NiTi合金表面液相阴极等离子体沉积氧化铝陶瓷涂层的研究

在NiTi合金表面通过液相阴极等离子体技术制备了氧化铝(Al2O3)陶瓷涂层。采用X射线衍射和扫描电镜对涂层的相组成以及表面形貌进行了表征和分析,证实在材料表面形成了由α-Al2O3和γ-Al2O3组成的涂层,发现涂层具有粗糙多孔结构。在模拟体液中对NiTi合金的Ni离子释放情况进行了检测,发现液相阴极等离子体改性后显著降低了Ni离子的释放。为NiTi合金植入体的表面改性提供了一条新途径。     

XPS and biocompatibility studies of titania film on anodized NiTi shape memory alloy

A dense titania film is fabricated in situ on NiTi shape memory alloy (SMA) by anodic oxidation in a Na₂SO₄ electrolyte. The microstructure of the titania film and its influence on the biocompatibility of NiTi SMA are investigated by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma mass spectrometry (ICPMS), hemolysis analysis, and platelet adhesion test. The results indicate that the titania film has a Ni-free zone near the surface and can effectively block the release of harmful Ni ions from the NiTi substrate in simulated body fluids. Moreover, the wettability, hemolysis resistance, and thromboresistance of the NiTi sample are improved by this anodic oxidation method.     

Characteristics and mechanical properties of a (Ti, O, N)/Ti composite coating fabricated on NiTi shape memory alloy via PIIID

In this investigation, (Ti, O, N)/Ti composite coating was fabricated on a NiTi shape memory alloy (SMA) to improve its biocompatibility, bioactivity and wear resistance for its long-term medical applications, using the plasma immersion ion implantation and deposition (PIIID) technique. Scanning electron microscopic (SEM) examination of coating cross-sections showed that the (Ti, O, N)/Ti composite coating was uniform and compact. Energy dispersive X-ray (EDX) analysis not only indicated that the interface between the coating and NiTi SMA substrate was gradual rather than sharp, but it also showed the thickness of the composite coating to be ∼ 1.0 μm. The EDX mapping of cross-sections of (Ti, O, N)/Ti composite coating revealed that Ni was not present on the surface of the coated samples. Nanoindentation tests were performed to evaluate mechanical properties of the composite coating. Pin-on-disc wear test results showed greatly improved wear resistance of (Ti, O, N)/Ti coated NiTi SMA.     

Electrochemical Corrosion Behavior of the DLC Coated and Uncoated NiTi Alloys

A dense and well-adhered diamond-like carbon （DLC） coating was prepared on the nickel-titanium （NiTi） alloys by plasma immersion ion implantation and deposition （PIIID）. Potentiodynamic polarization tests indicated the corrosion resistance of the NiTi alloys was markedly improved by the DLC coating. The Ni ions release of the NiTi alloys was effectively blocked by the DLC coating.     

Laser cladding composite coatings by Ni–Cr–Ti–B4C with different process parameters

To investigate the effect of laser process parameters on microstructure and properties of composite coating, the composite coatings were manufactured by laser cladding Ni–Cr–Ti–B₄C mixed powder on Q235 mild steel with different process parameters. The coatings are bonded with the substrate by remarkable metallurgical binding without cracks and pores. The composite coatings are consisted of in situ synthesized solid solution Ni–Cr–Fe, intermetallic compound (IMC) Ni₃Ti, Cr₂Ti, and ceramic reinforcements TiB₂, TiC. Results of scanning electron microscopy (SEM) revealed that the ceramic reinforcements became coarser with higher specific energy (E_s). There were independent ceramics TiB₂, TiC, eutectic ceramic TiB₂–TiC in coatings, and eutectic alloy–ceramic was detected. Compared with the substrate, the microhardness of coatings was increased significantly, and the maximum microhardness of coatings was approximately five times as high as the substrate. The wear resistance of coatings was improved dramatically than the substrate. Compared to the coatings with lower E_s, higher E_s led to lower microhardness and worse wear resistance ascribing to more Fe diffused into the coating from the substrate.     

碳化钛/钛镍金属间化合物复合涂层相组织研究

利用钛粉、镍粉和胶体石墨,真空条件下通过反应钎涂技术在低碳钢基体上制备了与基体冶金结合的碳化钛/钛镍金属间化合物复合涂层。采用扫描电子显微镜、能谱仪、X射线衍射仪及硬度计,研究了涂层的相组成、组织结构和成分分布。涂层组织由NiTi2、NiTi、TiC和hcp Ti组成,而涂层界面由NiTi和少量的hcp Ti构成,并且TiC主要分布在涂层中层。涂层中的NiTi2、NiTi、TiC是在钎涂过程中原位反应合成的,而且TiC和NiTi的量随碳含量的增加而增加。涂层表面硬度达到85HR15N,但不随TiC和NiTi含量增加而增高。     

激光熔覆制备原位自生TiC增强Ni3（Si,Ti）复合涂层研究

运用激光熔覆技术修复受损的烟汽轮机叶片,在GH864镍基合金表面制备原位自生TiC颗粒增强Ni3(Si,Ti)金属间化合物复合涂层.利用扫描电镜、能谱分析仪、X射线衍射仪及显微硬度计研究了(Ti+C)的加入量对熔覆层组织及硬度的影响.研究表明:在优化的工艺参数下可获得宏观质量完好,无裂纹、气孔等缺陷,且与基体呈冶金结合的激光熔覆层,熔覆层由Ni(Si)、Ni3(Si,Ti)和TiC组成;当合金粉末中(Ti+C)的加入量为20%时熔覆层的硬度最高可达780Hv,是基体材料的2.4倍.     

Growth morphology and mechanism of primary TiC carbide in laser clad TiC/FeAl composite coating

TiC-reinforced FeAl intermetallic matrix composite (IMC) coatings were fabricated on substrate of 1Cr18Ni9Ti stainless steel using laser cladding. X-ray diffraction (XRD) was used to identify the phases in the laser clad composite coating and the growth morphologies of TiC carbide were observed by optical microscope (OM), scanning electron microscope (SEM) and transmission electron microscope (TEM). The results showed that there are two phases in the laser clad composite coating: TiC and FeAl intermetallic matrix alloy. The primary TiC carbide in laser clad coating nucleates heterogeneously on the surface of oxide particles; its growth morphology is found to be in a unique radial-branching dendrite with strongly faceted feature. The growth mechanism of TiC is confirmed to be lateral growth from the ledges or steps existing on the growing fronts.     

Effects of microstructural mechanisms on the localized oxidation behavior of NiTi shape memory alloys in simulated body fluid

Localized oxidation and corrosion behavior of a nickel–titanium (NiTi) shape memory alloy (SMA) was investigated via static immersion experiments in a simulated body fluid solution. Detailed electron microscopy examinations on the sample surfaces revealed preferential formation of local oxide particles around dislocation networks, which constitute high-energy zones. Moreover, various intermediate phases were detected in addition to the parent NiTi phase around dislocation networks. These are also areas with enhanced diffusion, which promotes Ni release. These findings emphasize the significant role of fine microstructural features, such as dislocation networks, on the oxidation and Ni release, and thus, the biocompatibility of the NiTi SMAs.     

Alumina coating formed on medical NiTi alloy by micro-arc oxidation

Al₂O₃ coatings were prepared on NiTi alloy by micro-arc oxidation in an aluminate solution. Thin-film X-ray diffraction (TF-XRD) indicated that the coating consisted of only Al₂O₃ crystal phase. Energy dispersive X-ray spectrometer (EDS) showed that there was about 2.53 at.% Ni in the surface layer, which was greatly lower than that of NiTi substrate. Scanning electron microscopy (SEM) showed that the coating exhibited a typical porous surface and excellent adhesive interface between the coating and the substrate. Direct pull-off test showed that the coating had a mean coating-substrate bonding strength of 28 ± 2 MPa. The results of electrochemical impedance spectroscopy (EIS) study and potentiodynamic polarization test indicated that the corrosion resistance of the coated sample was increased by two orders of magnitude compared with uncoated sample.     

多元氮化物薄膜及其沉积工艺对NiTi记忆合金性能和组织的影响

采用真空阴极电弧沉积技术,在NiTi记忆合金表面沉积了TiAlBN和TiAlCrFeSiBN多元膜和TiN薄膜,研究了薄膜成份及沉积工艺对NiTi合金性能和组织的影响.结果表明,在NiTi合金表面沉积TiAlBN和TiAlCrFeSiBN多元膜和TiN薄膜均可降低合金在Hank溶液中的Ni溶出速率,其中多元膜的Ni溶出速率最小;提高偏压对沉积了TiAlBN多元膜的NiTi合金的Ni溶出速率无明显影响,但使沉积了TiAlCrFeSiBN膜的NiTi合金的Ni溶出速率降低.在TiAlBN和TiAlCrFeSiBN多元膜表面存在较多细小的钛滴和孔隙,钛滴与薄膜基体之间的融合良好;在TiN薄膜表面存在一些大钛滴和孔隙,钛滴与薄膜基体之间的融合不好.镀膜后,NiTi基体的加热相变点移向低温区,其幅度与薄膜成份及沉积工艺有关,提高偏压使沉积了两种多元膜的NiTi基体的相变点移动幅度增大,但却使沉积了TiN膜的NiTi基体的相变点的移动幅度减小.镀膜过程均使NiTi中的M体尺寸增大.     

NiTi superelastic orthodontic archwires with polyamide coating

Twenty orthodontic archwires with 55.2 % Ni and 44.8 % Ti (% weight) were subjected to a dipping treatment to coat the NiTi surface by a polyamide polymer. It has been selected a Polyamide 11 due to its remarkable long lasting performance. The transformation temperatures as well as the transformation stresses of the NiTi alloy were determined in order to know whether the coating process can alter its properties. The adhesive wear tests have been demonstrated that the wear rates as well as the dynamic friction coefficients μ of polymer coated wires are much lower than metallic wires. The corrosion studies have shown that the use of this polymer, as coating, seals the NiTi surface to prevent corrosion and the release of nickel ions. The average decrease of Ni ions release due to this coating is around 85 %.     

不同等离子源形成的DLC涂层对NiTi合金腐蚀行为的影响

采用等离子浸没离子注入和沉积(PIIID)法分别以C2H2和石墨为等离子源在NiTi合金表面形成DLC涂层来提高该合金的耐腐蚀性.利用Raman光谱和扫描电镜分析膜层结构.利用电化学测试和原子吸收光谱测试涂层前后基体的耐腐蚀性和Ni离子析出.结果表明:采用等离子浸没离子注入和沉积法以乙炔和石墨为等离子源在NiTi合金表面形成均匀致密、结合力良好的DLC涂层.两种涂层都明显地提高了NiTi合金的耐腐蚀性能和有效地抑制了Ni离子的溶出.     

Characteristics and in vitro biological assessment of (Ti, O, N)/Ti composite coating formed on NiTi shape memory alloy

In this investigation, plasma immersion ion implantation and deposition (PIIID) was used to fabricate a (Ti, O, N)/Ti coating on NiTi shape memory alloy (SMA) to improve its long-term biocompatibility and wear resistance. The surface morphology, composition and roughness of uncoated and coated NiTi SMA samples were examined. Energy dispersive X-ray elemental mapping of cross-sections of (Ti, O, N)/Ti coated NiTi SMA revealed that Ni was depleted from the surface of coated samples. No Ni was detected by X-ray photoelectron spectroscopy on the surface of coated samples. Furthermore, three-point bending tests showed that the composite coating could undergo large deformation without cracking or delamination. After 1 day cell culture, SaOS-2 cells on coated samples spread better than those on uncoated NiTi SMA samples. The proliferation of SaOS-2 cells on coated samples was significantly higher at day 3 and day 7 of cell culture.     

Carbon plasma immersion ion implantation and DLC deposition on Ni−Ti alloy

Carbon plasma immersion ion implantation (PIII-C) has been performed on Ni?Ti alloy surface using methane as a precursor gas at low temperature and it has been followed by deposition of diamond-like carbon (DLC) coating. Untreated and coated alloys are characterized with field emission scanning electron microscopy, atomic force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electrochemical impedance spectroscopy, and corrosion testing in Hanks’ solution which is simulated body fluid show that corrosion resistance has been enhanced in PIII-C?+?DLC-coated alloy compared to untreated alloy. The in vitro studies of untreated and PIII-C?+?DLC-coated alloys have been evaluated using osteoblast-like cells (MG-63). Cellular behavior in terms of cell morphology along with the viability and cell spreading has been evaluated using scanning electron microscopy and in vitro cell culture assay, respectively. In comparison to Ni–Ti alloy, the coated alloy exhibits better cell viability indicating their biocompatibility.     

Fabrication and biocompatibility of polyethyleneimine/heparin self-assembly coating on NiTi alloy

NiTi alloy has been used widely as biomaterials. But because of toxic effects possibly caused by excess Ni ions released during the corrosion process in the physiological environment, it is still a controversial material. Fabricating medicine-loaded coating, which is expected to decrease the release of Ni ions and improve the biocompatibility of the materials, is a potential way to solve the problem. In this paper, NiTi alloy is coated by polyethyleneimine/heparin films via layer-by-layer (LBL) self-assembly method. UV-Vis, FT-IR, atomic force microscopy (AFM) and contact angle measurements are used to characterize the microstructure of coatings and select the best fabrication conditions. Potentiodynamic polarization researches in sodium chloride and dynamic clotting time experiment are utilized to study its corrosion resistance capability and biocompatibility of coatings, respectively. The results indicate that PEI/heparin multilayer coating can improve the biocompatibility of NiTi alloy surface.     

TiC coatings deposited onto carbon and molybdenum surfaces by electron beam evaporation

TiC coatings were deposited onto graphite and molybdenum substrates by an electron beam evaporation method. A titanium film 1000–10000 Å thick was evaporated onto the graphite substrate which was then heated at 1000 °C for 5 min to form the TiC film by an interdiffusion process. In the case of the molybdenum substrate, a double-layer film consisting of titanium and carbon (Ti/C/Mo) was prepared by evaporation and the subsequent heat treatment was performed at 700 °C or at 1000 °C for 5 min. The properties of the coatings were examined by various surface analysis techniques including Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and Rutherford backscattering (RBS). The atomic ratio of carbon to titanium in these coatings was found to be 0.9. The in-depth profiles obtained by XPS examination showed that the coating prepared at 700 °C had a carbon layer between the TiC layer and the molybdenum substrate, while that prepared at 1000 °C had an Mo₂C layer between the coating and the substrate.     

NiTi 合金表面激光原位反应合成TiN增强金属基复合材料涂层

采用连续高功率固体Nd-YA G激光辐照, 使预置于NiTi 合金表面的Ti 粉在N₂ 环境中形成TiN 增强Ti 基复合材料涂层。选择适当的激光辐照工艺参数, 获得致密的TiN 增强金属基复合材料激光改性层。SEM 观察及EDAX 成分分析结果表明, TiN/ Ti 金属基复合材料表面改性层与基体NiTi 合金存在良好的冶金结合, 界面处成分均匀过渡, 表面Ni 含量极低。显微硬度测试及磨损实验表明, TiN/ Ti 金属基复合材料改性层显著提高了NiTi 合金的表面硬度和耐磨性, 激光表面改性层可有效地改善NiTi 合金作为生物医学材料使用的表面成分和性能。      

激光熔覆原位自生TiC颗粒增强镍基复合涂层的组织与耐磨性

采用预置粉末法在45钢表面进行激光熔覆镍基Ni60A+x%(SiC+Ti)(质量分数,下同)复合粉末涂层的实验研究。使用往复式磨损试验机对不同涂层材料的熔覆层进行干摩擦磨损实验,利用金相显微镜、扫描电镜(SEM)观察和分析熔覆层的显微组织与磨损形貌。结果表明:复合粉末通过原位反应生成弥散分布的TiC颗粒增强复合涂层,随着(SiC+Ti)含量的增加,颗粒状TiC的尺寸和数目逐渐增加;复合粉(SiC+Ti)含量达到60%时,微观组织有气孔和夹杂缺陷;复合粉(SiC+Ti)含量为48%时,熔覆层耐磨性最佳;复合涂层的磨损主要为磨粒磨损,机理为微观切削和挤压剥落。     

Interfacial structure, residual stress and adhesion of diamond coatings deposited on titanium

The interfacial structures of diamond coatings deposited on pure titanium substrate were analyzed using scanning electron microscopy and grazing incidence X-ray diffraction. Results showed that beneath the diamond coating, there was one titanium carbide and hydride interlayer, followed by a heat-affected and carbon/hydrogen diffused Ti layer. Residual stress in the diamond coating and TiC interlayer under different process parameters were measured using Raman and X-ray diffraction (XRD) methods. Diamond coatings showed large compressive stress on the order of a few giga Pascal. XRD analysis also showed the presence of compressive stress in the TiC interlayer and tensile stress in the Ti substrate. With increasing deposition duration, or decreasing plasma power and concentration of CH₄ in gas mixture, the compressive residual stress in the diamond coating decreased. The large residual stress in the diamond coating resulted in poor adhesion of the coatings to substrate, but adhesion was also related to other factors, such as the thickness and nature of the TiC interlayer, etc. A graded interlayer design was proposed to lower the thermal stress, modify the interfacial structure and improve the adhesion strength.