电沉积磷酸钙生物活性陶瓷

在医用合金Ti6A14V基底上研究了电流密度、阴极电位和电解液温度等实验条件对磷酸钙生物陶瓷电沉积层的组成、结构和表面形貌等特性的影响，用扫描电子显微镜（SEM）、X射线衍射（XRD）、傅立叶变换红外光谱（FTIR）和感耦等离子体原子发射光谱（ICP／AES）等技术对磷酸钙陶瓷沉积层进行了表征．依据各种用酸钙盐的热力学性质，采用低温城液后处理的方法将前驱体转化为均匀单一的多孔状纯羟基历灰石沉积层．     

镍钨硼合金沉积机理及镀层微晶尺寸

应用循环伏安、恒电位阶跃和Ｘ射线衍射（ＸＲＤ）等研究了Ｎｉ－Ｗ－Ｂ合金电沉积特点和镀层微晶尺寸。结果表明,在以柠檬酸铵为络合剂的溶液中,Ｎｉ－Ｗ－Ｂ合金沉积层较Ｎｉ－Ｗ合金有较低的电化学活性。电位阶跃ｉ￣ｔ曲线分析表明,在玻碳电极上Ｎｉ－Ｗ－Ｂ合金电结晶过程遵循扩散控制瞬时成核三维成长模式,且随过电位的增加,电极表面晶核数增多。ＸＲＤ测试结果表明,随沉积电流密度提高,合金镀层微晶尺寸逐渐增大,说明     

镍钨磷合金电结晶机理及其镀层结构与显微硬度

应用循环伏安、恒电位阶跃和 X射线衍射（ XRD）等方法研究了 Ni-W-P合金电沉积特点和镀层结构与显微硬度 .结果表明,在以柠檬酸铵为配体的溶液中, Ni-W-P合金沉积层较 Ni-W合金有较低的电化学活性 .根据电位阶跃的 i～ t曲线分析表明,在玻碳电极上 Ni-W-P合金电结晶过程遵从扩散控制瞬时成核三维成长模式进行,随着过电位的增加,电极表面上晶核数增多 . XRD试验结果表明, Ni-W-P合金镀层呈现明显的非晶态特征 .所获得的 Ni-W-P合金电沉积层的显微硬度在 450 kg· mm－ 2左右 .     

二甲基亚砜中电沉积钬钴合金的研究

研究了在二甲基亚砜中钬与钴的电解共沉积。测定循环伏安曲线获知钬钴共沉积的沉积电位较钴单独析出为负而较钬的析出为正,属于诱导共沉积类型,恒电位电解表明在一定浓度范围内电位是影响合金成分的主要因素,而镀液组成的影响较小,在－1.8V下恒电位电解得到了均匀、致密的非晶态合金沉积层。     

采用AlCl_3-EMIC-MgCl_2室温离子液体电沉积制备铝-镁合金（英文）

采用恒电流和恒电位技术,以及路易斯酸氯化铝(III)-1-乙基-3-甲基咪唑氯化物离子液体中添加氯化镁(II),室温下在铂和铜阴极表面电沉积制备了铝-镁合金.合金层中镁的含量随离子液体中氯化镁浓度和所施加的阴极电流密度的增加而增加.采用X-射线衍射谱(XRD)、扫描电子显微镜(SEM)和能量散射X-射线谱(EDAX)技术,研究了不同电沉积实验条件得到的电沉积层的晶体结构及表面形貌.增加沉积电流密度,可以制备出致密、光亮和结合力良好的电沉积层.铝-镁合金电沉积的阴极电流效率可达99%.应用电化学石英晶体微天平(EQCM)技术研究了电沉积合金的组成.根据重声阻抗分析得到的质量-电荷(m-Q)曲线斜率计算了金属共沉积层的化学成分.     

镍钨磷合金电结晶机理及其镀层结构与显微硬度

应用循环伏安,恒电位阶跃和Ｘ射线衍射（ＸＲＤ）等方法了Ｎｉ－Ｗ－Ｐ合金电沉积特点和镀层结构与显微硬度,结果表明,在以柠檬酸铵为配体的溶液中,Ｎｉ－Ｗ－Ｐ合金 层较Ｎｉ－Ｗ合金有较低的电化学活性,根据电位阶跃的ｉ－ｔ曲线分析表明,在玻碳电极上Ｎｉ－Ｗ－Ｐ合金电结晶过程遵从扩散控制瞬时成核三维成长模式进行,随着过电位的增加,电极表面上晶核数增多,ＸＲＤ试验结果表明,Ｎｉ－Ｗ－Ｐ合金镀层呈现明显的非晶态特征,所获得的Ｎｉ－Ｗ－Ｐ合金电沉层的显微硬度在４５０ｋｇ．ｍｍ＾－２左右。     

两步电化学沉积技术制备功能陶瓷/金属复合镀层

通过两步电化学沉积技术,在医用金属表面得到羟基磷灰石生物活性陶瓷/金属复合镀层.从含有硝酸钙和磷酸二氢氨的溶液中,首先通过恒流模式电化学沉积钙磷生物陶瓷;然后采用恒压模式,在多孔的生物陶瓷沉积层中嵌入金属骨架,从而得到具有良好结合力的羟基磷灰石/金属复合镀层.实验结果表明在复合镀层中作为骨架的金属镍含量约为31%时,复合镀层与基底合金之间的结合力达到21.2MPa.     

Ni—Mo—PTFE复合电极的制备及其对甲醇电氧化的催化性能

在０．２２ｍｏｌ／Ｌ硫酸镍，０．０６ｍｏｌ／Ｌ钼酸钠，０．３ｍｏｌ／Ｌ柠檬酸钠，３０ｇ／ＬＰＴＦＥ乳液，０．１ｇ／ＬＦＣ－４００表面活性剂的电解液（ｐＨ＝９）中，于温度４５℃，通以１０ｍＡ／ｃｍ２的电流，在纯Ｃｕ片上沉积出Ｎｉ－Ｍｏ－ＰＴＦＥ复合沉积层，ＸＲＤ、ＸＰＳ表征结果表明，该复合沉积层属立方晶系，其点阵型式为面心点阵Ｆ，晶胞参数ａ为０．３５７３ｎｍ，镍钼合金为固溶体结构，其（１１１）织构度ＴＣ（１１１）为６８％，表明该沉积层呈（１１１）择优取向．沉积层表面的氟以（ＣＦ２）ｎ的形式存在，ＳＥＭ观察结果表明沉积层含有ＰＴＦＥ时表面的粗糙度增大．镍－钼－ＰＴＦＥ复合电沉积过程经历吸附态物种氢氧化镍和钼的氧化物，它们继续捕获电子被还原为镍钼合金，ＰＴＦＥ粒子以包埋的形式沉积于镀层中．循环伏安结果表明该复合电极在ＮａＯＨ溶液中对甲醇的电氧化具有催化活性．     

Ni-Mo合金电沉积层织构及形成机理

在组成为：０．２２ｍｏｌ／Ｌ硫酸镍、０．０６ｍｏｌ／Ｌ钼酸钠和０．３ｍｏｌ／Ｌ柠檬酸钠的溶液,于纯铜片上采用恒电流沉积,所得Ｎｉ－Ｍｏ合金沉积层经Ｘ射线衍射测定,结果表明在温度为２５℃～５０℃,电流密度为１０ｍＡ·ｃｍ－２～３０ｍＡ·ｃｍ－２范围,Ｎｉ－Ｍｏ合金沉积层表现为（１１１）择优取向．循环伏安和电位阶跃实验表明镍钼合金电结晶过程按照连续成核和三维生长方式进行．Ｎｉ－Ｍｏ合金电沉积过程的电化学交流阻抗谱表明Ｎｉ－Ｍｏ共沉积过程经历了吸附中间产物步骤,由于吸附态物种氢氧化镍和钼的氧化物将阻化晶粒（１１１）晶面的生长,从而使镍钼沉积层表现为（１１１）择优取向．     

镍钨硼合金电沉积机理及镀层微晶尺寸

应用循环伏安、恒电位阶跃和X射线衍射 (XRD)等方法研究了Ni_W_B合金电沉积特点和镀层微晶尺寸 .结果表明 ,在以柠檬酸铵为络合剂的溶液中 ,Ni_W_B合金沉积层较Ni_W合金有较低的电化学活性 .电位阶跃i～t曲线分析表明 ,在玻碳电极上Ni_W_B合金电结晶过程遵循扩散控制瞬时成核三维成长模式 ,且随过电位的增加 ,电极表面晶核数增多 .XRD测试结果表明 ,随沉积电流密度提高 ,合金镀层微晶尺寸逐渐增大 ,说明电流密度提高将更加有利于Ni_W_B合金电结晶过程中的晶核生长 .     

造孔剂对电泳沉积制备多孔HA涂层及其生物活性的影响

采用水热法制得的羟基磷灰石(HA)纳米粉体,分别与造孔剂葡萄糖(Glu)、壳聚糖(CS)、炭粉(C)3种微粒(＜38.5 μm)配置成质量比1∶1的悬浮液,电泳沉积 烧结制备钛基多孔HA涂层,并对制得的3种多孔HA涂层在模拟体液浸泡前后的表面形貌、化学组成及物相变化进行表征。 结果表明,经700 ℃烧结处理后制得的3种多孔HA涂层在1.5倍人体模拟体液中浸泡5 d后,多孔HA涂层表面均被层状生长的碳磷灰石颗粒完全覆盖,颗粒直径在5~25 μm,说明这些多孔HA涂层均具有良好的生物活性。 其中以CS为造孔剂制得的多孔HA涂层结合强度最高,达19.5 MPa,有望开发成为新型的人骨植入生物陶瓷材料。     

脉冲电沉积制备HA/ZrO2纳米复合涂层的稳定性及生物相容性评价

采用脉冲电化学沉积法成功地在生物医用钛金属表面制备出均匀的纳米HA/ZrO₂复合涂层. 通过热处理提高涂层的致密性, 同时保留涂层的微纳结构. 考察了热处理后复合涂层的成分、形貌、生物相容性及生理稳定性. X射线衍射分析表明, 复合涂层成分为HA和ZrO₂. 扫描电镜观察发现, 热处理后复合涂层的致密性有所提高. 研究发现, ZrO₂的加入大大降低了HA/ZrO₂复合涂层中钙离子的释放速度, 提高了HA/ZrO₂复合涂层的生理稳定性. 纳米划痕实验结果表明, HA/ZrO₂复合涂层具有较好的结合强度. 通过培养成骨细胞考察了复合涂层的生物相容性. Alamar Blue检测表明, HA/ZrO₂复合涂层表面细胞黏附及增殖能力较好. ALP检测发现, 热处理后HA/ZrO₂复合涂层表面的细胞分化能力较强. 综合细胞培养结果显示, HA/ZrO₂复合涂层有较好的生物相容性.     

Applying diamond like carbon layer on carbon/carbon composites and its effect on the deposition of hydroxyapatite coating

The biomedical application of carbon/carbon (C/C) composites is limited by lacking bioactivity and releasing carbon debris. Hydroxyapatite (HA) coating has been used to improve the bioactivity of C/C composites, but it cannot reduce the release of carbon debris effectively because of poor wear resistance property. In this work, a wear‐resistant layer of diamond like carbon (DLC) is applied on C/C composites, followed by an ultrasound‐assisted electrochemical deposition to prepare HA coatings. The microstructure, morphology and chemical composition of the DLC layer and the HA coating are characterised by scanning electron microscopy, X‐ray diffraction, energy dispersive spectroscopy (EDS), X‐ray photoelectron spectroscopy, Fourier transformed infrared spectroscopy and Raman spectrum. The bonding strength between the HA coating and the DLC layer modified C/C composites is examined by a tensile test. The results show that the DLC layer has a spherical morphology and provides a uniform surface for the deposition of the HA coating. The HA coating shows flaky morphology with a compact structure. The tensile strength of the HA coating on the DLC layer modified C/C composites is 6.24 ± 0.40 MPa, which is significantly higher than that of HA coating on unmodified C/C composites(3.04 ± 0.20 MPa). Copyright © 2013 John Wiley & Sons, Ltd.     

羟基磷灰石涂层的电化学可控制备及生物性能的初步表征

控制不同沉积条件制备不同结构形貌的羟基磷灰石涂层,主要获得3种由不同尺寸晶粒构成的直立状、花簇状和多孔状典型形貌特征的涂层;XRD物相分析显示,该涂层主要由结晶良好的羟基磷灰石组成;FT-IR组分分析未检测到其他钙磷盐成分的存在.体外细胞培养试验表明,以上各种形貌的羟基磷灰石涂层均具有良好的生物相容性,但其生物活性则因形貌而异,其中纳米有序多孔状羟基磷灰石涂层表现出最高的生物活性,而花簇状的涂层生物活性相对较低.     

钛基多孔HA/SiO2复合涂层的制备及性能研究

为了制得表面多孔且与基材结合强度高的羟基磷灰石(HA)涂层,实验中以正丁醇为分散介质,以SiO2粉末为添加剂,纯钛片为基材,电泳沉积制备羟基磷灰石/二氧化硅/壳聚糖/(HA/SiO2/CS)复合涂层,经后续热处理得到多孔HA/SiO2复合涂层,采用扫描电镜(SEM)、傅立叶红外光谱仪(FT-IR)、X射线衍射仪(XRD)、万能材料试验机对涂层的表面形貌、组成、结构和结合强度进行测试和表征,并通过模拟体液(SBF)浸泡法对复合涂层的生物活性进行评价.结果表明:当悬浮液中的HA/SiO2/CS质量比为1∶1∶1时,制得的HA/SiO2/CS涂层经700℃热处理后获得的HA/SiO2复合涂层孔洞分布均匀,大孔孔径在10～15μm,小孔孔径在1～5μm;涂层与基材的结合强度达到25.5 MPa;多孔HA/SiO2复合涂层在SBF中浸泡7 d后,涂层表面碳磷灰石化;说明实验中添加SiO2所制得的多孔HA/SiO2复合涂层与钛基材结合强度高,且具有良好的生物活性.     

钛表面生物活性榍石/氧化钛复合涂层的结构和磷灰石形成机理

采用微弧氧化和热处理复合技术,在钛表面制备了具有双层结构的榍石/氧化钛复合涂层。榍石/氧化钛复合涂层的外层是由微弧氧化涂层经热处理后晶化生成;而内层是由钛基底的氧化生成,并且氧化钛表现出不同的Ti,O原子比。由于钛基底的氧化,孔径在50~500nm的微孔呈层状结构分布在涂层内层。与微弧氧化涂层相比,该复合涂层具有很好的磷灰石诱导能力,这是由于榍石沿着特定晶面和晶向与羟基磷灰石表现出良好的晶体学匹配关系,从而为磷灰石的成核和取向沉积过程提供良好的位点。     

钛表面生物活性榍石/氧化钛复合涂层的结构和磷灰石形成机理(英文)

采用微弧氧化和热处理复合技术,在钛表面制备了具有双层结构的榍石/氧化钛复合涂层。榍石/氧化钛复合涂层的外层是由微弧氧化涂层经热处理后晶化生成;而内层是由钛基底的氧化生成,并且氧化钛表现出不同的Ti,O原子比。由于钛基底的氧化,孔径在50~500 nm的微孔呈层状结构分布在涂层内层。与微弧氧化涂层相比,该复合涂层具有很好的磷灰石诱导能力,这是由于榍石沿着特定晶面和晶向与羟基磷灰石表现出良好的晶体学匹配关系,从而为磷灰石的成核和取向沉积过程提供良好的位点。     

Sol-Gel Derived Calcium Phosphate Coatings for Biomedical Applications

Hydroxyapatite (HA) coatings have received considerable attention because they exhibit bone bonding capabilities. Unfortunately the common forms of coating production result in cracking and degradation of HA due to the thickness of the coatings and the elevated temperatures employed. This study demonstrates the production of sub-micron, crack-free calcium phosphate coatings on quartz glass substrates using a sol-gel dip-coating technique and firing temperatures below 1000°C.Coatings fired at 1000°C comprised a mixture of hydroxyapatite (HA) and tricalcium phosphate (TCP). XPS analysis of the coating surface showed that the Ca/P ratio lay in the range 1.5–1.67, and that there was a contribution from carbon in the form of carbonate.It is proposed that the sol-gel coatings comprising a resorbable (TCP) and an insoluble (HA) phase have potential benefits in certain implant applications.     

Fabrication and In vitro Bioactivity of Robust Hydroxyapatite Coating on Porous Titanium Implant

Compared witli the traditional dental implant, TixOs■ manufactured by direct laser metal forming(DLMF) technology exhibits improved capability for bone osteointegration due to its porous surface structure, and has achieved remarkable clinical effect. However, like the traditional titanium and other alloyed implants, the porous titanium implant TixOsR also has relatively weak bioactivity. To address this issue, a proper surface modification method may be needed. Hydroxyapatite(HA) has been widely used in implant surface coating for its similar chemical composition to bone tissue and its osteoconductive properties. Thus, combining TixOs■ implants with hydroxyapatite can be an efficient way to enhance their bioactivity. We herewith reported a competent pulsed laser deposition(PLD) method of coating nano-sized HA thin film onto the porous TixOs■ implant. The HA coatings were characterized by means of scanning electron microscopy(SEM), energy dispersive X-ray spectroscopy(EDS), X-ray photoelectron spectroscopy(XPS) and focused ion beam(FIB) method, and nanocrystal sized thin HA films were identified on the surface of TixOs■ implants. The low cytotoxicity and improved cell proliferation ability of HA coated implants were further tested and verified using MC 3T3 E1 cells with the consideration of the controlling group. Our results show that a stable and bioactive HA tliin film is able to form on the surtace of the porous titanium implant by PLD method.This may benefit the fiirther clinical application of TixOs■ implants.     

Characterization and cytocompatibility of polydopamine on MAO‐HA coating supported on Mg‐Zn‐Ca alloy

Magnesium has been suggested as a potential biodegradable metal for the usage as orthopaedic implants. However, high degradation rate in physiological environment remains the biggest challenge, impeding wide clinical application of magnesium‐based biomaterials. In order to reduce its degradation rate and improve the biocompatibility, micro‐arc oxidation coating doped with HA particles (MAO‐HA) was applied as the inner coating, and polydopamine (PDA) film was synthesized by dopamine self‐polymerization as the outer coating. The microstructure evolution of the coating was characterized using scanning electron microscopy (SEM), atomic force microscope (AFM), X‐ray diffraction analyses (XRD), Fourier transform infrared spectroscopy (FT‐IR), and X‐ray photoelectron spectroscopy (XPS). The results showed that PDA film had covered the entire surface of MAO‐HA coating and the pore size of MAO‐HA coating decreased. The root mean square (RMS) roughness of PDA/MAO‐HA coatings was approximately 106.46 nm, which was closer to the optimum surface roughness for cellular attachment as compared with MAO‐HA coatings. Contact angle measurement indicated that the surface wettability had been transformed from hydrophobic to hydrophilic due to the introduction of PDA. The PDA/MAO‐HA coatings exhibited better corrosion resistance in vitro, with the self‐corrosion potential increasing by 150 mV and the corrosion current density decreasing from 2.09 × 10^?5 A/cm ² to 1.46 × 10^?6 A/cm ² . In hydrogen evolution tests, the corrosion rates of the samples coated with PDA/MAO‐HA and MAO‐HA were 4.40 and 5.95 mm/y, respectively. MTS assay test and cell‐surface interactions experiment demonstrated that PDA/MAO‐HA coatings exhibited good cellular compatibility and could promote the adhesion and proliferation of MC3T3‐E1 cells.