Microstructure and tribological performance of self-lubricating diamond/tetrahedral amorphous carbon composite film

In order to smooth the rough surface and further improve the wear-resistance of coarse chemical vapor deposition diamond films, diamond/tetrahedral amorphous carbon composite films were synthesized by a two-step preparation technique including hot-filament chemical vapor deposition for polycrystalline diamond (PCD) and subsequent filtered cathodic vacuum arc growth for tetrahedral amorphous carbon (ta-C). The microstructure and tribological performance of the composite films were investigated by means of various characterization techniques. The results indicated that the composite films consisted of a thick well-grained diamond base layer with a thickness up to 150 μm and a thin covering ta-C layer with a thickness of about 0.3 μm, and sp³-C fraction up to 73.93%. Deposition of a smooth ta-C film on coarse polycrystalline diamond films was proved to be an effective tool to lower the surface roughness of the polycrystalline diamond film. The wear-resistance of the diamond film was also enhanced by the self-lubricating effect of the covering ta-C film due to graphitic phase transformation. Under dry pin-on-disk wear test against Si₃N₄ ball, the friction coefficients of the composite films were much lower than that of the single PCD film. An extremely low friction coefficient (∼0.05) was achieved for the PCD/ta-C composite film. Moreover, the addition of Ti interlayer between the ta-C and the PCD layers can further reduce the surface roughness of the composite film. The main wear mechanism of the composite films was abrasive wear.     

The structure, surface topography and mechanical properties of Si-C-N films fabricated by RF and DC magnetron sputtering

Silicon carbon nitride thin films were deposited on Co-Cr alloy under varying deposition conditions such as sputtering power and the partial pressure ratio of N₂ to Ar by radio frequency and direct current magnetron sputtering techniques. The chemical bonding configurations, surface topography and hardness were characterized by means of X-ray photoelectron spectroscopy, atomic force microscopy and nano-indentation technique. The sputtering power exhibited important influence on the film composition, chemical bonding configurations and surface topography, the electro-negativity had primary effects on chemical bonding configurations at low sputtering power. A progressive densification of the film microstructure occurring with the carbon fraction was increased. The films prepared by RF magnetron sputtering, the relative content of the Si-N bond in the films increased with the sputtering power increased, and Si-C and Si-Si were easily detachable, and C-O, N-N and N-O on the film volatile by ion bombardment which takes place very frequently during the film formation process. With the increase of sputtering power, the films became smoother and with finer particle growth. The hardness varied between 6 GPa and 11.23 GPa depending on the partial pressure ratio of N₂ to Ar. The tribological characterization of Co-Cr alloy with Si-C-N coating sliding against UHMWPE counter-surface in fetal bovine serum, shows that the wear resistance of the Si-C-N coated Co-Cr alloy/UHMWPE sliding pair show much favourable improvement over that of uncoated Co-Cr alloy/UHMWPE sliding pair. This study is important for the development of advanced coatings with tailored mechanical and tribological properties.     

Synthesis of anodizing composite films containing superfine Al2O3 and PTFE particles on Al alloys

Anodized composite films containing superfine Al₂O₃ and PTFE particles were prepared on 2024 Al alloy using an anodizing method. The microstructures and properties of the films were studied by scanning electron microscopy, optical microscopy and X-ray diffraction. Friction wear tests were performed to evaluate the mechanical properties of the composites. Results indicate that the composite films with reinforced Al₂O₃ and PTFE two-particles have reduced friction coefficients and relatively high microhardness. The friction coefficient can be as small as 0.15, which is much smaller than that of an oxide film prepared under the same conditions but without adding any particles (0.25), while the microhardness can reach as high as 404 HV. When rubbed at room temperature for 20 min during dry sliding friction tests, the wear loss of the film was about 16 mg, which is about the half of that of the samples without added particles. The synthesized composite films that have good anti-wear and self-lubricating properties are desirable for oil-free industrial machinery applications.     

Optimization of (002)-Oriented ZnO Film Synthesis in Sol-Gel Process and Film Photoluminescence Property

By orthogonal design theory, technological parameters of the (002)-oriented ZnO film prepared in sol-gel process are optimized. A set of technological parameters for growing highly (002)-oriented ZnO film is obtained. As a result, it is proven that the Zn²⁺ concentration is the most important factor to grow a highly (002)-oriented ZnO film. We take an appropriate Zn²⁺ concentration 0.35mol/L for the aimed film, of which photoluminescence property is better than those of the films derived from other Zn²⁺ concentrations precursor solution. The Zn²⁺ concentration either larger or smaller than 0.35mol/L leads to the (002)-oriented degree decrease of films. By employing an atom force microscope, a hexagonal atom arrangement, which indicates that the film site detected is a ZnO single crystal, is observed in the surface of the highly (002)-oriented film.     

Characterization and structure study of the anodic oxide film on Zircaloy-4 synthesized using NaOH electrolytes at room temperature

Thick crystalline zirconium oxide films were synthesized on Zircaloy-4 substrates by anodic oxidation at room temperature in NaOH solution with a stable applied voltage (300 V). The film is approximately 4.7 μm in thickness. The XPS and SEM analysis shows that the film is a three-layer structure in water, hydroxide and oxide parts. The thickness of that order is ∼0.01 μm, ∼1 μm, ∼3.7 μm, respectively. The oxide layer is composed of tetragonal and monoclinic phases with the volume ratio about 0.2. Furthermore, the thick anodic film acts as a barrier to oxygen and zirconium migrations. It effectively protects zirconium alloys against the worse corrosion. An extremely low passive current density of ∼0.018 μA/cm² and a low oxidation weight gain of ∼0.411 mg/cm² were also observed in the films.     

Growth and characterization of Mg(OH)2 film on magnesium alloy AZ31

Magnesium-based biomaterials have been proposed as potential candidates for biodegradable implant materials, such as bone screws, bone plates, intraluminal stents and so on. However, the poor corrosion resistance inhibits their applications in surgery. They collapse before the injured tissues are healed. In this paper, Mg(OH)₂ nonstructural film was synthesized on the substrate of AZ31 magnesium alloy by hydrothermal method with NaOH solution as mineralizer to reduce the corrosion rate of magnesium-based materials. The obtained films were characterized by XRD, SEM, and XPS. The results showed that a Mg(OH)₂ film with nanostructure surface can be synthesized by hydrothermal method. It was observed that the thickness of film increased with the holding time. Corrosion rates of the films were studied by immersing the samples in Hank's solution (37 °C). Surface deposits of samples with films soaked in Hank's solution for 31 days were investigated by XRD, SEM, EDS, XPS, and FTIR. It verified that the corrosion rate of the magnesium alloy with grown film was slowed down in the Hank's solution and the behavior of corrosion was inhibited effectively. Amorphous calcium apatite precursor was observed to deposit on the surface of the film during corrosion experiments in Hank's solution. And the tape test revealed a strong adhesion between the film and the substrate.     

Simulating percolating behavior of conductive particles in anisotropically conductive composite films

A numerical scheme is developed to simulate the percolating behavior of conductive particles within a non-conductive matrix film with a preferential alignment of particles achieved via externally imposed deterministic driving forces. The sharp transition from non-conducting to conducting of the composite film is successfully revealed with the model. The percolation behavior is studied in terms of four percolation parameters, including the percolation probability, the normalized shortest percolation path, normalized gyration radius and density of the percolation cluster, subject to variation in five important system parameters. These include particle concentration, relative importance of the externally applied force, film thickness, film width and particle size. The threshold particle concentration can be reduced by increasing the strength of the deterministic driving force, decreasing film thickness, increasing film width or using smaller size particles. Our study suggests that using stronger applied force for wider and thinner films containing smaller particles may be a good practice to obtain anisotropically conductive films with a light particle loading that possess good conduction capability in the thickness direction and good insulation in the planar direction. Received: 19 February 2001 / Accepted: 30 May 2001 / Published online: 30 August 2001     

Corrosion protection by sonoelectrodeposited organic films on zinc coated steel

A variety of coatings based on electrosynthesized polypyrrole were deposited on zinc coated steel in presence or absence of ultrasound, and studied in terms of corrosion protection. Cr III and Cr VI commercial passivation were used as references. Depth profiling showed a homogeneous deposit for Cr III, while SEM imaging revealed good surface homogeneity for Cr VI layers. These chromium-based passivations ensured good protection against corrosion. Polypyrrole (PPy) was also electrochemically deposited on zinc coated steel with and without high frequency ultrasound irradiation in aqueous sodium tartrate-molybdate solution. Such PPy coatings act as a physical barrier against corrosive species. PPy electrosynthesized in silent conditions exhibits similar properties to Cr VI passivation with respect to corrosion protection. Ultrasound leads to more compact and more homogeneous surface structures for PPy, as well as to more homogeneous distribution of doping molybdate anions within the film. Far better corrosion protection is exhibited for such sonicated films.     

Effect of Chromium on Structure and Tribological Properties of Hydrogenated Cr/a-C:H Films Prepared via a Reactive Magnetron Sputtering System

Hydrogenated Cr-incorporated carbon films(Cr/a-C:H) are deposited successfully by using a dc reactive magnetron sputtering system.The structure and mechanical properties of the as-deposited Cr/a-C:H films are characterized systematically by field-emission scanning electron microscope,x-ray diffraction,Raman spectra,nanoindentation and scratch.It is shown that optimal Cr metal forms nanocrystalline carbide to improve the hardness,toughness and adhesion strength in the amorphous carbon matrix,which possesses relatively higher nano-hardness of 15.7GPa,elastic modulus of 126.8 GPa and best adhesion strength with critical load(L_c) of36 N for the Cr/a-C:H film deposited at CH_4 flow rate of 20 sccm.The friction and wear behaviors of as-deposited Cr/a-C:H films are evaluated under both the ambient air and deionized water conditions.The results reveal that it can achieve superior low friction and anti-wear performance for the Cr/a-C:H film deposited at CH_4 flow rate of 20 sccm under the ambient air condition,and the friction coefficient and wear rate tested in deionized water condition are relatively lower compared with those tested under the ambient air condition for each film.Superior combination of mechanical and tribological properties for the Cr/a-C:H film should be a good candidate for engineering applications.     

Low-temperature synthesis of AlN films through electron cyclotron resonance plasma-aided reactive pulsed laser deposition

Combination of pulsed laser ablation with electron cyclotron resonance microwave discharge was demonstrated for a novel method for low-temperature thin film growth. Aluminum nitride thin films were synthesized on silicon substrates at temperatures below 80 °C by means of reactive pulsed laser deposition in nitrogen plasma generated from the electron cyclotron resonance discharge. The synthesized films show a very smooth surface and were found to have a stoichiometric AlN composition. X-ray photoelectron spectroscopy analysis evidenced the formation of aluminum nitride compound. Fourier transform infrared spectroscopy revealed the characteristic phonon modes of AlN. The AlN films were observed to be highly transparent in the visible and near-IR regions and have a sharp absorption edge near 190 nm. The band gap of the synthesized AlN films was determined to be 5.7 eV. The mechanisms responsible for the low-temperature film synthesis are also discussed in the paper. The nitrogen plasma facilitates the nitride formation and enhances the film growth. Received: 17 March 2000 / Accepted: 28 March 2000 / Published online: 23 May 2001     

Mechanical properties of the plasma-enhanced magnetron sputtering Si-C-N coatings

The mechanical properties of plasma-enhanced magnetron sputtering Si-C-N hard coatings with various compositions are characterized. The effect of chemical composition on the microstructure and properties of coating is investigated. The results show that the microstructure and mechanical properties of Si-C-N coatings are very sensitive to chemical composition. The nanocrystalline/amorphous composite structure is beneficial to the coating's mechanical properties. It also reveals that Si-C-N coating with low Si and high C concentrations has the highest hardness (≥40 GPa) and the best wear property with dry friction coefficient about 0.2.     

Ultrasound-assisted development and characterization of novel polyphenol-loaded pullulan/trehalose composite films for fruit preservation

A novel food packaging film was developed by incorporating a tea polyphenols-loaded pullulan/trehalose (TP@Pul/Tre) into a composite film with ultrasound-assisted treatment of dual-frequency (20/35 kHz, 40 W/L) for 15 min to assess the physicochemical and mechanical properties of a composite film. The optimized ultrasound-assisted significantly increases elongation at break, tensile strength, and improves the composite film's UV/water/oxygen barrier properties. Structure analysis using attenuated total reflectance-Fourier transform infrared, X-ray diffraction and thermal stability revealed that these improvements were achieved through ultrasound-enhanced H-bonds, more ordered molecular arrangements, and good intermolecular compatibility. Besides, the ultrasound-assisted TP@Pul/Tre film has proven to have good antibacterial performance against Escherichia coli and Staphylococcus aureus, with approximately 100 % lethality at 4 h and 8 h, respectively. Moreover, the ultrasound-assisted TP@Pul/Tre film effectively delayed moisture loss, oxidative browning, decay, and deterioration in fresh-cut apples and pears, thereby extending their shelf life. Thus, ultrasound has proved to be an effective tool for improving the quality of food packaging films, with a wide range of applications.     

The influence of magnetic heat treatment on morphology,structure, magnetic properties of Fe-Co-P alloy films

FeCoP nanocrystalline films were successfully electrodeposited on the Cu film coated silicon substrate in the bath containing Fe²⁺, Co²⁺, as well as different concentration H₂PO^? ions ranging from 0.001 mol/L to 0.01 mol/L. And then the samples experienced magnetic heat treatment with different heating rates. Effects of H₂PO^? concentration and magnetic heat treatment on morphological, structural, and magnetic properties of the films were investigated by scanning electron microscopy, X-ray diffraction, vibrating sample magnetometer, and vector network analyzer. The results suggest that the as-deposited films do not exhibit obvious in-plane uniaxial magnetic anisotropy, and interestingly after magnetic heat treatment at heating rate of 6?°C/min, the FeCoP films will possess better in-plane uniaxial magnetic anisotropy. It has been obtained that morphology and grain size play important roles in determining magnetic properties. The magnetic performance of FeCoP films with different phosphorus content can be improved by appropriate magnetic heat treatment.     

Self-assembled L10 FePt thin films for high-density magnetic recording

A new technique, which utilizes the interlayer diffusion, for preparation of self-assembled nanodot magnetic structures has been proposed. L1₀-phase Pt/FeCu and Pt/FeAg films have been successfully synthesized by this technique. Both the coercivity of Pt/FeCu and Pt/FeAg films exhibited, respectively 4.1 and 8.0 kOe in perpendicular direction. Pt/Fe and Pt/FeAg films show positive values, while Pt/FeCu shows negative value in δm plot. The results indicate that the exchange coupling between the grains has been decoupled in the self-assembled nanodot structure in Pt/FeCu film.     

Influence of crystalline diamond nanoparticles on diamond-like carbon friction behavior

Crystalline diamond (CD) particles have been incorporated in diamond-like carbon (DLC) film structure in order to improve DLC electrochemical corrosion resistance. This paper shows the investigation of CD-DLC friction behavior according to the CD average sizes and concentration. The films were growth over 304 stainless steel using plasma enhanced chemical vapor deposition. The response surface methodology was used to develop a mathematical modeling of friction for these films, using the experimental results, in order to identify parameters that control friction and construct tribological maps according to the CD average sizes. The presence of bigger CD particles (250 and 500 nm) increased the film roughness. Films with CD particles of 4 nm presented the most homogeneous friction map, with minor variation in friction coefficient with the increase/decrease of load and sliding speed even when the CD concentration increase. This result suggests that in CD-DLC films containing CD particles of 4 nm average size, the nanoparticles are better incorporated in DLC structure due to its average size (4 nm) that is near than DLC grain size and could occupy the nanospaces between DLC grains.     

The electrochemical and mechanical properties of Ti incorporated amorphous carbon films in Hanks’ solution

Ti incorporated amorphous carbon (a-C) films with variant Ti contents were prepared by the unbalanced magnetron sputtering process. Scanning electron microscopy, ultraviolet Raman spectroscopy, X-ray photoelectron spectroscopy and transmission electron microscopy were used to characterize the microstructure of a-C films. The hardness and lubricated tribological properties were assessed using nanoindentation and ball-on-disk tribometer. As the Ti content in a-C films increases from 0 to 15.2 at.%, the sp³ volume fraction, the internal stress and the hardness of the films decreases gradually, while the disorder of sp² bond increases. The electrochemical tests reveal that the a-C films with lower than 1.5 at.% Ti possess good corrosion resistance in Hanks’ solution, while the a-C film with 15.2 at.% Ti is susceptible to crevice corrosion. The reduced friction of the a-C films is due to the sp² bonded film surface and boundary lubrication of the Hanks’ solution. The a-C film with 3.1 at.% Ti exhibits the best wear resistance in Hanks’ solution among the studied films.     

Hydrogenated diamond-like carbon film deposited on UHMWPE by RF-PECVD

In this work, investigations were conducted to analyze the properties of diamond-like carbon (DLC) film deposited on ultra-high molecular weight polyethylene (UHMWPE) by radio frequency plasma enhanced chemical vapor deposition (RF-PECVD) at a low temperature of 50 °C. Composition and structure of the films were characterized by scanning electron microscopy (SEM) and Raman spectroscopy. Hardness and wettability of the film were tested. Tribological characterizations were carried out on a universal micro-tribometer, and reciprocating friction against ZrO₂ ball was adopted with 25% bovine serum as lubrication. Results show that DLC film was successfully deposited on UHMWPE surface by RF-PECVD and the sp³ content was about 20% in the film. The film increased the macrohardness of the substrate by about 42% and the wettability was improved too. Tribology test showed a higher friction coefficient but a much smaller wear volume after the deposition due to the surface roughening and strengthening.     

XPS and AES investigations of hard magnetic Nd-Fe-B films

Nd-Fe-B is a promising material system for the preparation of thin films with good hard magnetic properties. One problem of this material class is the sensitivity against oxidation, resulting in a degradation of the magnetic properties. Using XPS depth profiling in combination with peak-shape analysis it is shown that already after several hours oxygen can diffuse deep into the thin laser-deposited films and that Nd is mainly responsible for the oxidation. Local element analysis with AES revealed boron inhomogeneities from droplet formation during laser deposition. These problems can be solved by using a capping Cr layer and an FeB target for thin film preparation, respectively.     

Tribological properties of chemically bonded polyimide films on silicon with polyglycidyl methacrylate brush as adhesive layer

Polyimide thin films, which possess good stability and film uniformity, are successfully fabricated on single crystal silicon wafers coated with a thin polymer brush by suface-initiated polymerization (SIP) as an adhesive layer. The growth kinetic of polyglycidyl methacrylate (PGMA) brush was studied by the means of ellipsometry. The nano-scale morphology and chemical composition of PGMA brush and polyimide film were studied with atomic force microscopy (AFM), Fourier transform infrared spectrum (FT-IR), and X-ray photoelectron spectroscopy (XPS). The tribological behaviors of the thin films sliding against AISI-52100 steel ball were examined on a static-dynamic friction precision measurement apparatus and UMT-2MT tribometer. The worn surface of the polyimide thin films was investigated with scanning electron microscopy (SEM). The results indicated that the chemically bonded polyimide films exhibited better friction reduction and antiwear behavior compared to the polymide films on bare silicon surface. At a load of 0.5 N and sliding speed of 20 mm s⁻¹, the durability life of the polyimide thin films is over 25,000 sliding cycles and the friction coefficient is about 0.08.     

Au/TiN复合薄膜制备及其表面增强拉曼光谱研究

表面增强拉曼散射光谱(SERS)已用于环境监测、生物医药、食品卫生等领域,而高活性SERS基底是表面增强拉曼散射光谱技术应用的关键。TiN作为新型等离子材料具有较强的SERS性能,同时化学稳定性及生物相容性较好,但其SERS性能不如贵金属金强。该研究采用氨气还原氮化法和电化学沉积法,在TiN薄膜表面沉积贵金属Au纳米颗粒制备出Au/TiN复合薄膜。在Au/TiN复合薄膜中单质Au和TiN两种物相共存;随着电化学沉积时间延长,TiN薄膜表面单质金纳米颗粒数量逐渐增多,金纳米颗粒尺寸增大,颗粒间距减小。由于金与TiN两者的本征表面等离子共振耦合作用,Au/TiN复合薄膜的共振吸收峰发生了偏移。利用罗丹明6G为拉曼探针分子,对Au/TiN复合薄膜进行SERS性能分析,发现Au/TiN复合薄膜上的R6G探针分子的拉曼峰信号强度随沉积时间延长呈现先增大后减小的规律;当电化学沉积时间为5 min时,R6G拉曼信号峰较高,复合薄膜样品的SERS活性最大。将Au/TiN复合薄膜和Au薄膜分别浸泡在10-3,10-5,10-7,10-8及10-9 mol·L-1 R6G溶液5 min,进行检测限分析,发现Au/TiN复合薄膜检测极限达10-8 mol·L-1,增强因子达到8.82×105,与Au薄膜和TiN薄膜相比,Au/TiN复合薄膜上对R6G探针分子SERS活性最高。这得益于Au/TiN复合膜中表面等离子体产生的耦合效应,使得局域电磁场强度增强,从而引起R6G探针分子拉曼信号增强。通过2D-FDTD模拟电场分布发现Au/TiN,Au及TiN薄膜具有电场增强作用,其中Au/TiN复合薄膜的增强作用尤为显著,这也证实了氮化钛与金纳米颗粒之间存在耦合效应。另外发现TiN与Au之间可能存在电荷转移,促进了4-氨基苯硫酚氧化反应,进而证实了TiN与Au薄膜的协同作用。此外,Au/TiN复合薄膜均匀性较好,相对平均偏差仅为7.58%。由此可见,采用电化学沉积制备的Au/TiN复合薄膜具有作为SERS基底材料的应用潜力。