Study of adhesion of TiN grown on a polymer substrate

TiN films were deposited on polycarbonate substrates by cathodic vacuum arc using the plasma immersion ion implantation and deposition (PIII&D) method. The biaxial intrinsic stress in the film deposited using PIII&D with 3 kV applied bias was 0.3 GPa — much lower than that found in films deposited without the application of high-voltage pulsed bias. It was found that the dominant mechanism for generating stress in the TiN film was thermal stress arising from the large difference between the thermal expansion coefficient of TiN and that of the polymer. Tensile testing was used to ascertain film adhesion and a model was used to estimate the adhesion between the film and the substrate. It was found that PIII&D strongly reduced the stress in the TiN film and increased the adhesion to the polycarbonate. The ultimate shear strength of adhesion is of the same order of magnitude as that of TiN on stainless steel.     

Rolling contact fatigue and mechanical properties of titanium carbide film synthesized on bearing steel surface

The effect of plasma immersion ion implantation and deposition (PIII&D) titanium carbide (TiC) film on the rolling contact fatigue (RCF) life of coated on AISI52100 bearing steel surface is studied experimentally. Testing include plan-view optical microscopy (OM), X-ray diffraction (XRD), friction and wear behaviors, rolling contact fatigue life and nano-indentation measurements. XRD patterns show that titanium carbide phase is formed in the film, and the microhardness of treated samples is higher than that of substrate. Rolling contact fatigue failure tracks were observed using conventional light microscope. Surface wear and adhesive delamination existed. Results indicate that the maximum RCF life of the treated sample prolong by 6.5 times at a Hertzian stress level of 5.1 GPa and 90% confidence level, respectively. Comparison with the substrate, the maximum microhardness of treated specimen is increased by 28.4%. The friction coefficient decreased from 0.95 to 0.15 under identical wear conditions. This remarkable fatigue performance appears to be due to a combination of improved microstructure, adhesion, hardness and surface topography. Therefore, the PIII&D is regarded as one of the promising technologies for improving the RCF life of bearing.     

A biasing method for plasma immersion ion implantation and deposition process to enhance coating adhesion

A multi-purpose high voltage pulse (HVP) supply was developed for PIII&D process, to provide bias voltage of DC, HVP and HVP + DC to the workpiece. The pretreatment (sputtering cleaning) of the workpiece, ion implantation, hybrid PIII&D or normal deposition, can be finished in one vacuum cycle. In the system a vacuum bend-guide microwave ECR source is used to produce plasma. Ti/TiN_x coating was prepared in this biasing manner with the PIII&D system. The result shows that the adhesion of the coating is enhanced with the HVP + DC composite biasing when the pulse amplitude and the DC voltage are chosen properly. The deposition rate can be maintained relatively high at an intermediate level between the conditions with pure HVP and DC bias. This work shows that the composite biasing is an effective method to improve the coating's properties in PIII&D process.     

A study of TiN-coated metal-on-polymer bearing materials for hip prosthesis

The TiN-coated metal-on-polymer hip prosthetic pair has the potential to reduce wear debris of UHMWPE (ultra-high molecular weight polyethylene) and to prevent metallic-ion-induced cytotoxicity. However, high quality and adherent film is a key to the clinical success of hip prostheses. In this study, titanium nitride (TiN) films were deposited on stainless steel using plasma immersion ion implantation & deposition (PIII&D) technique to create high-quality film and an adherent interface. The chemical state and composition were analyzed by X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and energy dispersive spectroscopy (EDS). The mechanical properties of the films were characterized using a micro-hardness tester and a pin-on-disk wear tester, and an x-ray diffractometer (XRD) was used for a crystallographic analysis. The PIII&D-treated TiN films showed a stoichiometric and (200) preferred orientation and micro-hardness up to 150 % higher than untreated film. A TiN-coated specimen using the PIII&D process also showed less UHMWPE wear compared to untreated specimens. The volumetric wear rate of UHMWPE could be reduced by as much as 42 % compared to when Co-Cr alloy was used. The results of this study show that advanced TiN-coating via the PIII&D process is a viable means of reducing UHMWPE wear in the metal-on-polymer bearing couple.     

Phase composition and in-vitro bioactivity of plasma sprayed calcia stabilized zirconia coatings

Zirconia coatings stabilized with different calcia content (12.8 mol%, 16 mol% and 30 mol%) were fabricated on titanium alloy substrates using atmospheric plasma spraying technology. The in-vitro bioactivity of coatings was evaluated by simulated body fluid (SBF) soaking test. The morphology and phase composition of the coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), micro Raman spectroscopy, energy dispersive spectrometry (EDS) and infrared spectroscopy (IR). The results showed that the apatite was formed on the surface of the calcia stabilized zirconia coatings soaked in SBF for 28 days and the formation ability of apatite decreased with the increase in calcia content of the coating. The bioactivity of zirconia coatings was thought to be related to the Zr-OH formed on their surfaces during the phase transformation in the presence of water. Osteoblast-like MG63 cells were cultured on the surfaces of the coatings to evaluate their cytocompatibility. Results showed that MG63 cell grew and proliferated well on all coating surfaces, indicating that plasma sprayed calcia stabilized ZrO₂ coatings were cytocompatible.     

Effect of plasma treatment on corrosion-electrochemical interaction between titanium and chloride-nitrate melt

The corrosion-electrochemical behavior of titanium in a chloride melt containing 1–30 wt % sodium nitrate at a temperature of 790–900 K in an argon atmosphere is studied. Depending on the sodium nitrate content, either oxide layers of various structures can appear on the titanium surface or titanium dioxide nanopowder can form in the bulk of the melt. Treating VT-1 titanium with hydrogen or helium high-temperature pulsed plasma substantially changes the morphology and protective properties of the oxide films produced on titanium.     

The influence of plasma power on the temperature-dependant conductivity and on the wet chemical etch rate of sputter-deposited alumina thin films

Aluminum oxide (Al₂O₃) thin films are synthesized by reactive d.c. magnetron sputter deposition on silicon substrates. The impact of varying plasma power P_p (i.e. 400 to 1000 W) and of thin film temperatures T up to 540 °C on the electrical performance are evaluated, as these dielectric layers with a thickness of 450 nm are targeted as potential candidates for high temperature sensor applications. From 150 °C to 500 °C, the current-voltage measurements show a leakage current behavior according to the Poole-Frenkel electron emission with an activation energy of 1.16 eV. At T > 500 °C, the conductivity increases above average, in respect to the extrapolated Poole-Frenkel behavior at T < 500 °C, most probably due to the migration of charged ions, such as Ar⁺, incorporated into the film during deposition. Basically, samples synthesized at higher plasma levels show an enhanced electrical insulation behavior. This result is supported by measurements applying optical ellipsometry as well as by the determination of the wet chemical etching behavior in phosphoric-based acid at different bath temperatures. At higher plasma power, the refractive index shows a slight tendency to increase, staying, however, below the value of single-crystalline Al₂O₃. In contrast, the etch rate decreases by a factor of 1.5 at samples deposited at 1000 W when lowering the temperature of the etchant from 90 °C to 60 °C. These results indicate an enhanced film density at higher P_p values as the microstructure of the Al₂O₃ films is X-ray amorphous independent of plasma power and post-deposition annealing temperatures up to 650 °C.     

Bioactivity and cytocompatibility of plasma-sprayed titania coating treated by sulfuric acid treatment

Titania coatings were fabricated on titanium alloy substrate using atmospheric plasma spraying technology, and treated by sulfuric acid (H₂SO₄) at room temperature for 24 h. The as-sprayed and acid-treated titania coatings were soaked in simulated body fluid (SBF) to investigate the formation of apatite on their surfaces. Human mesenchymal stem cells (MSCs) were used to evaluate the cytocompatibility of titania coatings. The results indicated that bone-like apatite was formed on the surfaces of acid-treated titania coatings after soaked in SBF for a period of time. The concentration of sulfuric acid had an effected on the bioactivities of titania coatings. The bioactivity of titania coating could not be improved by 0.01 M sulfuric acid treatment. The MSCs could attach, grow and proliferate well on the surface of titania coatings. The results showed that plasma-sprayed titania coating after acid treatment exhibited favorable bioactivity and cytocompatibility.     

Plasma-Sprayed Titanium Patterns for Enhancing Early Cell Responses

Titanium coating has been widely used as a biocompatible metal in biomedical applications. However, the early cell responses and long-term fixation of titanium implants are not satisfied. To obviate these defects, in this paper, micro-post arrays with various widths (150-1000 μm) and intervals (100-300 μm) were fabricated on the titanium substrate by template-assisted plasma spraying technology. In vitro cell culture experiments showed that MC3T3-E1 cells exhibited significantly higher osteogenic differentiation as well as slightly improved adhesion and proliferation on the micro-patterned coatings compared with the traditional one. The cell number on the pattern with 1000 µm width reached 130% after 6 days of incubation, and the expressions of osteopontin (OPN) as well as osteocalcin (OC) were doubled. No obvious difference was found in cell adhesion on various size patterns. The present micro-patterned coatings proposed a new modification method for the traditional plasma spraying technology to enhance the early cell responses and convenience for the bone in-growth.     

医用钛合金表面形貌与成分对生物相容性影响研究综述

生物医用钛合金表面物化特性作为影响细胞生物学行为的关键因素,决定了骨-植入体之间的结合质量和速率。针对作者所在研究小组在钛合金表面改性技术研究中所取得的一系列进展进行了综述。在表面形貌制备方面,利用喷砂、激光和微细铣削等机械加工方法和酸蚀、碱热处理、阳极氧化等化学处理方法,在钛合金表面获得了微纳米双级结构。在表面化学成分方面,采用离子置换的方式在微纳米结构表面植入生物活性离子,通过富氧切削方式改善表面钝化膜的质量。通过电化学腐蚀试验和一系列体外细胞培养实验,验证各表面物化改性方法对钛合金植入体生物相容性的影响。研究表明,微纳米结构化的表面能够提高材料表面的亲水性,促进细胞的粘附、增殖和矿化等,而植入生物活性离子后与微纳结构表面产生了协同效应,进一步增加了其生物相容性。此外,在富氧加工气氛下,钛合金表面的氧化膜厚度相比自然条件下加工有明显增加,提高了生物相容性,同时耐腐蚀性也得到显著增强。     

Effect of atmospheric microwave plasma treatment on organic lubricant on a metallic surface

Coaxial injection microwave excited plasma torch, operating at atmospheric pressure has been tested to treat greased metallic surfaces. The treatment conditions were controlled using optical emission spectroscopy. The plasma treatment was carried out using argon plasma, with argon or oxygen in the periphery. The effect of plasma treatment on the grease was evaluated, using gravimetric analysis by weighing the sample before and after treatment, surface energy and X-ray photoelectron spectroscopic measurements. Initial period of treatment yielded etching of the grease, but, later on, the grease stabilized forming polymeric films, independent of the gas present in the periphery. The etching behavior was explained by different mechanisms involved in the plasma grease surface and sub-surface interactions.     

Preparation and cell-materials interactions of plasma sprayed strontium-containing hydroxyapatite coating

The use of strontium-containing hydroxyapatite (Sr-HA) as a biomaterial has been reported recently. In vitro and in vivo studies have shown that Sr-HA promotes osteoblast response and stimulates new bone formation. In order to extend its usage to major load-bearing applications, such as artificial hip replacement, it has been proposed that the material could be used in the form of a coating on implant surfaces. This paper reports a preliminary study of biocompatibility of plasma sprayed Sr-HA coatings on a metallic substrate. Coatings of Sr-HA containing 10 mol% Sr²⁺ was produced on titanium alloy substrates. The coating exhibited good bonding with the substrate. The bioactivity of Sr-HA coating was evaluated in vitro by immersion in simulated body fluid (SBF). After immersion in SBF, Sr-HA coating exhibited great ability to induce apatite precipitation on its surface. The possible effects of cell-materials interactions of Sr-HA coating were examined by culturing osteoprecursor cells (OPC1) on coating surfaces. The effect of Sr-HA was also compared to a hydroxyapatite (HA) coating, which is widely used in orthopedics and dentistry. The results indicated that Sr-HA coating had good biocompatibility with human osteoblasts. OPC1 cells survived and proliferated well on the surface of coating. Sr-HA coating promoted OPC1 cells attachment, and more local contacts were produced on the surface. The presence of Sr stimulated OPC1 cell differentiation and ALP expression. No deleterious effect on ECM formation and mineralization was found with Sr-HA coating. The results indicated that Sr-HA coating had good mechanical properties and bioactivity in vitro.     

Formation of adherent polypyrrole coatings on Ti and Ti–6Al–4V alloy

Highly adherent polypyrrole coatings were electrodeposited at etched Ti and Ti–6Al–4V from 0.2 M oxalic acid and 0.2 M pyrrole at a constant applied potential of 0.8 V versus SCE. The substrates were etched in an alkaline peroxide solution at ambient temperature for a 10 min period prior to the electropolymerization reactions. Chemical etching of the substrate gave rise to an increase in the hydrophilicity of the surface, the formation of a micro-etched surface and the formation of a semiconducting titanium oxide film. There was a considerable increase in the density of nucleation sites for polypyrrole growth at the micro-etched surface. Growth of the polypyrrole proceeded slowly from a high number of nucleation sites at the etched surface to give rise to a highly adherent polypyrrole coating. Adhesion of the polypyrrole coating was attributed to micro-etching of the substrate and the conductivity of the oxide film generated during the chemical etching process.     

表面形貌对TB8钛合金/环氧树脂粘结性能的影响

目的 通过在基体表面构建出不同的微观结构,提升环氧树脂与钛合金的粘结强度。方法 采用等离子刻蚀设备,调节气体流量、处理时间、RF功率对TB8钛合金样品进行处理,并对处理过的样品进行单搭接接头制备。利用扫描电子显微镜对等离子刻蚀前后的样品表面形貌进行研究,利用XPS分析刻蚀前后样品表面化学成分变化,利用水接触角表征样品表面润湿性,利用电子万能试验机对等离子刻蚀处理后的样品与环氧树脂的粘结强度进行研究。结果 采用CF4对样品进行等离子化学刻蚀,不同的刻蚀时间形成了不同类型的表面微观结构,其中圆粒状结构比蜂窝坑结构表面的粘结性能优越。采用Ar对样品进行等离子溅射刻蚀,样品表面形成纳米级片状微坑结构。等离子刻蚀后,基体表面更加洁净,活性增强,水接触角基本降为0°,润湿性显著提升。等离子刻蚀处理前,样品与环氧树脂的粘结强度为5.32MPa;等离子刻蚀处理后,样品与环氧树脂的粘结强度可达23.25 MPa,而经喷砂后,等离子刻蚀处理的样品与环氧树脂的粘结强度高达30.29 MPa。最佳等离子刻蚀处理工艺参数为RF功率540 W,气体流量120 mL/min,处理时间50 min,喷砂后最佳等离子刻...     

Oxygen adsorption on γ-TiAl surfaces and the related surface phase diagrams: A density-functional theory study

We have constructed the surface phase diagrams for oxygen adsorption on γ-TiAl low-index surfaces using density-functional theory calculations. From these surface phase diagrams, the selective oxidation behaviors of the γ-TiAl surfaces and the corresponding polycrystalline systems can be easily understood and predicted. For the (1 0 0) surface, complete selective oxidation of titanium is favored and a titanium oxide layer may be produced at the initial stage of oxidation. For the (1 1 0) and (0 0 1) surfaces, only titanium oxides may form. For the γ-TiAl polycrystalline system, O may induce complete Ti and Al surface segregations on the Ti-rich and Al-rich conditions, respectively. In addition, the microscopic oxidation mechanisms are identified and the experimental results are successfully explained. More importantly, by comparing the different TiAl surface orientations, a comprehensive surface phase diagram is constructed to study the oxidation behaviors of polycrystalline γ-TiAl. This method can also be applied to other polycrystalline materials.     

Etching mechanisms during plasma jet machining of silicon carbide

The material removal of the C- and Si-face of 4H-SiC using a 13.56 MHz RF excited plasma jet source at atmospheric pressure using helium as feed gas and CF₄ as reactive gas has been investigated. Additionally O₂ is provided together with the peripherally injected N₂ shielding gas and it is shown that a decrease of the etching rate with an increase of the O₂ gas flow occurs.Furthermore, etching experiments under sample heating have been carried out for different [CF₄]/[O₂] mixtures to obtain the activation energy of fluorine and oxygen with the surface. A minimum in the etching rate at a temperature of approximately 150 °C has been found. Therefore XPS and SEM analyses have been carried out for surfaces etched at sample temperatures of 25 °C, 150 °C and 400 °C showing an elevated fraction of silicon oxides and film thickness at 150 °C.     

Deposition of titanium dioxide from TTIP by plasma enhanced and remote plasma enhanced chemical vapor deposition

Photocatalytic materials, and especially titanium dioxide, have gained wide popularity in recent years in reason of their interesting properties which can be useful in various fields of application, in particular as self-cleaning materials. When submitted to an illumination (in most cases UV-light), the surface of a photocatalytic material becomes chemically active and simultaneously displays a photo-generated hydrophilic activity (PSH effect).Classically, photocatalytic properties are displayed by crystalline titanium dioxide. In this paper we detail the chemical vapor deposition of TiO₂ carried out in two experimental set-ups: one is plasma enhanced reactor and the other is remote plasma enhanced reactor. Both experiments were carried out with titanium(IV) isopropoxide (TTIP). Titanium(IV) tetrachloride (TiCl₄) and titanium(IV) ethoxide (TEOT) were also used in the first setup.In RF-diode plasma reactor, titanium dioxide films were deposited in amorphous form and crystallization of amorphous films was obtained with the help of thermal post-treatments, since seeding and under-layers appeared unable to trigger the crystallization of films. In the remote plasma CVD reactor, allowing high plasma density and ion energy, deposition of crystalline anatase titanium dioxide was achieved at a deposition temperature of 400 °C.Conclusions are presented and suggest control mechanisms for the stoichiometry of titanium dioxide films.     

Surface pretreatment of austenitic stainless steel and copper by chemical, plasma electrolytic or CO2 cryoblasting techniques for sol-gel coating

The surface pretreatments of the austenitic stainless steel and copper surfaces for the sol-gel coating were carried out by chemical, plasma electrolytic or CO₂ cryoblasting techniques. With the austenitic stainless steel the smoothest surfaces were obtained with plasma electrolytic cleaning, after which the measured contact angles of water were clearly decreased revealing improved hydrophilicity. As well with the copper samples the smooth surface and improved hydrophilicity was obtained with the plasma electrolytic cleaning, but oxide layer formed to the copper surface immediately after the treatment. CO₂ cryoblasting provided rough surface with wetting properties close to the original surface both for austenitic stainless steel and copper surfaces. CO₂ cryoblasting provided best appearance for the copper surface because no oxidation happened with that treatment. XPS and SIMS studies showed that with the plasma electrolytic treatment the surface layer of the austenitic stainless steel enriched of chromium and the oxide layer formed on the surface was less than 10 nm thick. With the chemical cleaning and CO₂ cryoblasting, the chromium enrichment to the stainless steel surface was less. However XPS and SIMS studies showed that chemical treatment provided thinner oxide layer to copper surface than plasma electrolytic treatment.     

Preparation and Characterization of CaO-ZrO2-SiO2 Coating for Potential Application in Biomedicine

In this paper, chemically synthesized CaO-ZrO₂-SiO₂ (CZS) powder was plasma sprayed onto a Ti-6Al-4V alloy substrate for its potential applications in biomedicine. Surface morphology and phase composition were analyzed by scanning electron microscopy (SEM) and x-ray diffraction (XRD). The degradation behavior of the coating in biological environment was in vitro appraised in Tris-HCl buffer. The mass loss was much lower than that of the wollastonite coating (WC) and close to that of the hydroxylapatite coating (HC). The bond strength with titanium alloy substrate was 31.8 ± 4.7 MPa. In vitro bioactivity appraisement results showed that apatite could be formed on the surfaces after soaking in simulated body fluid (SBF) for 14 days. Canine marrow stem cells (MSCs) also showed well adhesion and proliferation on the coating surfaces. In summary, results suggest that the coating possesses well cytocompatibility and may be an appropriate candidate for application in biomedicine.     

Electrochemical polishing as a 316L stainless steel surface treatment method: Towards the improvement of biocompatibility

A 316L stainless steel (316L-SS) surface was electrochemically polished (EP) in an electrolyte of a new chemical composition at different cell voltages, with the aim of improving its corrosion resistance and biocompatibility. X-ray photoelectron spectroscopy results revealed that the EP-formed oxide films were characterized by a significantly higher atomic Cr/Fe ratio and film thickness, in comparison to the naturally-grown passive oxide film formed on the untreated (control) 316L-SS surface. As a result of the increase in the oxide film thickness and relative Cr enrichment, the EP-treated 316L-SS surfaces offered a notable improvement in general corrosion resistance and pitting potential. In addition, the attachment of endothelial cells (ECs) and smooth muscle cells (SMCs) to the 316L-SS surfaces revealed a positive effect of electropolishing on the preferential attachment of ECs, thus indicating that the EP surfaces could be endothelialized faster than the control (unmodified) 316L-SS surface. Furthermore, the EP surfaces showed a much lower degree of thrombogenicity in experiments with the platelet-rich plasma. Therefore, the use of the electrochemical polishing technique in treating a 316L-SS surface, under the conditions presented in this paper, indicates a significant improvement in the surface’s performance as an implant material.