Corrosion performance of diamond-like carbon (DLC)-coated Ti alloy in the simulated body fluid environment

DLC coatings have been deposited onto substrate of Ti alloy (Ti-6Al-4V) using r.f. PACVD (plasma-assisted chemical vapor deposition) with C₆H₆, and mixture of C₆H₆ and SiH₄ as the process gases. Three kinds of DLC coatings were prepared as a function of diverse bias voltage and Si incorporation. Corrosion performance of DLC coatings was investigated by electrochemical techniques (potentiodynamic polarization test and electrochemical impedance spectroscopy) and surface analyses (atomic force microscopy and scanning electron microscopy). The electrolyte used in this test was a 0.89% NaCl solution of pH 7.4 at temperature 37°C. The porosity and protective efficiency of DLC coatings were obtained using potentiodynamic polarization test. Moreover, the delamination area and volume fraction of water uptake of DLC coatings as a function of immersion time were calculated using electrochemical impedance spectroscopy. This study provides the reliable and quantitative data for assessment of the effect of Si incorporation and an increase of bias voltage on corrosion performance. In conclusion, electrochemical measurements showed that DLC coatings with Si addition and an increase of bias voltage could improve corrosion resistance in the simulated corrosive environment of the body fluid by a 0.89% NaCl solution. This could be attributed to the formation of a dense and low-porosity coating, which impede the penetration of water and ions.     

In-situ atomic force microscopy of silicon(100) in aqueous potassium hydroxide

Growth dynamics of pyramid-shaped features that emerge during etching of silicon(100) surfaces in 2 M aqueous potassium hydroxide solutions have been investigated using in-situ atomic force microscopy. Micropyramids were found to grow continuously from a scale-shaped structure that is present on the surface during etching. In addition, two characteristic removal mechanisms of fully developed pyramids could be identified. It is suggested that these etching mechanisms are unique to pyramids and not comparable to the etching properties of single crystal surfaces.     

The influence of nitrogen on the dielectric constant and surface hardness in diamond-like carbon (DLC) films

In this work a carbon target was sputtered by a methane/argon/nitrogen plasma in order to produce nitrogenated diamond-like carbon films (a-C:H:N). As the N₂ content in the sputtering gas was increased, the deposition rate increased markedly. Rutherford backscattering spectrometry (RBS) was used to investigate the chemical composition of the films. This nitrogen incorporation modifies the chemical bonding structure of the films, as shown by the analysis of the Raman spectra, including the occurrence of two extra peaks at approximately 2200 and 690 cm⁻¹. Electrical properties were measured through capacitance–voltage (C–V) curves. The hardness of the films decreased with the N content as shown by measurements performed by indentation method. A correlation among the Raman studies, the N content in the films, the dielectric constant and the surface hardness is presented.     

Biaxial elastic modulus of very thin diamond-like carbon (DLC) films

The biaxial elastic modulus of very thin diamond-like carbon (DLC) films was measured by the recently suggested free overhang method. The DLC films of thickness ranging from 33 to 1100 nm were deposited on Si wafers by radio frequency plasma-assisted chemical vapor deposition (r.f.-PACVD) or by the filtered vacuum arc (FVA) process. Because the substrate was partially removed to obtain sinusoidal free overhang of the DLC film, this method has an advantage over other methods in that the measured value is not affected by the mechanical properties of the substrate. This advantage is more significant for a very thin film deposited on a substrate with a large difference in mechanical properties. The measured biaxial elastic moduli were reasonable values as can be judged from the plane strain modulus of thick films measured by nanoindentation. The biaxial elastic modulus of the film deposited by r.f.-PACVD was 90±3 GPa and that of the film deposited by FVA process was 600±50 GPa. While the biaxial elastic modulus of the film deposited by FVA is independent of the film thickness, the film deposited by r.f.-PACVD exhibited decreased elastic modulus with decreasing film thickness when the film is thinner than 500 nm. Although the reason for the different behavior could not be clarified at the present state, differences in structural evolution during the initial stage of film growth seem to be the reason.     

Tribological analysis of glass fibers using atomic force microscopy (AFM)/lateral force microscopy (LFM)

By using atomic force microscopy (AFM)/lateral force microscopy (LFM), a comparative study of the topography as well as the tribological properties (at a micrometer scale) of sized E‐glass fibers was done. Normal and lateral deflection signals are recorded when an AFM tip scans a fiber surface. Friction force data were obtained from the forward and backward scans of lateral force images whose contrasts reveal differences in friction coefficient values and, hence, surface chemical heterogeneity of certain‐sized glass fibers. Sizes having an epoxy film former lead to a higher friction coefficient value than those containing a starch film former. Moreover, the epoxy‐containing size is more readily plowed by the AFM tip. Annealing of this size lowers its friction coefficient. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1013–1025, 2000     

Effect of diamond-like carbon (DLC) on the properties of the NiTi alloys

NiTi alloy has found wide application in the biomedical field due to its unique shape memory effect, superelasticity and biocompatibility. However, the materials are vulnerable to surface corrosion and the most serious issue is out-diffusion of toxic Ni ions from the substrate into body tissues and fluids. In this paper, NiTi alloys were coated with diamond-like carbon (DLC) fabricated by plasma immersion ion implantation and deposition (PIIID) to improve their corrosion resistance and blood compatibility without sacrificing their shape memory effect and superelasticity. The structure of the films and the depth profiles between the films and substrate were studied using Raman spectroscopy and XPS, respectively. The phase transformation temperature, superelasticity, anticorrosion behavior and Ni ions release of the coated and uncoated sample were investigated by DSC, tensile tests, potentiodynamic polarization and AAS, respectively. The hemocompatibilty of the coated and uncoated samples was measured using clotting time and platelet adhesion. The results shows that the films is DLC accompanying with the formation of the mixing layer, and the DLC films can markedly improve the corrosion resistance and the hemocompatibility, obviously increase the ratio of albumin-to-fibrinogen and effectively block the Ni ions release of the NiTi alloys without sacrificing its superelasticity and changing its phase transformation temperature. The research results suggest DLC films prepared by PIIID could improve the in vivo performance of NiTi alloys implanted into the human body.     

Relationship between static friction and surface wettability of orthodontic brackets coated with diamond-like carbon (DLC), fluorine- or silicone-doped DLC coatings

In orthodontics, it is important to reduce the static friction between brackets and wires in order to enable easy tooth movement. The goal of the present study was to deposit diamond-like carbon (DLC), fluorine-doped DLC (F-DLC), and silicon-doped DLC (Si-DLC) coatings onto the slot surface in stainless steel orthodontic brackets using the plasma-enhanced chemical vapor deposition (PECVD) method and to characterize the frictional property between the coated bracket and wire under dry and wet conditions.In order to characterize DLC-, F-DLC- or Si-DLC-coated surface, XPS, the surface roughness and surface wettability of three deferent surfaces were measured. A nanoindentation test and a scratch test were performed in order to measure the hardness and adhesiveness, respectively, of DLC-, F-DLC- or Si-DLC coatings. The static friction between DLC-, F-DLC-, Si-DLC-coated brackets and 0.019 × 0.025-in stainless steel (SS) orthodontic wires was measured for several angulations under dry and wet conditions using a universal testing machine equipped with a custom-made friction-testing device.The F 1s or Si 2p and Si 2s peaks were observed for F-DLC (27.8 at.%:F) or Si-DLC (26.8 at.%:Si), respectively. There were no significant differences in the surface roughness of the slot surface of the bracket among the four types of specimens. The F-DLC was significantly hydrophobic and Si-DLC was significantly hydrophilic as compared to DLC. Doping the DLC with fluorine or silicon caused the surface hardness to decrease significantly.The results of the present study indicate that DLC, F-DLC and Si-DLC coatings provided a significant reduction in static friction. Among the coatings examined herein, F-DLC-coated bracket exhibited the significantly lowest static friction between the bracket and wire under the wet condition, which was lower than that under the dry condition. The F-DLC coating is highly promising as a means of promoting effective tooth movement and shortening treatment time for orthodontic treatments.     

Instability of diamond-like carbon (DLC) films during sliding in aqueous environment

The instability of diamond-like carbon (DLC) film deposited on Ti-6Al-4V alloy substrate using the r.f.-PACVD method was investigated under sliding conditions in an aqueous environment. Significant adhesive wear was observed when tested in this environment, while normal abrasive wear occurred in an ambient air of relative humidity about 25%. A critical test was performed to elucidate the reason for the instability which limits the biomedical applications of the DLC coating. By employing a multi-step coating process, it was shown that the instability is closely related to the penetration of water molecules to the interface via through-film defects or pinholes. These results suggest that the stability of DLC film in aqueous environment can be improved by controlling the through-film defects in the DLC coating layer.     

Mechanical measurements of ultra-thin amorphous carbon membranes using scanning atomic force microscopy

The elastic modulus of ultra-thin amorphous carbon films was investigated by integrating atomic force microscopy (AFM) imaging in contact mode with finite element analysis (FEA). Carbon films with thicknesses of ～10 nm and less were deposited on mica by electron beam evaporation and transferred onto perforated substrates for mechanical characterization. The deformation of these ultra-thin membranes was measured by recording topography images at different normal loads using contact mode AFM. The obtained force-distance relationship at the center of membranes was analyzed to evaluate both the Young’s modulus and pre-stress by FEA. From these measurements, Young’s moduli of 178.9 ± 32.3, 193.4 ± 20.0, and 211.1 ± 44.9 GPa were obtained for 3.7 ± 0.08, 6.8 ± 0.12, and 10.4 ± 0.17 nm thick membranes, respectively. Raman spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy were used for characterizing the chemical and structural properties of the films, including the content of sp² and sp³ hybridized carbon atoms.     

Controlling the drug release rate from biocompatible polymers with micro-patterned diamond-like carbon (DLC) coating

During the past year, we have witnessed the evolution of an intense public controversy regarding late thrombosis following implantation of drug eluting stent (DES) in patients with obstructive coronary artery disease. To overcome the problem, DES should possess sufficient biocompatibility and non-thrombogenicity with a controlled drug release system. A new DES composed of biocompatible polymers coated with antithrombogenic diamond-like carbon (DLC) coating was proposed. In this study, the drug release profile of the newly proposed drug eluting system was thoroughly investigated. Three polymers were selected as base drug-reservoir materials: hydrophilic 2-methacryloyloxyethyl phosphorylcholine (MPC), hydrophobic poly (ethylene-co-vinyl acetate) (EVA) and less hydrophobic polyurethane (PU). The three polymers are currently used or studied for biomedical materials, while MPC and DLC were already confirmed as excellent biocompatible materials with antithrombogenicity. After coating the lattice-like patterned DLC on both polymers containing drug, samples were soaked in 2 ml of medium of phosphate-buffered saline with 10% ethanol. The drug release rate was measured by a spectrophotometer. The percentile cover area of patterned DLC on polymers was varied from 0% (without DLC) to 100% (fully covered). The sample without DLC coating presented an initial burst of the drug release from the polymer matrix, whereas the DLC-coated samples inhibited the initial burst release from polymers within the first five days of the experiments. It was found that the drug eluting profiles could be effectively controlled by changing the cover area of micro-patterned DLC coatings on polymers, which may be applicable to the next-generation DES system that eventually prevents late thrombosis.     

Local photoconductivity on diamond metal-semiconductor-metal photodetectors measured by conducting probe atomic force microscopy

Local photoconductivity characterizations have been carried out on planar interdigitated metal-semiconductor-metal (MSM) devices fabricated on homoepitaxial CVD diamond for UV application. For this purpose a deuterium light source with an integrated UV fibre was combined and adapted to a conducting probe atomic force microscope (CP-AFM) tool. In this study, photocurrent was evidenced by local electrical resistance mapping measurements and analyzed as a function of the applied voltage and time.     

Nano-patterning of through-film conductivity in anisotropic amorphous carbon induced using conductive atomic force microscopy

Direct nanometer patterning of through-film electrical conductivity on carbon films is crucial in the development of carbon materials for nanotechnology. Typically, nanometer topographical surface modification can be created using scanning probe microscopy techniques producing surface artifacts which do not extend through the film. Here, we demonstrate the direct nano-patterning of through-film conductivity on highly oriented anisotropic carbon films by applying single voltage pulses (6 V) to a conductive atomic force tip in contact with the film. The thus induced conductivity is at least four orders of magnitude higher than that of the nominal area.     

Nanopatterning of an organic monolayer covered Si (1 1 1) surfaces by atomic force microscope scratching

In the present work, an atomic force microscope (AFM) mounted with a diamond-coated tip was used to scratch through organic monolayer covered Si surfaces to create nanostructures by electrodeposition. The organic layer (1-octadecene) was covalently attached to a hydrogen-terminated Si (1 1 1) surface. Copper was deposited into the nanostructures either by immersion plating or electrodeposition. The morphology of copper deposits was studied using scanning electron microscope (SEM). The influence of the different types of semiconductor substrates (1-octadecene covered n-type Si and p-type Si) and different parameters such as immersion time on the copper deposition morphology is presented. Auger electron spectroscopy (AES) scans were performed to obtain information of the selectivity and the copper deposition. The results show clearly that under optimized conditions the organic layer can be used as an effective mask for the site selective patterning of copper nanostructures on Si.     

Pulse force nanolithography on hard surfaces using atomic force microscopy with a sharp single-crystal diamond tip

AFM-based technique of nanolithography is proposed. The method enables rapid point by point indentation with a sharp tip. When used in tandem with single-crystal diamond tips, this technique allows the creation of high aspect ratio grooves in hard materials, such as silicon or metals. Examples of fabricated groove arrays on Si surface with 30–100 nm pitches and 5–32 nm depths are presented. Cutting of a 63 nm thick metal magnetic film is demonstrated. The resulting structure is studied by the use of magnetic force microscopy.     

High-resolution Kelvin probe microscopy in corrosion science: Scanning Kelvin probe force microscopy (SKPFM) versus classical scanning Kelvin probe (SKP)

With the introduction of a Kelvin probe mode to atomic force microscopy, the so called scanning Kelvin probe force microscopy (SKPFM), the Kelvin probe technique finds application in a steadily increasing number of different fields, from corrosion science to microelectronics and biosciences. For many of these applications, high resolution is required as the relevant information lies in the sub-microscopic distribution of work functions or potentials, which explains the increasing interest in SKPFM. However, compared to the standard scanning Kelvin probe (SKP) technique SKPFM is prone to much more artefacts, which are often not taken into account in the interpretation of the results, as is also the case with the real physical nature of the measured data. A critical discussion of possible artefacts and on the interpretation of the data is presented in this paper, with the main focus on application in corrosion science.     

Study on the adsorption of poly(o-ethoxyaniline) nanostructured films using atomic force microscopy

Nanostructured films of poly(o-ethoxyaniline) (POEA) were studied by atomic force microscopy (AFM), which indicated a globular morphology for films containing one or more layers of POEA. Consistent with the nucleation and growth model for the adsorption process, the mean roughness and fractal dimension were found to increase with the time of adsorption and with the number of POEA layers in the initial stages of adsorption, reached maximum values and then decreased after 10 min of adsorption or after deposition of five POEA layers. Such behavior has been explained in terms of the decrease in the film irregularities, with voids being filled with polymeric material leading to smoother surfaces.     

Segregation in granular materials and the direct measurement of surface forces using atomic force microscopy

It is known that one of the dominant forces controlling the macroscopic motion of particles is the cohesive force due to the presence of liquid bridges between particles. In a mixing process, this force directly impacts the degree of homogeneity achievable by the system. The work presented here provides a quantitative analysis of this relationship through concurrent direct measurements of surface forces due to moisture and blending/segregation experiments. Atomic force microscopy (AFM) was employed to measure the force required to remove the AFM's cantilever from the surface of a glass bead with varying degrees of surface moisture. Corresponding blending/segregation experiments were performed using the same materials and conditions to develop a correlation between the interparticle forces due to the liquid layer and the final state of a mixing process. The extent to which greater moisture content increased the interparticle surface forces was quantified, and it was observed that segregation decreases proportionately to increases in surface forces.     

Studies of optical haze and surface morphology of blown polyethylene films using atomic force microscopy

Atomic force microscopy (AFM) has been used to examine the inner and outer surfaces of commercial blown polyethylene films. When this technique has been used, direct-space images of surface lamellae have been obtained, and the surface roughness determined. The haziness of the films has been measured, both in the as-produced state and when coated with suitable oil. Thus, both surface and bulk contributions to the apparent turbidity have been estimated. The aim of this study has been to correlate in turn the haziness, roughness, and surface morphology. Results obtained showed that the haze is related primarily to the surface roughness and can be reduced by lowering the frost line. AFM images unveiled lamellar features that were oriented predominantly in the transverse direction. The observed wide-angle X-ray diffraction (WAXD) intensities were consistent with an a-axis type of orientation.     

Miscibility and surface crystal morphology of blends containing poly(vinylidene fluoride) by atomic force microscopy

The miscibility and surface crystalline structure of blends containing poly(vinylidene fluoride) (PVDF) composed of and γ phases were investigated by atomic force microscopy (AFM) and differential scanning calorimeter (d.s.c.) measurements. It was found that the surface crystalline phase of PVDF and the degree of surface enrichment of a lower surface free energy component in a blend might strongly be affected by the magnitude of the intermolecular interaction, even though the blend is miscible. Also, the segmental interaction parameters was determined by combining the T_m depression of PVDF in a blend and the binary interaction model. According to the binary interaction model, the introduction of a carboxyl group for miscible [poly(methyl methacrylate)/PVDF] and [poly(vinyl acetate)/PVDF] blends decreased their miscibility.     

Characterization of protein immobilization on nanoporous gold using atomic force microscopy and scanning electron microscopy

Nanoporous gold (NPG), made by dealloying low carat gold alloys, is a relatively new nanomaterial finding application in catalysis, sensing, and as a support for biomolecules. NPG has attracted considerable interest due to its open bicontinuous structure, high surface-to-volume ratio, tunable porosity, chemical stability and biocompatibility. NPG also has the attractive feature of being able to be modified by self-assembled monolayers. Here we use scanning electron microscopy (SEM) and atomic force microscopy (AFM) to characterize a highly efficient approach for protein immobilization on NPG using N-hydroxysuccinimide (NHS) ester functionalized self-assembled monolayers on NPG with pore sizes in the range of tens of nanometres. Comparison of coupling under static versus flow conditions suggests that BSA (Bovine Serum Albumin) and IgG (Immunoglobulin G) can only be immobilized onto the interior surfaces of free standing NPG monoliths with good coverage under flow conditions. AFM is used to examine protein coverage on both the exterior and interior of protein modified NPG. Access to the interior surface of NPG for AFM imaging is achieved using a special procedure for cleaving NPG. AFM is also used to examine BSA immobilized on rough gold surfaces as a comparative study. In principle, the general approach described should be applicable to many enzymes, proteins and protein complexes since both pore sizes and functional groups present on the NPG surfaces are controllable.