钛表面FHAP涂层的电沉积制备及其FTIR特征研究

在含有Ca2+,PO3-₄和F-的电解液中,用电化学恒电流方法,在工作电流为0.9 mA温度为60 ℃的条件下沉积60 min,在医用钛(Ti)表面上制得含氟羟基磷灰石(FHAP)涂层。采用扫描电镜(SEM)、能量弥散X射线谱(EDS)、X射线衍射(XRD)对涂层进行表征,用傅里叶变换红外光谱(FTIR)考察了氟离子的引入对涂层构象和生物活性的影响。结果表明：氟部分取代磷灰石中的羟基,FHAP晶格常数变小,涂层相貌由疏松的微米级的菊花瓣状变化为致密的纳米级的尖锥状。FTIR分析表明,涂层中羟基的伸缩和弯曲振动模式的对称性发生了改变,模拟体液浸泡后涂层覆盖碳磷灰石,涂层生物活性良好。     

壳聚糖/SrHAP复合涂层的制备及其FTIR特征分析

在含有Sr2+,Ca2+,PO3-₄和壳聚糖(CHI)的电沉积液中,用恒电流沉积法,在医用纯钛(Ti)表面上得到壳聚糖/掺锶羟基磷灰石(SrHAP)复合涂层。采用扫描电镜(SEM)、能量弥散X射线谱(EDS)、X射线衍射(XRD)对涂层进行检测,用傅里叶变换红外光谱(FTIR)考察了壳聚糖和锶离子的掺杂对HAP涂层构象和生物活性的影响。结果表明：锶部分取代磷灰石中的钙,表面形貌由疏松的针状变为较致密的片状。FTIR分析表明,涂层中出现了典型的amideⅠ和amideⅡ的壳聚糖振动峰,则CHI与SrHAP杂化良好;模拟生理液浸泡后表面覆盖有球状类骨磷灰石,则涂层具备较好的生物活性。塔菲尔测试表明,复合涂层使得Ti表面的抗生理腐蚀性显著提高。     

Si，Ag，F离子共修饰HA纳米生物薄膜的制备与表征

采用单电流阶跃电化学沉积技术,在商业纯钛(CP-Ti)表面构建硅、银、氟离子共修饰羟基磷灰石(Si-Ag-F-HA)纳米复合薄膜。Ag+的持续释放可以提供有效的抗菌性,Si4+作为生物活性元素可以有效地抵消Ag+的潜在细胞毒性。采用电感耦合等离子体质谱法(ICP-MS)测定涂层中硅和银元素的释放规律。采用傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、能量弥散X射线谱(EDS)、X-射线衍射(XRD)等技术对得到的材料进行了表征。结果表明：Si,Ag和F三种元素均匀地掺杂到了HA的晶体结构中。Si-Ag-F-HA为纳米级的针状晶体结构,薄膜整体致密且均匀。Si-Ag-F-HA纳米生物薄膜可以在一周内很好地诱导类骨磷灰石的形成,具有优异的生物活性。塔菲尔曲线测试结果证实涂层的耐SBF腐蚀性较好。ICP-MS测试结果表明Si-Ag-F-HA纳米生物薄膜可以提供持续的Si和Ag离子释放。FTIR 和ICP-MS等光谱技术为开发新型抗菌硬组织修复材料提供了高效快速的检测手段。     

基于FTIR,ICP-MS的仿生Mg-Ag-HA/明胶抗菌生物涂层的制备与表征

目前,傅里叶变换红外光谱（FTIR）技术具有待测样品数量少、对特征基团灵敏度高、样品制备和分析简单等优点;电感耦合等离子体质谱（ICP-MS）的优势也较为显著：微量元素的高灵敏度检出率,低检测限和多元素的同时分析;协同上述两种方法,可快速对功能医用材料的化学元素和基团进行鉴定,从而为仿生医用抗菌材料的研发提供新的设计思路和理论依据。羟基磷灰石(HA)因其优异的骨传导和骨诱导特性被用于薄膜材料,钛植入表面HA薄膜已进入临床应用阶段。但是,HA的本真脆性和缺乏抗菌性,常常导致植入失败。因此,开发一种耐磨性好且抑菌性优的促成骨功能涂层成为当前急需要解决的难题。研究目的在于在钛表面制备耐磨性好且抑菌性优的促成骨功能涂层,初步探讨了涂层的抗菌离子缓释规律和生物活性。开拓性地在工业纯钛表面制备了明胶、银和镁离子改性的羟基磷灰石(Mg-Ag-HA/明胶)抗菌涂层。将银(Ag)引入羟基磷灰石涂层(HA)以改善其抗菌性能,镁(Mg)作为第二元素以提高生物相容性,明胶可以同时提高HA的生物相容性和力学性能。ICP-MS测定涂层中镁和银元素的释放量和可持续性。所得到的新型Mg-Ag-HA/明胶的SEM结果、Ca/P比值、化学特征峰和晶相通过FTIR, SEM,EDAX和XRD进行表征。结果表明：明胶的羧基与HA的钙离子之间已形成Ca-COO化学键,明胶和Mg-Ag-HA构成了有机-无机复合涂层;Mg和Ag元素被成功地引入到了HA晶格中,且分布均匀。模拟体液浸泡后,Mg-Ag-HA/明胶涂层试样表面有新的缺钙型的HA生成,且球形磷灰石中检测到新的Mg,Na和Cl元素;结果表明,新型复合涂层样品具有良好的生物活性。SEM和LSCM实验结果观察发现,小鼠颅骨成骨细胞在Mg-Ag-HA/明胶上粘附良好,细胞伸展大量伪足,未见细胞毒性。明胶的加入大大降低了复合镀层中Mg2+和Ag+的释放速率,提高了复合镀层的生理稳定性,为镀层保持长期抗菌功能提供了保证。Mg-Ag-HA/明胶作为钛基涂层材料具有良好的抗菌离子释放能力和优异的生物相容性,为新型抗感染外科植入体的研发提供了新思路。     

Si表面离子束辅助沉积Ti纳米膜的研究

用离子束技术探讨了Si表面纳米Ti薄膜制备的可行性以及Ti薄膜组织结构与离子束工艺之间的关系。实验进行试样表面预处理、轰击离子能量、离子密度、温度、沉积时间等离子束工艺参数对单晶Si(111)表面沉积的Ti薄膜结构的影响。采用原子力显微镜(AFM)和扫描电子显微镜(SEM)分析了Ti膜表面晶粒形貌，并用X射线衍射仪(XRD)和俄歇电子谱仪(AES)分析了Ti膜的结构和成分。由于残余气体的影响，Ti膜发生了不同程度的氧化，随温度升高和轰击离子强度增加氧化愈加明显。     

秦陵一号铜车马残件元素组成分析

本文采用光谱和化学分析方法对秦陵一号铜车马残件及其彩绘涂层的化学组成进行了元素分析和测定。残件材质的化学元素分析结果是：铜含量为84％－90％，锡为7％－13％，铅在1％以下，还有少量其它杂质元素总量约占2％左右。铜车巴的残件四折合页和马身上的表面彩绘涂层，经光谱和X射线衍射分析证明，前者含有羟基磷灰石[Ca5(PO4)3OH]；后者含有羟基磷灰石和白铅矿（PbCO3）。它们在秦陵一号和二号铜车马的部件彩绘涂层中作为白色而颜料而存在的矿物质均有发现。     

溶胶-凝胶生物活性玻璃在SBF中反应的形貌特征

利用溶胶 凝胶生物活性玻璃粉末二次烧结工艺 ,制备了CaO P2 O5 SiO2 系统溶胶 凝胶生物玻璃 ,并以其为原料制备了用于骨修复及骨组织工程支架的块状多孔生物活性材料 .并应用体外实验 (invitro)方法和XRD、SEM、FTIR技术研究了此烧结材料的显微形貌、晶相、和生物活性 .结果表明 ,经 80 0℃烧结 5min后 ,材料有硅磷酸钙 (Ca5(PO4 ) 2 SiO4 ,5CPS)析出 ,在模拟体液 (SBF)中浸泡 ,随着时间的增长 ,玻璃表面最初形成的无定形钙磷化合物矿化成碳酸羟基磷灰石 (HCA)纳米团簇 ,并逐渐相互融合形成HCA覆盖层 ;且HCA只在烧结体的玻璃相 (SG相 )表面生成 ,在 5CPS微晶相表面未发现HCA .     

具有阵列-簇双层结构的TiO2纳米棒的光电性能（英文）

选择硫酸氧钛(TiOSO4)作为无机钛源前驱体,通过温和的水热法在掺氟氧化锡导电玻璃基底(FTO)上直接合成单晶金红石相TiO2纳米棒薄膜,呈现阵列-簇双层结构。在模拟太阳光照射下,该纳米棒薄膜的短路电流可达到0.17 mA/cm2,是相同条件下由四异丙醇钛[Ti(iPro)4]为有机钛源而制备的TiO2纳米棒薄膜的2倍多。实验结果表明,多维层状结构和无机硫酸氧根离子(OSO4-4)的存在对TiO2纳米棒薄膜的光电流响应有促进作用。     

多弧离子镀TiN与不同金属基材间的接触界面与表面特性

用多弧离子镀技术在不同金属基材上进行TiN镀膜实验 ,制备了TiN/Fe、TiN/Cu和TiN/Cr/Cu复合膜 .借助扫描电子显微镜 (SEM)、X射线衍射仪 (XRD)和光电子能谱 (XPS) ,研究了TiN与Fe、Cu和Cr/Cu三种不同衬底接触界面的形貌、结构及其表面特性 .SEM观察发现 ,在一定离子镀膜条件下 ,TiN涂层可与Fe、Cu和Cr/Cu金属基材形成均匀平整的接触界面 ,在铜基上TiN界面清晰 ,在Fe与Cr/Cu界面有明显的层状晶界微结晶分布 .XRD分析显示 ,Fe、Cu和Cr/Cu表面生成的薄膜都包含TiN、Ti2 N等多晶相 ,在Cr/Cu界面还包含Ti-Cr的金属间化合物 .XPS结果表明 ,表面除了TiN膜外 ,还生成TiO2 和TiOxNy 等氧化膜 .Ar+ 刻蚀 5min后 ,TiO2 消失 ,TiOxNy 减少 ,TiN则呈增加趋势 .TiN与Cr/Cu界面形成明显的Ti-Cr和Cr-Ni互扩散层 ,这有助于增强薄膜附着力 ,形成较牢固的TiN涂层 .     

棒状纳米纤维素仿生矿化及光谱分析

以棒状纳米纤维素为模板,采用仿生矿化的方法制备纳米纤维素/纳米羟基磷灰石复合材料。并利用X射线衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜能谱分析(SEM-EDAX)对仿生矿化前后纳米纤维素中碳、氧、钙、磷元素的变化情况及分布状态进行了表征,并探讨了纳米羟基磷灰石的生长机理。结果表明纳米纤维素表面形成了纳米羟基磷灰石;纳米纤维素的碳氧比为1.81,仿生矿化后下降为1.54;仿生矿化后纳米纤维素的钙磷比nCa/nP=1.70;纳米羟基磷灰石成核是在纳米纤维素的羟基上,并且纳米纤维素表面羟基和纳米羟基磷灰石的钙离子之间发生了配位作用。纳米羟基磷灰石较为均一的形成在纳米纤维素的基体中。通过原子力显微镜(AFM)图片可以看出,直径为20nm左右的羟基磷灰石生长在纳米纤维素的表面。     

Surface characterisation and electrochemical behaviour of porous titanium dioxide coated 316L stainless steel for orthopaedic applications

Porous titanium dioxide was coated on surgical grade 316L stainless steel (SS) and its role on the corrosion protection and enhanced biocompatibility of the materials was studied. X-ray diffraction analysis (XRD), atomic force microscopy (AFM), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDAX) were carried out to characterise the surface morphology and also to understand the structure of the as synthesised coating on the substrates. The corrosion behaviour of titanium dioxide coated samples in simulated body fluid was evaluated using polarisation and impedance spectroscopy studies. The results reveal that the titanium dioxide coated 316L SS exhibit a higher corrosion resistance than the uncoated 316L SS. The titanium dioxide coated surface is porous, uniform and also it acts as a barrier layer to metallic substrate and the porous titanium dioxide coating induces the formation of hydroxyapatite layer on the metal surface.     

Development and evaluation of electroless Ag-PTFE composite coatings with anti-microbial and anti-corrosion properties

Electroless Ag-polytetrafluoroethylene (PTFE) composite coatings were prepared on stainless steel sheets. The existence and distribution of PTFE in the coatings were analysed with an energy dispersive X-ray microanalysis (EDX). The contact angle values and surface energies of the Ag-PTFE coatings, silver coating, stainless steel, titanium and E. coli Rosetta were measured. The experimental results showed that stainless steel surfaces coated with Ag-PTFE reduced E. coli attachment by 94-98%, compared with silver coating, stainless steel or titanium surfaces. The anti-bacterial mechanism of the Ag-PTFE composite coatings was explained with the extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory. The anticorrosion properties of the Ag-PTFE composite coatings in 0.9% NaCl solution were studied. The results showed that the corrosion resistance of the Ag-PTFE composite coatings was superior to that of stainless steel 316L.     

磁场辅助激光熔覆制备Ni60CuMoW复合涂层

采用磁场辅助激光熔覆技术,在Q235钢表面制备了Ni60CuMoW复合涂层,借助SEM,EDS 和XRD 等表征手段对涂层进行了微观组织和物相分析,利用维氏硬度计测试了复合涂层截面的显微硬度分布,通过摩擦磨损实验和电化学测试系统研究了复合涂层的磨损性能和耐腐蚀性能。研究结果表明:涂层主要由-Ni,Cu）固溶体、硅化物和硼化物组成,Cr3Si晶粒细化且均匀致密;磁场辅助作用下,激光熔覆涂层平均显微硬度达到913HV0.5,为无磁场辅助涂层的1.5 倍,磨损失重仅为无磁场涂层的36%,自腐蚀电位上升了100 mV,腐蚀电流密度降低了70%,耐磨耐蚀性能得到了显著改善。     

Comparison of coating properties obtained by MAO on magnesium alloys in silicate and phytic acid electrolytes

Anodic coatings were prepared by using microarc oxidation (MAO) on AZ91HP in silicate containing solution (Si-solution) and phytic acid containing solution (P-solution), respectively. The influence of the electrolytes on coating structure, morphology and composition was studied by using X-ray diffraction (XRD), environmental scanning electron microscope (ESEM) and energy dispersive X-ray spectroscopy (EDX). Potentiodynamic polarization test and immersion test were employed to evaluate the corrosion resistance of anodic coatings. Different electrolytes caused the differences in the MAO process and coating properties. The breakdown voltage and the final voltage in P-solution were higher than those in Si-solution. The pore uniformity of anodic coatings obtained in Si-solution (Si-film) was worse than that in P-solution (P-film). XRD analyses indicated that Si-film was amorphous, while P-film consisted of MgO. The corrosion resistance of the sample coated with P-film was better than that with Si-film.     

Molybdate and molybdate/permanganate conversion coatings on Mg-8.5Li alloy

A novel environment-friendly conversion coating for Mg-8.5Li alloy was obtained by immersing in a solution of molybdate. The concentration of ammonium molybdate and the addition of potassium permanganate were discussed in this experiment. The surface morphology of the conversion coatings was observed by scanning electron microscopy (SEM), and the chemical composition was investigated by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The corrosion resistance of Mg-8.5Li alloy and conversion coatings were investigated by means of potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and weight loss measurement. The results showed that the coatings with cracked morphology were homogeneous and uniform. The conversion coatings were mainly composed of metal-oxide as detected by XPS. The results of electrochemical measurement and weight loss measurement revealed that the molybdate conversion coating had better corrosion resistance than bare alloy and chromate conversion coating, and the molybdate/permanganate conversion coating had lower corrosion current density and higher coating resistance than the molybdate conversion coating.     

The effect of carbon nanotubes on the corrosion and tribological behavior of electroless Ni-P-CNT composite coating

In this study, Ni-P-CNT composite coating was successfully deposited on the surface of copper by electroless plating. X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) were used to characterize the coatings. The wear behavior of the coatings was investigated using a pin-on-disk test rig and subsequently friction coefficient data were reported. The corrosion behavior of the Ni-P and Ni-P-CNT coated specimen were evaluated through polarization curves and electrochemical impedance spectroscopy (EIS) in 3.5 wt.% NaCl aqueous solution at the room temperature. The results indicated that the incorporation of carbon nanotubes (CNTs) in the coating improved both tribological behavior and corrosion resistance. These improvements have been attributed to superior mechanical properties, unique topological structure and high chemical stability of nanotubes.     

Preparation of the Ni-P composite coating co-deposited by nano TiC particles and evaluation of it's corrosion property

In current research, low carbon steel plates were coated by Ni-P electroless method. The effect of adding different concentrations (ranging from 0.01 g/l to 0.5 g/l) of TiC nano-sized particles to the plating bath on deposition rate, surface morphology and corrosion behavior of Ni-P-TiC composite coatings were investigated. The surface morphology and the relevant structure were evaluated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Corrosion behavior of the coated steel was evaluated by electrochemical impedance spectroscopy (EIS) and polarization techniques. The results showed that addition of TiC nano-particles to Ni-P electroless bath not only changes the surface morphology of Ni-P coating, but also improves corrosion resistance of the steel in comparison with TiC free Ni-P electroless coating. In addition, the deposition rate of coating was also affected by incorporation of TiC particles. It was also found that improvement in corrosion resistance largely depends on the phosphorous and TiC concentrations on the coatings.