Preparation of titanium oxide and hydroxyapatite on Ti–6Al–4V alloy surface and electrochemical behaviour in bio-simulated fluid solution

In order to improve the bonding strength between hydroxyapatite (HA) coating and Ti–6Al–4V substrate, a uniform titanium oxide film was obtained by controlled anodic oxidation. After that an alkaline treatment with NaOH solution was used to make them more bioactive. Finally hydroxyapatite coating has been prepared on Ti–6Al–4V substrate through electrochemical deposition. Comparative electrochemical behaviour of untreated and surface modified Ti–6Al–4V alloy, in bio-simulated fluid solution was investigated by electrochemical techniques. SEM was used to observe the morphology of modified surfaces and the thicknesses of the oxide films prepared were evaluated on the cross-sections of the samples using SEM–FIB.     

Electrochemical deposition of hydroxyapatite coatings on titanium

1 Introduction Titanium implants have been used widely for various types of bone-anchored reconstructions due to their excellent corrosion resistance and mechanical properties. However, titanium exhibits poor osteoinductive properties, fortunately, which…     

可降解镁合金骨螺钉表面微弧电泳水热复合涂层的制备与性能

目的在医用镁合金骨螺钉表面构建羟基磷灰石涂层,有效控制其降解速率。方法利用微弧电泳/水热复合方法,在形貌复杂的骨螺钉表面制备涂层。该方法首先利用电解抛光对骨螺钉表面进行表面预处理,采用微弧电泳技术在其表面制备羟基磷灰石涂层,再利用水热合成对微弧电泳涂层进行封孔。利用XRD、SEM、AFM等分析手段对涂层显微结构进行分析,利用体外浸泡实验和电化学实验对涂层耐腐蚀性能及其对钙磷盐的诱导特性进行了评价。结果在电解抛光电流0.14 A、抛光时间2 min的工艺条件下进行电解抛光预处理,可以提高基体和涂层的结合性能。由于骨螺钉的特殊形状,在微弧电泳电解液中添加丙三醇,并通过调整电解液中丙三醇含量优化微弧电泳工艺(电压155 V,反应时间20 min),能有效抑制尖端放电现象,防止膜层组织疏松和大量的氧化物堆积,以及涂层剥落甚至基体烧蚀的现象。再优化水热合成工艺参数(处理液p H值8.5,反应时间1.5 h,反应温度393 K)对微弧电泳涂层进行封孔,得到微弧电泳/水热复合涂层。结论微弧电泳/水热复合涂层表面形貌为菜花状结构,由纳米棒状羟基磷灰石组装而成,均匀致密,结晶性好。电化学腐蚀测试表明,制备复合涂层后,骨螺钉的腐蚀电流密度降低了一个数量级。在模拟体液中浸泡6天,骨螺钉的形貌依然完整,说明水热复合涂层在改善生物相容性的同时,提高了骨螺钉的耐腐蚀性能。但微动摩擦磨损测试显示,水热复合封孔处理后磨损性能下降。     

20% Al2O3-SiO2(sf)/AZ91D镁基复合材料微弧氧化陶瓷层电化学腐蚀性能

在磷酸盐体系电解液中,对20%(体积分数)硅酸铝短纤维(Al2O3-SiO2)增强AZ91D镁基复合材料进行微弧氧化表面处理获得陶瓷层。利用扫描电子显微镜(SEM)和X射线衍射(XRD)仪分析陶瓷层的表面形貌、截面组织和相组成,采用动电位极化和电化学阻抗谱(EIS)测试评价微弧氧化陶瓷层的电化学腐蚀性能。结果表明,该陶瓷层主要由MgO和MgAl2O4相组成。陶瓷层的腐蚀电流密度比镁基复合材料基体低3个数量级,电化学阻抗大幅升高,耐腐蚀性能明显高于复合材料基体     

UPDHES电泳涂层材料的制备及其防腐性能

目的研究电泳沉积条件及光交联对沉积胶束制备涂层形貌、性能的影响。方法首先通过自由基聚合制备可光交联双亲性丙烯酸酯共聚物(UPDHES),通过全反射红外、氢核磁共振(1H-NMR)对共聚物进行结构表征。然后,将可光交联双亲性丙烯酸酯共聚物在选择性溶剂中自组装形成胶束纳米粒子溶液,利用纳米粒度分析仪、透射电子显微镜(TEM)对胶束粒子的粒径和形貌进行表征。最后,以上述胶束溶液为沉积液,控制不同沉积条件,通过电泳沉积在316L不锈钢表面制备光交联涂层,利用扫描电子显微镜(SEM)、原子力显微镜(AFM)研究了电泳沉积条件及光交联对涂层形貌及性能的影响。同时,通过电化学工作站研究不同条件制备的涂层在1 mol/L HCl中的耐腐蚀性能。结果当沉积电压为5 V、沉积时间为3min时,电泳沉积制备的涂层表面光滑,具有较好的致密性和均一性,此时涂层的自腐蚀电位为-0.36 V,远高于不锈钢(-0.43 V),耐腐蚀性能最优。光交联后,涂层的附着力由2级增加至1级,自腐蚀电位增加至-0.34 V,耐腐蚀性进一步提高。结论电泳沉积胶束制备光交联涂层过程中,沉积时间、沉积电压均存在一最优值,此时制备的涂层结构完整,耐腐蚀性能最好。光交联可进一步提高涂层的耐腐蚀性能。     

Electrodeposition of zinc and composite zinc–yttria stabilized zirconia coatings

Pure zinc and composite coatings of zinc and nano-sized yttria stabilized zirconia (YSZ) particles were prepared by cathodic electrodeposition from zinc sulphate-based electrolytes containing gelatin. The effects of gelatin on the morphology, crystallographic orientation of the zinc coatings and deposition mechanism of the composite Zn–YSZ coatings were studied. The coatings obtained were studied by scanning electron microscopy (SEM) with energy dispersion spectroscopy (EDS), X-ray diffraction and potentiodynamic polarization measurements. It was shown that the addition of gelatin to the electrolyte significantly changed the microstructure and crystallographic orientation of the zinc deposits and improved the coating microhardness. In the case of the composite coating co-deposition process, the YSZ particles were found to preferentially rest on the edges or macrosteps of the deposited zinc crystals. The incorporation of YSZ particles into the composite coating was enhanced by reducing the solution pH and through the addition of gelatin. The mechanical and electrochemical properties of conventional zinc coatings were observed to be significantly improved by the incorporation of YSZ particles.     

双级HPPMS靶电流对TiN镀层微观结构及耐蚀性的影响

高功率脉冲磁控溅射（HPPMS）利用较高的脉冲峰值靶功率密度（如：1-3kW/cm2）获得高密度的等离子体，可提高TiN镀层的微观结构和力学性能。然而，HPPMS技术的主要缺点是平均沉积速率较低，增加了镀层的制备成本。为了解决传统HPPMS平均沉积速率低的问题，研究提出一种新型的双级HPPMS技术，即在一个脉冲周期内具有两个连续的、独立可调的脉冲阶段。通过对双级HPPMS电场的合理调配，可制备得到结构致密的TiN镀层，研究了双级HPPMS靶电流对TiN镀层微观结构及耐蚀性的影响。结果表明，当靶电流增大至20A时，靶面形貌由小凹坑转变为大面积凹坑，说明镀料粒子的脱靶方式由碰撞溅射转变为升华或蒸发。同时，当靶电流为10A时，镀层颗粒呈现三棱锥状结构，平均晶粒尺寸为11nm；当靶电流增大至25A时，镀层颗粒呈现光滑致密的圆胞状结构，平均晶粒尺寸为18nm，光滑致密的组织结构使镀层具有较好的耐蚀性。     

有机溶剂中金属镁薄膜的电沉积行为研究

配制有机非质子极性溶剂EtMgCl/THF溶液作为镁电沉积电解液,采用循环伏安法对镁薄膜在基体铜上的初始电化学沉积行为做了研究,结果表明,镁薄膜的电沉积行为遵循形核/生长机制;采用直流沉积法,分别改变电解液浓度和电流密度,得到光亮致密均匀的镁镀层;利用SEM和XRD分别对镀层表面形貌和相组成进行了表征;采用脉冲电沉积法制得金属镁镀层,与恒流电沉积相比,脉冲电沉积能够细化晶粒,并存在着[002]面的择优取向。     

电泳沉积制备Ca10(PO4)6(OH)2/TiO2/Ti复合涂层

采用电泳沉积法在经阳极氧化的钛板表面形成羟基磷灰石涂层,研究了电解液浓度、电压、时间对氧化膜及涂层的影响,并进行了XRD和SEM表征。得出了阳极氧化的最佳工艺参数:电解液H2SO4的体积分数为20%,电压为120V,氧化时间为10min;电泳沉积的最佳工艺参数为:悬浮液的质量浓度为15g/L,沉积电压为250V,沉积时间为3min。     

Structural evaluation of brushite/gelatine coatings on graphite substrate

Brushite is one of the most frequently formed products of the electrochemical deposition. It has shown excellent biological behaviour of calcium phosphate coatings on carbon composites. Calcium phosphate coatings were obtained by the electrochemical deposition from the solution of calcium and phosphate ions at pH = 2.4 and with 0.2 or 1 wt.% gelatine addition. Graphite substrate was used as cathode and Pt basket as anode. Electrochemical deposition of brushite/gelatine composite layer was carried out at current densities from 5 to 20 mA/cm². Coatings were examined before and after annealing at 850 °C in Ar. The large channels were observed in coatings at higher concentrations of gelatine and high current densities in microstructure. The adhesive strength of thin brushite/gelatine coating was around 7 MPa. Linear dependence of deposit weight increase with electrolysis time was observed. Similarly, the gelatine content in coating rose linearly with gelatine concentration in electrolyte. After annealing of coatings at 850 °C in argon, the brushite was transformed to hydroxyapatite and CaO, the size of the needle-like brushite particles decreased and small spherical or regular shaped particles of CaO were formed. The weak bonding of thermal treated brushite/gelatine deposits to graphite was found.     

电压对TiAl合金含ZrO2微弧氧化膜生长特性的影响

目的在TiAl合金表面制备较厚的含ZrO_2相的微弧氧化膜层,并研究电压对微弧氧化膜层生长特性的影响。方法采用可溶性锆盐电解液体系,分别在480、500、520 V电压下对TiAl合金试样进行微弧氧化处理。分别采用涡流测厚仪、扫描电子显微镜和X射线衍射仪,检测膜层的厚度、微观形貌和物相组成。结果在480、500、520 V电压下制备的膜层厚度分别为18、28、48μm,电压小幅度的增加使膜层厚度大幅度增加。膜层的主晶相为t-ZrO_2,并含有m-ZrO_2、Al2O3和Ti O2相,随着电压的升高,m-ZrO_2相的含量略有增加。膜层表面有许多大小不一的类似于"火山口"的微孔和一些陶瓷颗粒,随着电压的升高,微孔孔径增加,膜层表面粗糙度增加。结论电压对膜层相组成的影响较小,对膜层微观形貌和厚度具有显著影响。较高电压有利于提高膜层的厚度,同时会增加膜层的粗糙度和表面微孔孔径。     

HVAP 及 HVOF 工艺制备 WC10Co4Cr 复合涂层及其性能研究

目的对比研究超音速等离子喷涂(HVAP)技术与超音速火焰喷涂(HVOF)技术制备WC10Co4Cr涂层,并根据涂层组织形貌与电化学特性判断两种工艺的优劣。方法采用SEM及XRD分析WC10Co4Cr复合涂层的微观形貌和物相,在3.5%(质量分数)Na Cl溶液中对涂层进行电化学分析。结果 WC10Co4Cr涂层由较大的WC颗粒及粘结相组成,在喷涂过程中WC颗粒不断累积形成层片状结构,涂层有较小程度的失碳,形成了具有脆性的W2C。电化学极化测试表明,超音速等离子喷涂技术制备的涂层表现出优异的抗电化学腐蚀性能。结论超音速等离子喷涂技术制备的WC10Co4Cr涂层显微硬度为1197HV,孔隙率为0.50%,腐蚀电位为-0.3947 V,腐蚀电流密度为9.19×10-7A/cm2,腐蚀速率为1.01×10-2g/(m2·h),腐蚀深度为1.09×10-2mm/a,具有与超音速火焰喷涂涂层相似的耐腐蚀性能。     

等离子喷涂Cr2O3/TiO2高温氧化物陶瓷 复合涂层的微观组织及电化学性能

目的 通过等离子喷涂工艺,在油气管道X70管线钢表面制备出Cr2O3/TiO2高温氧化物陶瓷复合涂层,研究该涂层的微观组织与电化学性能。方法 采用9MC Plasma Control Unit等离子喷涂系统,基于线切割尺寸为40 mm×24 mm×6 mm的X70管线钢基体表面,沉积Cr2O3/TiO2高温氧化物陶瓷复合涂层。利用金相显微镜和扫描电子显微镜观察该复合涂层的微观组织与形貌,利用X射线衍射仪分析该复合涂层的物相组成,利用电化学工作站测定该复合涂层的电化学腐蚀性能。结果 Cr2O3/TiO2高温氧化物陶瓷复合涂层由完全熔化区和半熔化区双态组成,呈典型的等离子喷涂层状结构,层与层之间结合较紧密,分布着富Cr2O3沉积区与富TiO2沉积区,无相变产生,完全熔融的TiO2液相可嵌入到未完全熔融的Cr2O3结构间隙中形成固溶结构。经电化学腐蚀性能测试,其自腐蚀电位介于-0.4 ~ -0.3 V之间,高于X70管线钢基体的自腐蚀电位-0.6 ~ -0.5 V,腐蚀倾向滞后,表现出好的抗腐蚀性能。结论 研究选取的等离子喷涂参数较合适,并成功制备出了能明显提高油气管道X70管线钢抗电化学腐蚀性且组织分布均匀的Cr2O3/TiO2高温氧化物陶瓷复合涂层。     

纳米SiO2粒子/镍基复合镀层腐蚀行为

将纳米SiO2粒子通过超声分散引入到化学镀Ni-P合金镀液中,在碳钢基体表面共沉积得到纳米SiO2粒子/镍基复合镀层。通过X射线衍射(XRD)、扫描电镜(SEM)对Ni-P镀层和纳米SiO2粒子/镍基镀层的微观结构形貌进行了分析;采用失重法和电化学方法研究了纳米SiO2粒子/镍基复合镀层在3.5%NaCl溶液中的腐蚀行为。结果表明,纳米SiO2粒子/镍基复合镀层仍是非晶态,纳米SiO2粒子的加入提高了镀层的致密性,提高了镀层的耐腐蚀性能。     

Cr颗粒对Ni-Graphene复合沉积层组织结构及性能的优化

目的电沉积技术制备Ni-Cr-Graphene复合沉积层,调查不同Cr颗粒浓度对复合沉积层组织结构及性能的优化影响。方法利用电沉积技术在镍铝青铜(NAB)表面制备出Ni-Cr-Graphene复合沉积层。采用X射线衍射仪(XRD)、扫描电镜(SEM)、能谱仪(EDS)与拉曼光谱仪(Raman),对复合沉积层的形貌、成分与组织结构(晶粒大小、结晶形状及结晶织构)进行表征,并采用显微硬度计与电化学工作站分别对沉积层的硬度及耐腐蚀性能进行调查。结果Graphene颗粒使得纯Ni沉积层中的Ni晶粒尺寸由175.3 nm减小到Ni-0Cr-4Graphene沉积层中的Ni晶粒尺寸60.5nm。随着Cr颗粒质量浓度进一步从0g/L增加到100 g/L,Ni-Cr-Graphene复合沉积层中的Cr质量分数从0%增加到23.8%,且Ni晶粒尺寸进一步减小到Ni-100Cr-4Graphene沉积层的29.1nm,Ni[200]结晶织构被消除。Graphene与Cr颗粒显著提高了Ni-CrGraphene复合沉积层的表面硬度,所有复合沉积层的显微硬度均高于纯Ni沉积层(260.1HV0.2),且在100 g/L Cr颗粒浓度下,沉积层平均显微硬度为489.8HV0.2。同时Graphene与Cr颗粒改善了Ni-Cr-Graphene复合沉积层在3.5%NaCl溶液中的耐腐蚀性能,在100 g/L Cr颗粒浓度下,复合沉积层的自腐蚀电位(Ecorr)为-0.21 V,自腐蚀电流密度(Jcorr)为0.25μA/cm^2,其相对纯Ni沉积层Jcorr(7.01μA/cm^2)降低了1个数量级。结论溶液中Cr颗粒浓度的增加引起了Ni-Cr-Graphene复合沉积层中Cr含量的增加,使得更多Cr颗粒与Graphene颗粒共同作为Ni金属结晶形核点,促进了Ni的晶粒细化与织构转变,最终提高了复合沉积层的硬度与耐腐蚀性能。     

AZ91D镁合金的均一化前处理与化学镀Ni-P

采用新型环保的均一化前处理工艺在AZ91D镁合金表面制备了化学镀Ni-P镀层。研究了前处理过程中AZ91D基体微观形貌、镀层沉积过程、成分和相结构。研究结果表明：基体表面的β相在前处理过程中被选择性去除,表面组织得到均一化,从而获得均匀致密的浸Zn层。Ni-P颗粒均匀形核生长,并最终形成致密的镀层。镀层具有优良的耐腐蚀性能。     

1.10-菲啰啉在以HCHO为还原剂的化学镀铜体系中的作用

通过实时分析镀液中HCHO含量,结合极化曲线、电化学阻抗谱及扫描Kelvin探针技术,研究了1.10-菲啰啉对化学镀铜液中HCHO利用率及镀层沉积行为的影响;采用SEM,XRD分析铜镀层微观形貌及结构。结果表明：1.10-菲啰啉能够加速HCHO的氧化,提高HCHO利用率;化学镀铜液中加入1.10-菲啰啉,能够明显降低镀液阻抗,提高混合电位下的自腐蚀电流密度,降低Cu在镀液中的表面电势,提高镀层沉积速率。镀液中加入1.5 mgL^-1 1.10-菲啰啉可使HCHO利用率从28%提高到39%,镀速增加50%;1.10-菲啰啉的加入可以提高Cu(111) 晶面的择优取向程度,获得细致均匀的铜镀层。     

多孔ZrO2/HA医用钛合金微弧氧化复合陶瓷膜层生物力学性能研究

为了获得具有生物力学性能的陶瓷膜层材料并满足临床医学上的需要。以Ti6Al4V钛合金为基体材料,通过微弧氧化工艺方法在电解液中制备氧化锆和羟基磷灰石复合陶瓷膜层材料。利用能谱分析仪和扫描电镜分析膜层结构特点。建立并改进了多孔性膜层力学性能数学模型,利用理论计算与实验测试相结合的方法对膜层相关生物力学性能进行了研究。实验结果表明,氧化锆/羟基磷灰石医用钛合金复合陶瓷能够取得比单一的羟基磷灰石陶瓷膜层更好的生物力学性能。生物陶瓷力学性能与孔隙率及生成的新相有关,通过实验与理论模型相结合的方法能够更好的对生物陶瓷膜层力学性能进行研究,所建立数学模型科学合理,具有一定理论意义。     

Study on Fabrication and Corrosion Resistance of Ni-Based Alloy Coating on P110 Steel by Electro Spark Deposition

In this study, a Ni-based alloy coating has been fabricated on P110 oil casing tube steel (P110 steel) surface by electro spark deposition (ESD) process, aiming to improve the latter’s corrosion resistance and increase the life in operation. Scanning electron microscope (SEM), energy dispersive x-ray spectrometer (EDS), and x-ray diffraction (XRD) were used to investigate the surface morphology/composition, cross-sectional microstructure, and phase constitutions of the ESD coating. Electrochemical experiments, including open-circuit potential (OCP), potentiodynamic polarization, and electrochemical impedance spectroscopy (EIS) were carried out in simulated oilfield brine and simulated stratum water to examine the anticorrosion property of the ESD coating. The results revealed that the ESD coating was continuous and compact and exhibited higher OCPs, charge transfer resistance, and lower corrosion current densities than the uncoated P110 steel in the selected corrosion media.     

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.