn3（PO4）2·4H2O、少量的Zn和ZnO;在55℃温度下制备的磷酸盐转化膜的耐蚀性能最好;在40~50℃下制备的膜,由于镁基体与锌之间形成的电偶腐蚀而加快了其析氢速率。     

镁合金表面谷氨酸、丙氨酸、天冬氨酸诱导Ca–P涂层耐蚀性能比较

目的 细化Ca-P涂层晶粒,提高其致密性、耐蚀性,得到氨基酸等电点(Isoelectric point,pI)的作用及生物矿化机制。方法 选取谷氨酸、丙氨酸、天冬氨酸,通过60℃水浴,在AZ31镁合金表面制备无氨基酸和3种氨基酸Ca-P涂层,即丙氨酸Ca-P涂层(Ca-P_Ala)、谷氨酸Ca-P涂层(Ca-P_Glu)、天冬氨酸Ca-P涂层(Ca-P_Asp)。采用高分辨扫描电子显微镜(SEM)、X射线衍射仪(XRD)和傅里叶红外光谱仪(FTIR)对涂层的微观形貌及成分进行表征分析;通过电化学极化、交流阻抗(EIS)及析氢实验探究涂层在Hank’s人体模拟体液中的耐蚀性能。结果 Ca-P、Ca-P_Ala、Ca-P_Glu、Ca-P_Asp涂层的厚度分别为(8.46±0.43)、(14.39±0.96)、(8.48±0.16)、(10.07±0.94)μm。涂层的主要组成物相为透钙磷灰石(Ca HPO₄·2H₂O,DCPD...     

Characterization and wear resistance of macro-arc oxidation coating on magnesium alloy AZ91 in simulated bedy fluids

The mechanical characteristics ofthe macro-arc oxidation(MAO) coating on Mg alloy AZ91 were examined by means of nano scratch tester.The corrosion and erosion corrosion behavior of AZ91 with and without MAO coating were investigated by using potentiodynamic electrochemical technique and micro-abrasion tribometer in simulated body fluids,respectively.The influence of HCO3-ions on the erosion corrosion was discussed.The results show that the coating and its substrate are in a pronounced bond.The MAO coating inereases1-2 orders of magnitude of the corrosion resistance of AZ91 alloy.HCO3-ions enhance the corrosion rates of the AZ91 alloys more significantly than the alloys with MAO coating.However,there exists an obvious passivation process of AZ91 without coating in the HCO3-solutions.Moreover,an MgCO3 film formed in HCO3-containing solutions leads to an enhancement in micro-wear resistance.MAO coating deteriorates the erosion corrosion resistance of AZ91 alloy due to the formation of oxidation debris resulted from the broken MAO coating.     

Characterization and wear resistance of macro-arc oxidation coating on magnesium alloy AZ91 in simulated body fluids

The mechanical characteristics of the macro-arc oxidation(MAO) coating on Mg alloy AZ91 were examined by means of nano scratch tester.The corrosion and erosion corrosion behavior of AZ91 with and without MAO coating were investigated by using potentiodynamic electrochemical technique and micro-abrasion tribometer in simulated body fluids,respectively.The influence of HCO_3~- ions on the erosion corrosion was discussed.The results show that the coating and its substrate are in a pronounced bond.The MAO co...     

医用镁基HA复合涂层的研究及发展现状

镁及镁合金由于其良好的生物相容性和可降解性能,在生物医用材料领域具有巨大的应用潜力。然而,过快的降解速率限制了其临床应用。羟基磷灰石(HA)涂层具有良好的骨诱导性和骨传导性,可以有效地延缓镁及镁合金的腐蚀速率。但是,单一的羟基磷灰石涂层不能满足镁基植入物的使用寿命要求,因此需对其进一步的改性。本文从生物相容性、可降解性以及力学性能等方面综述镁合金表面以羟基磷灰石为基础,以高分子材料、无机材料以及离子掺杂而成的可降解镁基HA复合涂层的发展和研究现状。     

表面涂覆含氟羟基磷灰石和缺钙羟基磷灰石的镁合金体外降解行为(英文)

通过电化学沉积方法,在生物降解镁合金表面覆盖含氟羟基磷灰石(FHA)涂层和缺钙羟基磷灰石(CDHA)涂层。采用X射线衍射、傅立叶变换红外光谱、透射电子显微镜、扫描电子显微镜和能量色散X射线光谱研究涂层特性。结果表明:涂覆纳米FHA涂层的样品具有垂直于样品表面的纳米针状结构,比涂覆CDHA涂层样品的结构更致密和更均匀。纳米FHA涂层比纳米CDHA涂层具有更小的晶粒尺寸,分别为65 nm和95 nm。然而,CDHA涂层比FHA涂层更厚,厚度分别为19μm和15μm。通过极化、浸泡和析氢实验研究的腐蚀行为表明:纳米FHA涂层和纳米CDHA涂层显著降低腐蚀速率并引起钝化。纳米FHA和纳米CDHA涂层可以加速骨状磷灰石层的形成,相比未覆盖的镁合金可以显著减少溶出速率。纳米FHA涂层能对镁合金提供有效的防护并具有更高的腐蚀性能。因此,覆盖纳米FHA涂层的镁合金在整形外科领域具有良好的应用前景。     

医用镁合金表面肝素/蒙脱石涂层耐蚀性研究

目的 为解决镁合金血管支架使血管内皮化、造成再狭窄等问题,在AZ31镁合金表面制备具有抗凝特性的肝素(HS)/蒙脱石(MMT)复合涂层,并研究其耐蚀性能.方法 采用水热法在AZ31镁合金表面制备钠蒙脱石(Na-MMT)涂层,在此基础上通过浸泡法以蒙脱石为载体,制备肝素/蒙脱石复合涂层.利用扫描电子显微镜(SEM)、傅里...     

Biomedical Magnesium Alloys: Composition,Microstructure and CorrosionEI北大核心CSCD

Magnesium alloys, with good biocompatibility and mechanical-compatibility, can be developed as next generation promising biomaterials. This paper summerizes the principle and the cutting-edge advances of alloying of magnesium alloys as degradable biomaterials. The effects of alloy elements on the material and biological properties of magnesium alloys are analyzed. The focus is laid on the influence of microstructure (grain size, secondary phase or intermetallic compound, long-period stacking ordered (LPSO) phase and quasi-crystal phase), heat treatment and surface oxide film on degradation and their critical progress on corrosion morphology and mechanism. Several outlooks on bio-magnesium alloys are proposed.     

Mg合金的防蚀处理

综述了Mg合金的防蚀处理方法,重点论述了涂层处理 的研究进展.     

医用镁合金丝材的微弧氧化表面改性(英文)

在硅酸盐-磷酸盐复合电解质中添加羟基磷灰石纳米粉体和氢氧化钠进行改性处理,然后采用该电解质对医用镁合金丝材进行微弧氧化处理。研究电解质中氢氧化钠含量对镁合金丝材表面陶瓷涂层微观组织结构和性能的影响。结果表明:对电解质改性后,镁合金丝材的微弧氧化起弧电压大降低且氧化速度更快。镁合金丝材在添加2 g/L氢氧化钠的电解质中进行微弧氧化处理后的耐腐蚀性能改善幅度显著。在模拟体液的早期浸泡过程中,微弧氧化处理过的镁合金丝材表现为缓慢且稳定的腐蚀降解。在浸泡28 d后,镁合金丝材表面的保护性陶瓷涂层尚未破坏,但浸泡60 d后,镁合金丝材出现了显著的腐蚀降解。     

Al扩散涂层对AZ91D Mg合金耐腐蚀性能的影响

通过磁控溅射Al和真空退火的方法,在AZ91DMg合金表面得到Al扩散涂层.利用XRD衍射和SEM观察表征了表面层的相组成和形貌;利用动电位极化测试研究了原始的和经表面处理的AZ91D在3.5%NaCl溶液中的腐蚀行为.结果表明:经上述表面处理的合金表面层结构为Mg-Al金属间化合物,自腐蚀电位提高,腐蚀电流密度减小,耐腐蚀性能提高.     

AZ31镁合金表面含纳米羟基磷灰石微弧氧化涂层的制备及性能研究

目的改善AZ31镁合金的耐腐蚀性能及生物活性。方法使用微弧氧化技术,分别在以六偏磷酸钠为主盐的电解液和以六偏磷酸钠为主盐、以纳米羟基磷灰石(HA)为添加剂的电解液中,在AZ31镁合金表面制备了微弧氧化涂层。通过扫描电子显微镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)表征了涂层的微观形貌、元素特征和相组成。通过电化学方法和浸泡实验考察了涂层的耐蚀性。通过细胞实验评价了两种涂层的细胞相容性。结果电解液中的HA可以进入到微弧氧化涂层中,含HA的微弧氧化涂层较不含HA的更致密,且有封孔现象。电化学方法及浸泡实验结果表明,含HA的微弧氧化涂层的耐腐蚀性能更好。细胞表面粘附实验和细胞增殖实验也表明,经表面纳米HA微弧氧化处理后的AZ31镁合金生物相容性更好,且对MC3T3-E1细胞的增殖有促进作用。结论六偏磷酸钠电解液中添加纳米HA,可以在AZ31镁合金表面制备出含HA的微弧氧化涂层,且其耐腐蚀性能和生物活性均优于不含HA的微弧氧化膜。     

Anodization of AZ91 magnesium alloy in alkaline solution containing silicate and corrosion properties of anodized films

The anodization of AZ91 magnesium alloy in an alkaline electrolyte of 100g/L NaOH 20g/L Na2B4O7·10H2O 50g/L C6H5Na3O7·2H2O 60g/L Na2SiO3·9H2O was studied.The corrosion resistance of the anodized films was studied by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques.The microstructure of the films was examined with scanning electronic microscope (SEM) and X-ray diffractometer (XRD).The results show that,under the experimental conditions,the optimum anodizing time and the optimum anodizing current density are 40min and 20mA/cm2 respectively for obtaining the anodic film with high corrosion resistance.The XRD pattern shows that the components of the anodized film consist of MgO and Mg2 (SiO4).     

酸根离子对镨盐化学转化膜的组成及性能的影响

为探究转化液主盐酸根在成膜过程中的重要作用,采用扫描电子显微镜、能谱仪、x射线光电子谱仪结合电化学测试对两种常见酸根对应镨盐在镁合金表面形成转化膜后的形貌、成分、元素化学状态以及耐腐蚀性能进行比较,并基于酸根离子在水溶液中的反应过程分析其对转化膜成分及性能的作用机制.结果表明,以PrCl3作为主盐比以Pr(NO3)3作为主盐形成的化学转化膜更加致密;且前者受基体成分的影响较小,形成膜层的Pr、O含量(质量分数)明显高于后者;前者的耐腐蚀性能优于后者.酸根离子对转化膜成分及性能的影响主要体现在镨盐电离后在转化液中形成的相应稀酸与基体合金的作用机制及其对转化膜形成过程的影响.     

AZ91 D 镁合金表面铈转化膜及环氧 / 氟碳涂层附着性研究

利用化学浸泡法在AZ91D镁合金表面制备铈盐转化膜,优化了铈盐转化处理工艺,研究了铈盐转化膜的微观形貌、组织结构及耐蚀性能。在转化膜表面分别涂覆环氧树脂和氟碳树脂涂层,测试了两种复合涂层的力学性能。结果表明:铈盐转化膜由双层膜组成,在优化的工艺条件下进行转化处理能够提高镁合金的耐腐蚀能力;铈盐转化膜对环氧树脂的适应性要优于氟碳树脂。     

聚苯胺含量对镁合金上聚苯胺环氧涂层防腐性能的影响

在AZ31B镁合金表面制备了含本征态聚苯胺O%,1%,2%,4%,6%的聚苯胺/环氧防腐涂层,通过Tafel极化曲线、电化学阻抗谱测试及中性盐雾实验对比了其在3.5%NaCl溶液中的防腐性能.结果表明:聚苯胺的含量时聚苯胺环氧涂层的防腐性能有较大影响,聚苯胺的质量分数为2%时,涂层具有最佳的防腐性能.     

In vitro corrosion and biocompatibility of phosphating modified WE43 magnesium alloy

Phospahting coated WE43 magnesium alloy was prepared by an immersion method. The microstructure, corrosion resistance and biocompatibility of the coated alloy were investigated. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) were used to examine the microstructure and the composition of the coated alloy. The corrosion resistance was studied by means of potentiodynamic polarization method and the biocompatibility of the surface modified WE43 alloy was evaluated by (3-(4,5)-Dimethylthiazol-2, yl)-2,5-diphenyltetrazolium bromide (MTT) and hemolysis test. The results show that the phosphating coating can enhance the corrosion resistance of WE43 alloy and can be a good candidate to increase the biocompatibility of WE43 alloy.