Surface characteristics of anodized and hydrothermally treated titatnium with an increasing concentration of calcium ion

Titanium is widely used as an implant material due to its good mechanical properties and the excellent biocompatibility of the oxide film on the surface. To modify the unstable oxide surface of pure titanium, plasma electrolytic oxidation was applied in this study. The electrolyte used for anodizing was a mixture of GP (glycerophosphate disodium salt) and CA (calcium acetate). In addition, a hydrothermal treatment was performed to precipitate a calcium phosphate crystal on the titanium oxide layer for bioactivity. The effect of the CA concentration of the electrolyte on the surface of titanium was investigated, with CA concentrations at 0.1 M, 0.2 M, and 0.3 M. A high concentration of CA results in a low breakdown voltage; hence many large micropores were formed on the anodized surface. Moreover, the size of the HA crystals was more minute in proportion to the increasing concentration of CA. The crystal phase of titanium dioxide was mainly anatase, and a rutile phase was also observed. As the size and/or amount of HA crystals increased, the surface roughness increased. However, the surface roughness could be decreased by fully and uniformly covering the surface with HA crystals. The corrosion resistance in the saline solution was increased by anodic spark oxidation. In addition, it was slightly increased by a hydrothermal treatment. It is considered that a more stable and thicker titanium oxide layer is formed by anodic oxidation and a hydrothermal treatment.     

The effect of fluoride treatment on titanium treated with anodic spark oxidation

This study examined the effect of fluoride on the surface characteristics of an anodized titanium implant. Commercial pure titanium plate 20mm×10mm×2mm in size, and discs 1.5 mm thick and 1.5 mm in diameter, were used. The prepared samples were polished with #200 to #1, 000 SiC papers and were then washed sequentially with distilled water, alcohol and acetone. Anodic oxidation was performed using a regulated DC power supply in an electrolyte containing a mixture of 0.015 M DL-α-glycerophosphate disodium salt hydrate (DL-α-GP) and 0.2 M calcium acetate hydrate (CA) with an electric current density of 30mA/cm² and voltage ranging from 0 to 290 V. The specimens were divided into four groups and a fluoride treatment was carried out. Group 1 was thermally treated in a 0.05 M TiF₃ solution at 90°C, Group 2 was electrochemically treated at 150 V in a 0.05 M TiF₃ solution, Group 3 was electrochemically treated at 150 V in a 0.05 M NaF solution, and Group 4 was electrochemically treated at 150 V in a 0.05 M HF solution. A porous oxide layer containing pores 1–4 μm in size was observed on the surface treated with anodic oxidation. The diameter of the pores was higher in the protrusion areas than in the sunken areas. A significant amount of fluoride ions was released in the initial period, with small amounts being released continuously thereafter. The viability of MC3T3 cells was high when the fluoride ion concentration was 10 ppm, but decreased with further increases in the fluoride concentration. A six-week immersion test in simulated body fluid (SBF) showed dense HA crystals in the group immersed in 0.05 M TiF₃ at 90°C, which indicated good biocompatibility.     

Preparation of biocompatible structural gradient coatings on pure titanium

In order to overcome the poor osteo-inductive properties of titanium implant, some methods have been used. The efforts to improve implant biocompatibility and durability by applying a hybrid technique of composite oxidation (pre-anodic and micro-arc oxidation) and hydrothermal treatment were described. Pure titanium was used as the substrate material. An oxalic acid was used as the electrolyte for the pre-anodic oxidation. A calcium and phosphate salt solution was acted as the electrolyte of micro-arc oxidation and the common pure water was used for hydrothermal treatment. X-ray diffraction (XRD), and scanning electron microscopy (SEM) have been used to investigate the microstructure and morphology of the coatings. The results show that a compact TiO2 film can be made by pre-anodic oxidation, which is effective as chemical barriers against the in-vivo release of metal ions from the implants. A porous TiO2 coating can be produced by micro-arc oxidation on titanium plate, which is beneficial to bone tissue growth and enhancing anchorage of implant to bone. De-calcium HA can be formed on the coating using hydrothermal treatment, which is similar with the primary component of bone and has a very good osteo-inductivity.The porous gradient titania coating made by the hybrid oxidation and hydrothermal treatment should show good biocompatibility in the environment of the human body.     

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…     

HA coating on titanium with nanotubular anodized TiO2 intermediate layer via electrochemical deposition

Hydroxyapatite（HA） coating has been prepared on titanium substrate through an electrochemical deposition approach. In order to improve the bonding strength between HA coating and Ti substrate, a well oriented and uniform titanium oxide nanotube array on the surface of titanium substrate was applied by means of anodic oxidation pre-treatment. Then the calcium hydrogen phosphate（CaHPO4·2H2O, DCPD） coating, as the precursor of hydroxyapatite coating, was electrodeposited on the anodized Ti. At the initial stage of electro-deposition, the DCPD crystals, in nanometer precipitates, are anchored in and between the tubes. With increasing the deposition time, the nanometer DCPD crystals are connected together to form a continuous coating on titanium oxide nanotube array. Finally, the DCPD coating is converted into hydroxyapatite one simply by being immersed in alkaline solution.     

钛及钛合金的激光表面改性研究现状

硬度低、耐磨性能差是制约钛合金发展的关键问题,而激光表面改性处理是解决这一问题的有效途径。结合近年来激光表面改性处理的研究进展,综述了激光表面处理的影响因素,激光表面处理表层的组织、性能及缺陷控制,并指出了目前存在的问题和今后研究的重点方向。     

电化学沉积法制备钛基HA涂层

在钛基材表面获得羟基磷灰石（HA）涂层以改善钛与生物体的相容性，本项工作采用电沉积的方法在阳极氧化处理过的钛基体上制备了羟基磷灰石涂层。用扫描电子显微镜（SEM）、X射线衍射（XRD）等手段对涂层进行了表征。试验结果表明：电沉积初期的羟基磷灰石涂层呈多孔层片状：随电压、时间、电解液浓度的增大，涂层变厚，层片呈花瓣状发散排列：对基体阳极氧化处理有助于提高钛基与涂层的结合强度。     

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.     

医用钛合金及其表面活化的研究现状

医用Ti合金具有良好的力学性能、耐腐蚀性能和生物相容性,在医学临床上获得广泛应用,但是其耐磨性能和生物活性等方面仍不够理想,耐腐蚀性能也有待于进一步提高.开发具有更佳综合性能的医用钛合金,或对现有成熟医用钛合金进行表面改性是解决上述问题的有效途径.本文综述了医用钛合金的发展及其存在的问题和表面活化研究进展,并对医用Ti合金的表面活化的前景进行了展望.     

两段式阳极氧化法制备大管径TiO2纳米管

应用电化学阳极氧化方法,在自选的电解液中,通过调节氧化电压和氧化次数制备不同管径的TiO2纳米管。其管径可分别控制在50,100和200nm左右。其中50和100nm范围的纳米管是一次氧化所制得。通过再次氧化突破了一次氧化对尺寸的限制,所制得纳米管的最大管径达到280nm。实验证实,在一定的电压范围内,通过调节阳极氧化的电压可以控制TiO2纳米管的管径大小。但是,在本实验的电解液条件下,在一次氧化过程,通过调节电压制备出的纳米管最大管径只能达到120nm。采用两次氧化能将TiO2纳米管的管径扩大到更大的尺寸,可以扩展TiO2纳米管的应用范围。     

粉末冶金多孔钛表面生物活化的研究

采用粉末冶金法制备了具有适合人体组织长入孔径的多孔钛,并对其进行生物活化处理.利用EPMA、SEM、XRD等研究了不同预处理方法和浸泡时间对多孔钛表面羟基磷灰石(HA)的形貌及形成速度的影响.结果表明,多孔钛的表面以及孔的内表面上均有纳米晶TiO2生成,预钙化处理能够明显提高多孔钛表面生成羟基磷灰石的速率,促进HA的形核长大,预钙化后磷含量增加明显,验证了Na2HPO4在预处理中对多孔钛的活化是有利的.     

钛及钛合金表面转化膜的应用及发展

对钛及钛合金的表面转化膜处理技术进行了综述,主要包括化学氧化、阳极氧化、硅烷化、磷酸盐转化等。阐述了各种处理方法的工艺过程及其作用效果,分别指出了各种方法的优缺点。同时展望了其今后的应用及发展前景。     

微弧氧化工艺参数对Ti-6Al-4V钛合金表面氧化膜厚度及表面形态的影响

为了提高Ti-6Al-4V钛合金表面的生物活性,在乙酸钙和磷酸二氢钠溶液中对Ti-6Al-4V钛合金进行微弧氧化,研究氧化时间,电压,占空比等对氧化膜厚度及其表面形态的影响。结果表明,在一定条件下,随氧化时间的增加,氧化膜厚度以指数关系增加,而膜层表面孔洞逐渐变小,最终封闭;随着电压的提高,膜层厚度增加平缓,但电压过大时,膜层反而变薄,氧化膜表面微孔的数量减少,但微孔的孔径逐渐增大;占空比的提高使得膜层厚度增加,同时伴随有膜层孔洞分布的均匀性变差,表面粗糙度增加。     

Surface Characteristics and Indentation Deformation of Porous Anodic TiO2 Layer Before and After Hot Water Treatment

Hot water treatment was performed to modify the surface of porous TiO2 layer prepared by anodic spark oxidation technique for better biocompatibility.The oxide layer without water treatment exhibited a porous surface with few nanometer features and consisted of poorly crystallized oxides.During water treatment,the poorly crystallized oxides were transformed into crystalline anatase gradually and numerous nanoparticles formed on the oxide surface,leading to increased surface roughness at the nanoscale.The indentation deformation behaviors of oxide layer before and after water treatment were investigated and compared.Results show that under the indentation load,the untreated anodic TiO2 layer exhibited good adhesion to the substrate.In contrast,after water treatment,apparent oxides pile-up and spallation were observed around the indentation,indicating decreased adhesion strength.     

锆合金表面改性工艺的研究进展

以锆合金的表面改性技术为主线,简述了目前改性方法的种类及研究现状,重点介绍了物理气相沉积、激光表面处理、阳极氧化、微弧氧化及离子注入等常用表面改性制备技术的原理、研究进展及优缺点。探讨了锆合金表面改性过程中需要解决的理论问题和需要攻克的技术瓶颈。最后,结合相关研究进展,对锆合金表面改性今后的研究工作和工程应用前景进行了展望。     

Improvement of erosion resistance of titanium with different surface treatments

To improve the erosion resistance of titanium, several surface treatment methods were applied: (1) duplex treatment with carbon nitride film deposited on a plasma-nitrided layer, (2) diamond coating, and (3) laser alloying. Duplex treatment could improve the erosion resistance of titanium under a low impact velocity of erosion particles. However, under a high velocity of erosion particles, because of the shallow depth of the plasma-nitrided layer and low load-bearing capacity of carbon nitride layer on the plasma-nitrided specimen, the improvement of erosion resistance was not significant. Diamond coatings with a thickness of 15 μm made no significant improvement on the erosion resistance of the titanium substrate. The large-area spallation of diamond coating during erosion was observed, probably due to the high residual stresses, poor load-bearing capacity, and brittle nature of diamond coatings. Compared with untreated Ti substrate, the erosion resistance of the laser-alloyed (nitrided) specimen was improved significantly. The erosion mechanisms for laser-nitrided titanium were characterized by chipping, brittle fracture, and formation of large flakes in the laser-nitrided layers.     

Effects of applied voltage on the microstructure and properties of hydroxyapatite bioceramic coatings formed on Ti7Cu5Sn titanium alloy by micro-arc oxidation

The effects of the applied voltage on the morphology, composition and corrosion behaviour of Ti7Cu5Sn coated were investigated. At applied voltages lower than 250?V, the composite coatings consist of anatase-TiO₂, rutile-TiO₂, DCPD(CaHPO₄·2H₂O) and a small amount of amorphous calcium phosphate phase. When the applied voltage is increased, the ceramic coatings transform from DCPD (CaHPO₄·2H₂O) to HA (Ca₁₀(PO₄)₆(OH)₂, 300?V), and new phases of Ca₂P₂O₇, CaTiO₃ and TCP(Ca₃(PO₄)₂) form at 350?V. The passive current densities at body potential are one order of magnitude lower than that of the uncoated sample, indicating better corrosion resistance. The MAO film is a tri-layer system: a compact inner layer, a mesosphere porous oxide layer, and an outer layer.     

钛合金表面激光熔覆CoCrMo强化涂层路径选择与质量分析

针对生物医学上常用的钛合金材料表面硬度与耐磨性较差的问题,尝试采用同轴送粉激光熔覆技术,在纯钛板上制备CoCrMo新型高硬度耐磨熔覆层.为了保证熔覆层质量,在工艺参数优化的基础上,设计了单向搭接、矩形嵌套搭接和圆形螺旋搭接3种不同扫描路径.结果表明,通过对3种不同扫描路径下激光熔覆样件的宏/微观显微组织的对比分析,发现...     

电解液成分对纯钛表面微弧氧化膜结构与生物活性的影响

采用微弧氧化处理技术,在纯钛TA2表面制备了含钙磷的多孔复合氧化膜,用SEM、XRD、EPMA等分析了电解液成分对氧化膜形貌、成分、相构成及生物活性的影响。结果表明:纯钛表面微弧氧化后原位生成的含钙磷多孔性复合氧化膜由锐钛矿相TiO2,金红石相TiO2和基体Ti组成;随电解液中钙磷摩尔比(Ca/P)值的增大,表面孔洞数量增多、直径变小,膜中Ca/P值增大,锐钛矿相TiO2减少、金红石相TiO2增多;当电解液中Ca/P=5时得到的氧化膜的Ca/P值为1.528,将该样品经碱液处理后再在快速钙化溶液(FCS)中浸泡2 d后即有羟基磷灰石HA形成,表明其具有良好的生物活性。