纯镁表面硅烷/透明质酸钠复合涂层的结构及腐蚀性能研究

纯镁因较快的腐蚀速率使其用于手术移植材料成为了一个障碍。为了控制其降解速率,本研究采用BTSE(1,2-(三乙氧基硅基)乙烷)硅烷化处理和共键嫁接1-(3-二甲氨基丙基)-3-乙基碳二亚胺盐酸盐(EDC)/N-羟基丁二酰亚胺(NHS)交联改性的透明质酸钠涂层的两步制备工艺在纯镁上制备复合涂层。同时使用红外光谱(FTIR)、X射线光电子能谱(XPS)、原子力显微镜(AFM)和静态接触角方法(CA)分析涂层的物化性能,通过电化学行为分析涂层在模拟体液中的耐腐蚀性能。FTIR和XPS结果表明在纯镁表面上成功的制备出复合涂层;其他结果显示,交联透明质酸钠涂层表面较裸镁、硅烷表面更平整、光滑,且呈现出亲水性,提高了其生物活性;与未改性的纯镁相比,复合涂层的腐蚀电流密度减小了2个数量级,阻抗值提高3个数量级,表现出很好的耐腐蚀性能。表明这种复合涂层作为手术移植材料在医学上具有很大的应用前景。     

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.     

纯镁的生物腐蚀研究

镁及其合金作为生物医用材料具有明显的优势,可以利用其耐蚀性差的特点,发展新型医用可降解镁金属材料．本文选择纯镁为主要研究对象,从杂质含量、加工处理状态等方面研究了两种纯镁在生理盐水中的腐蚀规律,表明降低纯镁中杂质元素的含量和细化晶粒可以提高纯镁在生理盐水中的开路腐蚀电位,减缓腐蚀速率．纯镁的腐蚀速率可以通过调整杂质含量、晶粒细化和固溶处理等方法进行控制,适宜发展成为一类新型的医用可降解金属材料．     

Fabrication of Cr coating on AZ31 magnesium alloy by magnetron sputtering

Chromium-plating is considered an effective method to improve surface properties of metal materials.Magnetron sputtering was applied to prepare Cr coating on AZ31 magnesium alloy and the influence of bias voltage on properties of Cr coating was investigated.The obtained coatings present an(110) preferred texture and have a developed columnar structure.With increasing bias voltage,the surface structure of Cr coating becomes denser.All of the Cr-coated AZ31 have much higher surface microhardness than bare ...     

Preparation and properties of a cerium-containing hydroxyapatite coating on commercially pure titanium by micro-arc oxidation

A porous cerium-containing hydroxyapatite coating on commercially pure titanium was prepared by micro-arc oxidation （MAO） in an electrolytic solution containing calcium acetate, p-glycerol phosphate disodium salt pentahydrate （β-GP）, and cerium nitrate. The thickness, phase, composition morphology, and biocompatibility of the oxide coating were characterized by X-ray diffraction （XRD）, electron probe microanalysis （EPMA）, scanning electron microscopy （SEM） with energy dispersive X-ray spectrometer （EDS）, and cell culture. The thickness of the MAO film is about 15-25 ~tm, and the coating is porous and uneven, without any apparent interface to the titanium substrates. The results of XRD and EDS show that the porous coating is made up of hydroxyapatite （HA） film containing Ce. The favorable osteoblast cell affinity makes the Ce-HA film have a good biocompatibility. The Ce-HA film is expected to have significant medical applications as dental implants and artificial bone joints.     

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...     

Enhanced corrosion performance of magnesium phosphate conversion coating on AZ31 magnesium alloy

Magnesium phosphate conversion coating (MPCC) was fabricated on AZ31 magnesium alloy for corrosion protection by immersion treatment in a simple MPCC solution containing Mg²⁺ and PO^3?₄ ions. The MPCC on AZ31 Mg alloy showed micro-cracks structure and a uniform thickness with the thickness of about 2.5 µm after 20 min of phosphating treatment. The composition analyzed by energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy revealed that the coating consisted of magnesium phosphate and magnesium hydroxide/oxide compounds. The MPCC showed a significant protective effect on AZ31 Mg alloy. The corrosion current of MPCC was reduced to about 3% of that of the uncoated surface and the time for the deterioration process during immersion in 0.5 mol/L NaCl solution improved from about 10 min to about 24 h.     

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。     

Si基上羟基磷灰石/Al2O3复合生物涂层的制备

采用物理气相沉积(PVD)与阳极氧化与电沉积相结合的复合技术在Si基表面制备了羟基磷灰石(HA)/Al2O3复合生物涂层。采用SEM研究了阳极氧化Al2O3和HA/Al2O3复合生物涂层的形貌,并采用EDS与XRD研究了HA/Al2O3复合生物涂层的组成和物相。结果表明:扩孔处理后阳极氧化的Al2O3孔径约为1.5~3.0μm,电沉积HA的n(Ca)/n(P)约为1.61,最终获得了以HA为外层、HA/Al2O3为中间过渡层、Si为基底的复合材料。其中,HA不仅沉积于阳极氧化Al2O3的孔洞中,且外延生长并覆盖在阳极氧化Al2O3表面,从而在HA外层与HA/Al2O3中间过渡层之间形成了一种T形分布的结构特征,该结构特征将有助于增强HA外层与中间过渡层的界面结合强度。     

Novel electrodeposition process for preparing hydroxyapatite coating on titanium substrate

A novel process for electrodeposition of hydroxyapatite coating on titanium substrate was developed. The mechanism of the electrochemical reaction on the cathode was changed by adding H2 O2 into the electrolyte. The evolution of H2 gas was erased. And owing to the fact that H2O2 posesses high tendency of being reduced, a fairly high cathodic current can be gained at a more positive potential than -- 1.0 V. During the electrodeposition, 6% H2O2 is added, the temperature of deposition is fixed at 55 ℃ and pH of electrolyte is adjusted to 5.5. Dense and homogeneous film is crystallized at high rate. The mechanism of crystallize process was discussed.     

Laser-assisted laser ablation method for high-quality hydroxyapatite coating onto titanium substrate

Hydroxyapatite (HAp) coating on titanium (Ti) or Ti alloy implant materials is one of the important technologies for improving the bioactivity of their surface. We recently developed a new HAp coating method using two laser beams, laser-assisted laser ablation method (LALA method). In this method, two excimer lasers were used. One laser beam from KrF laser, the ablation laser, is used for ablation of a HAp target. The other beam from ArF laser, the assist laser, is used to irradiate a Ti substrate surface during formation of the HAp coating. The assist laser plays an important role in the formation of a crystalline HAp coating and improves the strength of adhesion to the Ti substrate.The coating quality varied with the timing of the assist laser irradiation. A coating deposited with a long assist laser delay contained a large amorphous component. High-quality coatings were obtained with delay time between 2 and 10 μs.Using the present method, we succeeded in fabricating thin (≤1 μm) HAp coatings with high crystallinity and high adhesion strength.     

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。     

Microstructure and properties of oxalate conversion coating on AZ91D magnesium alloy

The oxalate coating formed on AZ91D magnesium alloy by chemical conversion treatment methods in oxalate salt solutions was investigated. The surface morphologies and chemical composition of coating were examined using scanning electron microscopy (SEM) equipped with energy dispersive analysis of X-ray (EDX). Electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves and salt spray tests were employed to evaluate corrosion protection of the coating to substrate in 5% NaCl solution. The mechanism of coating formations was also considered in details. The results indicate that a compact and dense surface morphology with fine particle clusters of the oxalate coating on magnesium alloy is presented, which mainly consists of oxide or/and organic of Mg, Al and Zn. And the anti-corrosion of the magnesium after oxalate conversion treatment is better than that of the magnesium substrate. The results of salt spray test for oxalate coating is evaluated as Grade 9 according to ASTM B117. The electric resistance of oxalate chemical conversion coating to substrate is below 0.1 Ω.     

Improvement in corrosion resistance of magnesium coating with cerium treatment

Corrosion protection afforded by a magnesium coating treated in cerium salt solution on steel substrate was investigated using open circuit potential, polarization curves, and electrochemical impedance spectroscopy (EIS) in 0.005 M sodium chloride solution (NaCl). The morphology of the surface was characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). The cerium treated coating was obtained by immersion in CeCl3 solution. The results showed that the corrosion resistance of the treated magnesium coating was improved. The corrosion potential of the treated coating was found to be nobler than that of the untreated magnesium coating and the corrosion current decreased significantly. Impedance results showed that the cerium treatment increased corrosion protection. The improvement of anti-corrosion properties was ataibuted to the formation of cerium oxides and hydroxides that gave to a physical barrier effect.     

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。     

镁合金微弧氧化陶瓷膜的制备及耐蚀性能

利用微弧氧化技术在AZ91D镁合金表面原位生成含有钙、磷元素的陶瓷膜层.用SEM、XRD、EDS等研究陶瓷膜微观形貌、相组成及元素含量,利用Tafel和EIS技术来评价陶瓷膜的腐蚀性能.结果表明,所制备的陶瓷膜层成功地引入了钙和磷元素,陶瓷膜层主要由Mg2SiO4和MgO相组成.增加钙盐浓度,可以使膜层内的钙元素含量增多,微孔增加并且出现了微裂纹.电化学测试表明陶瓷膜使得镁合金在0.9%NaCl生理盐水中的耐蚀性提高了1～2个数量级,当钙盐浓度为0.3 g/L时,陶瓷膜层的耐蚀性最好.     

Fabrication and properties of the superhydrophobic ceria-based composite coating on magnesium alloy

A superhydrophobic ceria-based composite coating is developed to improve anticorrosion properties of AZ61 magnesium alloy, fabricating via chemical conversion method followed by hydrothermal treatment. The cerium conversion coating has a block structure with microcracks. After the hydrothermal treatment, a dense CeO₂ layer, porous CeO₂ nanorods, and stearic absorbing layers are grown stepwise on the conversion coating. And the composite coating is hydrophobic or even superhydrophobic and has almost no microcracks. As the hydrothermal reaction time increases, the water contact angle of the composite coating first increases and then decreases, and it reaches the maximum value of 152° after hydrothermal treatment for 4 h. Both the dense CeO₂ layer and the superhydrophobic stearic absorbing layer can effectively prevent the electrolyte from contacting the substrate; the corrosion current density of the superhydrophobic composite coating is lower than that of the hydrophilic composite coating and the cerium conversion coating, and has the best corrosion resistance.     

AZ31镁合金表面液相渗铝的工艺与性能

采用液相扩渗技术在挤压态AZ31镁合金表面快速渗入铝，在合金表面获得过共晶渗层，并对渗层的成分、相组成、扩渗过程、纳米硬度和腐蚀性能进行分析。结果表明：AZ31镁合金在480℃热扩渗铝过程中发生了“熔化—凝固”变化，渗层为典型的过共晶组织：渗铝层含有Mg17A112相和镁的铝饱和固溶体，这种渗层具有较高的纳米硬度和较好的耐腐蚀性能；通过提高扩渗温度进行液相扩渗可以大大提高扩渗速度，但由于快速凝固收缩会造成表层产生起伏现象，控制冷却速度可以将表层起伏控制在可接受的范围。     

Effect of heat diffusion on properties of zinc-aluminum coating on AZ91D magnesium alloys

A protecting zinc and aluminum coating on the surface of AZ91D magnesium alloys was obtained by thermal spraying to improve the corrosion and wear resistance performances. In order to enhance the combination between magnesium alloy matrix and zinc and aluminum coating, the sample was heat-treated at 300 ℃ for 2 h, then, the cross-section patterns, XRD pattern, micro-hardness, wear and corrosion resistance abilities were researched. The results indicate that the interface between the coating and substrate is metallurgical bond, and a transitional fusion layer is formed by diffusion. The micro-scale abrasion test and polarization test in 3% NaCl solution show that the diffusion-treated specimen has better wear and corrosion resistance performances in comparison with the undiffusion-treated and substrate magnesium alloys; in addition, it has relatively higher micro-hardness than the undiffusion-treated magnesium alloys.     

Corrosion resistance,composition and structure of RE chemical conversion coating on magnesium alloy

Golden yellow rare earths chemical conversion coating was obtained on the surface of magnesium alloy by immersing in cerium sulfate solution.The corrosion resistance of RE conversion coating was evaluated using inmersion test and potentiodynamic polarization measurements in 3.5%NaCl solution.The morphologies of samples before corrosion and after corrosion were observed by SEM.The structures and compositions of the RE conversion coating were studied by means of XPS,XRD and IR.The results show that,the con...