AFM and SEM characterization of non-toxic vanadium-free Ti alloys used as biomaterials

In this work, three titanium alloys have been studied by means of atomic force microscopy (AFM) and scanning electron microscopy (SEM) to determine their surface topography. The alloys investigated were Ti–6Al–7Nb, Ti–13Nb–13Zr, and Ti–15Zr–4Nb, with no presence of the toxic element V, and with a possible use as biomaterials for osteoarticular prostheses. These alloys were studied at room temperature and also after a thermal treatment at 750 °C during 24 h, which produces a protective surface oxide layer. The aim of the present work is to compare the surface structure and morphology of the alloys, both as-received and after the oxide layer was formed at elevated temperature.     

Pd对Ti合金钝化影响的电子理论研究

采用递归法计算了Ti合金的电子态密度、环境敏感镶嵌能、费米能级等电子结构参量.计算发现Pd在晶体体内比在其表面的环境敏感镶嵌能高,说明Pd易于在 Ti合金表面偏聚.Pd在表面时,原子团簇形成能为负值,说明Pd以团簇形式分布于合金表面.态密度计算结果表明,Pd的局域态密度局限在很窄的能量范围内(-20—-15 eV),使Ti合金的总态密度在此区出现尖峰.该尖峰的存在降低了Ti合金的费米能级,于是表面含Pd较多的区域费米能级较低,含Pd少或不含Pd的区域费米能级较高.费米能级不同的两区域接触会形成微电池,在腐 关键词： Ti合金 钝化 电子结构 表面     

Surface oxidability of pure liquid metals and alloys

The analysis of the oxygen-liquid metal interaction is a topic of particular technological interest. A deep knowledge of the kinetics and transport mechanisms involved in the oxidation phenomena is necessary: the effect of oxidation reactions taking place in the gas phase and the evaporation of oxides must be considered.This paper aims to review our works in order to provide a systematic analysis of the oxidation of pure metals and determine the most likely to keeping oxygen-free the surface in a binary alloy.In addition, the upgrading of this theoretical approach, here briefly described, is addressed to give a contribution to a better understanding of the evolution of oxidation phenomena close to the solid-liquid-gas interfaces.     

Ti75Al25合金微观结构演变的分子动力学模拟

本文利用分子动力学模拟方法, 研究了液态Ti75Al25合金在不同冷却条件下形成晶体及非晶的过程(Q1:1.0×1013 Ks-1, Q2: 1.0×1011 Ks-1). 利用平均原子体积、双体分布函数、键角分布函数、键对分析和Voronoi多面体方法研究了微观局域结构随温度的变化关系. 研究发现：在Q1冷却过程中,液态Ti75Al25合金在1000 K发生玻璃化转变,形成非晶结构; 而在Q2冷却过程中,液态Ti75Al25合金发生结晶,并最终形成hcp晶体结构。     

Ti75Al25合金微观结构演变的分子动力学模拟

本文利用分子动力学模拟方法,研究了液态Ti₇₅Al₂₅合金在不同冷却条件下形成晶体及非晶的过程(Q1:1.0×10¹³K Ks^-1,Q2:1.0×10¹¹Ks^-1).利用平均原子体积、双体分布函数、键角分布函数、键对分析和Voronoi多面体方法研究了微观局域结构随温度的变化关系.研究发现:在Q1冷却过程中,液态Ti₇₅A1₂₅合金在1000 K发生玻璃化转变,形成非晶结构;而在Q2冷却过程中,液态Ti₇₅Al₂₅合金发生结晶,并最终形成hcp晶体结构.     

Effect of different alloyed layers on the high temperature oxidation behavior of newly developed Ti2AlNb-based alloys

The application of titanium aluminide orthorhombic alloys (O-phase alloys) as potential materials in aircraft and jet engines was limited by their poor oxidation resistance at high temperature. The Ti₂AlNb-based alloys were chromised (Cr), chromium-tungstened (Cr-W) and nickel-chromised (Ni-Cr) by the double glow plasma surface alloying process to improve their high temperature oxidation resistance. The discontinuous oxidative behavior of Cr, Cr-W and Ni-Cr alloyed layers on Ti₂AlNb-based alloy at 1093 K was explored in this study. After exposing at 1093 K, the TiO₂ layer was formed on the bare alloy and accompanied by the occurrence of crack, which promoted oxidation rate. The oxidation behavior of Ti₂AlNb-based alloys was improved by surface alloying due to the formation of protective Al₂O₃ scale or continuous and dense NiCr₂O₄ film. The Ni-Cr alloyed layer presented the best high-temperature oxidation resistance among three alloyed layers.     

Surface oxidation behavior of MgNd alloys

The oxidation kinetics of MgNd alloys oxidized in pure O₂ at high temperatures has been investigated. The results revealed two stages of the reaction: A fast initial oxidation was followed by a slow oxide growth with a parabolic kinetics. For MgNd alloys (Nd = 25 wt.%), the oxidation rate increased with the enhancement of the oxidation temperature. A sudden ignition was found for this alloys oxidized at 873 K up to about 80 min. Moreover, the increase of the Nd content would harm the oxidation resistance of the MgNd alloys. By Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and scanning electron microscopy (SEM) analysis, it was found that a triplex structure of oxide film formed. The outer layer was composed of MgO, Nd₂O₃ and Nd(OH)₃, the middle layer mainly consisted of MgO and Nd₂O₃, and the inner layer was the transitional layer made of MgO, Nd₂O₃ and the content of the substrate. The protective oxidation was associated with the formation of the dense Nd₂O₃/MgO layer during isothermal oxidation process. The oxidation mechanisms for the formation of oxide film are discussed.     

Characterization of oxide layers formed on electrochemically treated Ti by using soft X-ray absorption measurements

The oxide layers of electrolytic oxidized titanium (Ti) were characterized using Ti L_2,3 and O K edge X-ray absorption. The spectra show that the structure of the oxide layers that are formed during a 1 min treatment are dependent on the concentration of the electrolyte (H₂SO₄ or Na₂SO₄) with which the Ti surface was treated, and also on the magnitude of the potential that was applied during the anodic oxidation process (100 V or 150 V). It is found that a potential of 150 V and an electrolyte concentration of 0.5 M or 1.0 M produces a layer of TiO₂ having rutile crystal structure.     

Surface modification of magnetite nanoparticles for biomedical applications

The preparation of magnetite nanoparticles with narrow size distributions using poly(ethylene glycol) (PEG-COOH) or carboxymethyl dextran (CMDx) chains covalently attached to the particle surface using carbodiimide chemistry is described. Particles were synthesized by thermal decomposition and modified with 3-aminopropyl trimethoxysilane (APS) to render particles with reactive amine groups (-NH₂) on their surface. Amines were then reacted with carboxyl groups in PEG-COOH or CMDx using carbodiimide chemistry in water. The size and stability of the functionalized magnetic nanoparticles was studied as a function of pH and ionic strength using dynamic light scattering and zeta potential measurements.     

Surface characterization of anodized zirconium for biomedical applications

Mechanical properties and corrosion resistance of zirconium make this material suitable for biomedical implants. Its good in vivo performance is mainly due to the presence of a protective oxide layer that minimizes corrosion rate, diminishes the amount of metallic ions released to the biological media and facilitates the osseointegration process.Since the implant surface is the region in contact with living tissues, the characteristics of the surface film are of great interest. Surface modification is a route to enhance both biocompatibility and corrosion resistance of permanent implant materials. Anodizing is presented as an interesting process to modify metal surfaces with good reproducibility and independence of the geometry.In this work the surface of zirconium before and after anodizing in 1 mol/L phosphoric acid solution at a fixed potential between 3 and 30 V, was characterized by means of several surface techniques.It was found that during anodization the surface oxide grows with an inhomogeneous coverage on zirconium surface, modifying the topography. The incorporation of P from the electrolyte to the surface oxide during the anodizing process changes the surface chemistry. After 30 days of immersion in Simulated Body Fluid (SBF) solution, Ca-P rich compounds were present on anodized zirconium.     

Mg-Zr合金微观组织电子结构研究

用递归法计算了α-Mg与α-Zr的结构能、原子结合能，Mg/Zr界面能与Mg的表面能，Mg中Zr及Zr中Fe，Mn，Si，H等杂质原子相互作用能，Mg，Zr原子态密度及其在合金中的电荷变化. 计算发现，在晶体中与Mg态密度差别很大的Zr在Mg/Zr界面却与Mg趋于相近，从而界面电子环境与Mg相似，为Mg形核生长提供有利条件；α-Zr的结构能、原子结合能低于相应的α-Mg，且Mg/Zr界面能低于Mg的表面能，从能量角度合理解释了Zr先于Mg从Mg熔体析出，并作为异质核心细化Mg晶粒的实验现象. 原子相互作用     

Mg-Zr合金微观组织电子结构研究

用递归法计算了α-Mg与α-Zr的结构能、原子结合能,Mg/Zr界面能与Mg的表面能,Mg中Zr及Zr中Fe,Mn,Si,H等杂质原子相互作用能,Mg,Zr原子态密度及其在合金中的电荷变化. 计算发现,在晶体中与Mg态密度差别很大的Zr在Mg/Zr界面却与Mg趋于相近,从而界面电子环境与Mg相似,为Mg形核生长提供有利条件;α-Zr的结构能、原子结合能低于相应的α-Mg,且Mg/Zr界面能低于Mg的表面能,从能量角度合理解释了Zr先于Mg从Mg熔体析出,并作为异质核心细化Mg晶粒的实验现象. 原子相互作用 关键词： 电子结构 晶粒细化 Mg合金     

递归法研究Pt对Ti合金腐蚀影响

采用递归法计算了Ti及Ti合金的电子态密度、环境敏感镶嵌能、费米能级和格位能等电子结构参量.计算发现Pt在晶体中环境敏感镶嵌能和格位能高于表面,从电子层面证实Pt易在 Ti合金表面偏聚.偏聚在表面的Pt有序能为正值,故Pt以有序相（Pt与Ti的化合物）形式分布在合金表面.晶体表面Pt 与Ti的化合物电极电位较低,它与Ti形成微电池.在腐蚀介质的作用下,Pt与Ti的化合物分解,Pt沉淀到晶体表面造成Pt在合金表面形成凹凸不平的Pt电催化层.Pt电催化层加强Ti钝化作用,从而提高了Ti合金的抗腐蚀能力. 关键词： 电子结构 Ti合金表面 钝化     

Self-lubricative coating grown by micro-plasma oxidation on aluminum alloys in the solution of aluminate-graphite

Aluminum trioxide ceramic coatings with high hardness were grown on surfaces of 2024 Aluminum alloys by micro-plasma oxidation in an aluminate electrolytic solution, which highly improve wear-resisting properties of 2024 Aluminum alloys. However, ceramic coating surfaces are porous and very coarse, which is disadvantageous to practical applications. In this paper, in order to increase the density of the pores and decrease the friction coefficient of the ceramic coatings, different concentrations (2-8 g/l) of graphite were added into the aluminate electrolytic solution. The thickness and hardness of the produced ceramic coatings were measured by HVS-100 micro-hardness tester and thickness tester. The friction coefficient of the coatings was studied by a frictionometer. The phase composition and surface morphology of the MPO films were evaluated through X-ray diffraction (XRD) and scanning electron microscope (SEM). The results show that the thickness of the ceramic coating is about 22 ± 1 μm, surfaces of the ceramic coatings are very uniform and that the coatings consist of mainly aluminum trioxides and a certain amount of graphite, which indicates graphite have entered the ceramic films during the micro-plasma oxidation process. Wear properties results show that the friction coefficient of the ceramic coatings decreased when graphite entered the ceramic films. When the concentration of graphite is 4 g/l, the wear properties of the coatings is the most excellent and the friction coefficient decreases to the lowest, that is 0.09.     

The effect of oxidation on physical properties of porous silicon layers for optical applications

In order to understand the optical loss mechanisms in porous silicon based waveguides, structural and optical studies have been performed. Scanning and transmission electron microscopic observations of porous silicon layers are obtained before and after an oxidation process at high temperature in wet O₂. Pore size and shape of heavily p-type doped Si wafers are estimated and correlated to the optical properties of the material before and after oxidation. The refractive index was measured and compared to that determined by the Bruggeman model.     

Studies on electrodeposition of Fe-W alloys for fuel cell applications

Electrodeposition of Fe-W alloy has been carried out from acidic triammonium citrate (TAC) complex bath solution. The deposit is characterised by XRD, SEM, EDAX, XPS and polarization techniques. The alloys are amorphous and become partially crystalline on heat treatment. The composition (Fe/W) of elements in the coating and their oxidation states vary from the surface to the bulk of the material. The coatings exhibit as novel electrode material with low over voltage and good corrosion resistance for anodic oxidation of methanol in H₂SO₄ medium. The anodic peak current, a measure of oxidation reaction rate is considerably high on Fe-W alloy when compared to pure Fe and also the relative surface area of Fe by alloying it with W found to increase by 1200-fold.     

ESCA investigation of the oxide layers on some Cr containing alloys

Cr is an important constituent of many technically important alloys, such as stainless steels and those used for metal implants. The following characteristics of such alloys are revealed by ESCA measurements: (1) Heating the sample in air below 400°C leads to oxide layers with high contents of Fe or Co oxides. For temperatures higher than 400°C the Cr becomes mobile enough to migrate to the surface and to build up Cr-enriched oxide layers. (2) In H₂O and HNO₃ a Cr-rich oxide layer is always observed. (3) The chemical shift for Fe oxide in stainless steels is smaller than for pure Fe or Fe-Si alloys; i.e. there is a larger amount of Fe(II) oxide. (4) The intensity ratio Fe_metal : Cr_metal or CO_metal : Cr_metal after exposure of the sample to H₂O or HNO₃ is lower than for oxidation in air, i.e. Cr is enriched not only in the oxide layer but in the metal underneath. (5) If the alloy also contains Mo, the intensity ratio Cr_oxide : Mo(VI)_oxide is about 10 : 1 for exposure to H₂O, as well as to diluted and concentrated HNO₃. In H₂O and diluted HNO₃, Mo(IV) is found also.The ESCA results were obtained without any ion bombardment because the sampling depth is large enough to permit analysis of oxide layers below contamination and even of the metal below a thin oxide layer. This non-destructive method is of great advantage because in ion bombardment of the sample Cr is preferentially sputtered.     

掺Ti对ZnO纳米颗粒的微观结构与光学特性的影响

本研究利用溶胶凝胶法制备了Ti_xZn_(1-x)O纳米粒子,并且分析了Ti掺杂对ZnO纳米粒子晶体结构与光学特性的影响.微观结构分析得知Ti掺杂会使ZnO结晶较差,晶格常数与压缩应力增大,但可使晶粒缩小至5 nm左右.光致发光(PL)光谱分析得出Ti掺杂会造成氧空位缺陷减少,近带边发光(NBE)峰值蓝移,但NBE峰值强度增幅变化却不大.拉曼光谱分析表明Ti_xZn_(1-x)O的结晶品质不佳且NBE峰值强度的增幅未完全依循多声子模态信号减弱而增强的规律,其原因是NBE峰值强度除受多声子模态信号影响外还受其它因素的影响.TC(002)值越高时样品的多声子模态信号会越弱,而NBE峰值强度增幅越大.     

添加Ti对Al-Bi难混溶合金组织和性能的影响

难混溶合金在凝固过程中极易发生液-液相分离,造成第二相的宏观偏析,失去了合金的应用价值.本文将第三组元Ti添加到Al-Bi难混溶合金中,研究了Ti的添加对合金的凝固组织和性能的影响,探索了原位生成的金属间化合物的存在形式,分析了第二相Bi颗粒的分布.研究结果表明,凝固过程中原位生成的长针状Al_3Ti化合物,均匀分布在Al基体中,穿插在Bi相颗粒之间,阻碍了Bi相颗粒的沉降及凝并,防止了Bi相颗粒的碰撞及长大,制备了Bi相弥散分布在Al基体中的难混溶合金;同时弥散分布在基体中的硬质相Al_3Ti还增强了基体的强度,提高了合金的硬度,使合金表现出优异的耐磨性能.     

Quantum parameters for guiding the design of Ti alloys with shape memory and/or low elastic modulus

Electronic structure calculations based on density functional theory have been applied to clusters of titanium with different alloying elements in order to obtain quantum parameters that give some information on the interaction between the mother and alloying atoms. Average values of these parameters weighted with the molar fractions have been calculated for 146 titanium alloys that exhibit shape memory and/or low elastic modulus. These values have been mapped in order to identify zones that group the alloys with either property. This information was used as a guide for designing seven new alloys with desired properties. These have been microstructurally and mechanically characterized; the results confirm the usefulness of the method.