Hemocompatibility of diamondlike carbon–metal composite thin films

We have investigated the hemocompatibility of diamondlike carbon–silver composite and diamondlike carbon–titanium composite thin films prepared using a multicomponent target pulsed laser deposition process. These materials were examined using transmission electron microscopy, Raman spectroscopy, nanoindentation, electrochemical charge transfer testing, and platelet adhesion testing. Cross-sectional transmission electron microscopy revealed that silver self-assembles into nanoparticle arrays within the diamondlike carbon matrix in the diamondlike carbon–silver composite film. On the other hand, titanium self-assembles into alternating nanometer-thick titanium carbide layers within the diamondlike carbon matrix in the diamondlike carbon–titanium composite film. The hemocompatibility of these materials was examined using electrochemical charge transfer testing and platelet adhesion testing. A few small, widely scattered crystals were observed on the surface of the unalloyed diamondlike carbon film exposed to platelet rich plasma. On the other hand, dense fibrin networks with densely aggregated platelets were observed on the surfaces of diamondlike carbon–silver and diamondlike carbon–titanium composite thin films exposed to platelet rich plasma. Electrochemical testing revealed that the time constant for the diamondlike carbon thin film (λ = 1) was significantly higher than those for the diamondlike carbon–silver and diamondlike carbon–titanium composite thin films. These results suggest possible uses for diamondlike carbon thin films and diamondlike carbon–metal composite thin films as coatings in next generation cardiovascular implants.     

Antibacterial activity of DLC and Ag–DLC films produced by PECVD technique

Diamond-like carbon (DLC) films have been the focus of extensive research in recent years due to its potential application as surface coatings on biomedical devices. Doped carbon films are also useful as biomaterials. As silver (Ag) is known to be a potent antibacterial agent, Ag–DLC films have been suggested to be potentially useful in biomedical applications. In this paper, DLC films were growth on 316L stainless steel substrates by using Plasma Enhanced Chemical Vapour Deposition (PECVD) technique with a thin amorphous silicon interlayer. Silver colloidal solution was produced by eletrodeposition of silver electrodes in distilled water and during the deposition process it was sprayed among each 25 nm thickness layer DLC film. The antibacterial activity of DLC, Ag–DLC and silver colloidal solution were evaluated by bacterial eradication tests with Escherichia coli (E. coli) at different incubation times. With the increase of silver nanoparticle layers in Ag–DLC, the total compressive stress decreased significantly. Raman spectra showed the film structure did not suffer any substantial change due to the incorporation of silver. The only alteration suffered was a slightly reduction in hardness. DLC and Ag–DLC films demonstrated good results against E. coli, meaning that DLC and Ag–DLC can be useful to produce coatings with antibacterial properties for biomedical industry.     

Pulsed laser deposition of functionally gradient diamondlike carbon–metal nanocomposites

Diamondlike carbon thin films possess atomic smoothness, chemical inertness, and hardness properties close to those of diamond. Unfortunately, these films exhibit poor adhesion to metals and polymers used in medical prostheses. This paper presents the processing and characterization of diamondlike carbon–copper, diamondlike carbon–silver, diamondlike carbon–silicon, and diamondlike carbon–titanium nanocomposite films with enhanced adhesion to Ti–6Al–4V alloy substrates. Silver forms nanoparticle arrays within the diamondlike carbon matrix in diamondlike carbon–silver nanocomposite films. On the other hand, titanium forms layers of titanium carbide within the diamondlike carbon matrix in diamondlike carbon–titanium nanocomposite films. These films were characterized using electron energy loss spectroscopy, transmission electron microscopy, Raman spectroscopy, Rutherford backscattering spectrometry, nanoindentation, wear testing, and scratch adhesion testing. Diamondlike carbon–metal nanocomposite films have numerous potential medical applications, including use on the surfaces of medical prostheses.     

Biological activity of silver-doped DLC films

The technique of combined DC metal arc and carbon pulsed arc was used to deposit thin solid films containing up to 6.5 at.% of silver. The microstructure and antibacterial properties of silver-doped diamond-like carbon (DLC) films have been investigated. Silver nanoparticle of flat disk shape located inside of an amorphous carbon matrix revealed excellent antibacterial properties concerning Staphylococcus аureus bacteria. Titanium substrates with DLC films doped with silver have an inhibiting effect on growth of some tumors, in particular, on rat neoplastic С6 glioma. This result is new and opens further possibility for application of DLC:Ag composite in medicine.     

Corrosion and tribological properties of ultra-thin DLC films with different nitrogen contents in magnetic recording media

The corrosion spot density and contact–start–stop tribological properties that correlate to mechanical properties, electrical resistivity and lubricant bonded ratio of DLC overcoats on different disks of various surface roughness were investigated. DLC overcoats of hydrogenated carbon (CH) and nitrogenated carbon (CN) films were deposited by ion beam deposition (IBD) and sputter, respectively. Results show that the intensity ratio I(D)/I(G) increases with decreasing IBD-CH film thickness and increasing N₂ concentration of sputtered-CN layer, which implies that the films prepared at higher N₂ concentration contain a relatively lower sp³ bonded carbon. The composite hardness and Young's modulus of DLC films decrease with decreasing IBD-CH thickness and increasing N₂ concentration of sputtered-CN layers. Compared to disk overcoats deposited with only IBD-CH of comparable thickness, the lubricant bonded ratio is dramatically increased from 12 to 30% when the 0.5 nm CN is deposited on IBD-CH film. By increasing the N₂ concentration in the CN layer from 10 to 50 at.%, the electrical resistivity decreased from 3.6 to 0.8 kΩ and the lubricant bonded ratio increased from 30 to 46%. The corrosion spots density of sputtered-CN film surface decreases with increasing N₂ concentration. It is concluded that the dual layer of 1.5 nm IBD-CH/0.5 nm sputtered-CN with 30% N₂ deposition has the best integrated performance of corrosion resistance and CSS tribological properties.     

Pulsed laser deposition of hydroxyapatite-diamondlike carbon multilayer films and their adhesion aspects

We have developed a layered hydroxyapatite/diamondlike carbon/functionally gradient diamondlike carbon-silver/titanium carbide/titanium carbonitride/titanium nitride composite film using pulsed laser deposition. A diamondlike carbon interlayer between a hydroxyapatite coating and the Ti-6Al-4V alloy can serve several purposes, including preventing corrosion of Ti-6Al-4V alloy, overcoming poor adhesion between the hydroxyapatite coating and the titanium oxide surface, and reducing inflammation at the implant/tissue interface. Titanium nitride, titanium carbonitride (TiC _x N _y ), titanium carbide and functionally gradient diamondlike carbon-silver layers were used to improve the adhesion of diamondlike carbon films to Ti-6Al-4V alloy. We envision several potential medical applications for these multilayer materials, including use in orthopedic and dental devices.     

A superhard diamond-like carbon film

A superhard hydrogen-free amorphous diamond-like carbon (DLC) film was deposited by pulsed arc discharge using a carbon source accelerator in a vacuum of 2×10⁻⁴ Pa. The growth rate was about 15 nm/min and the optimum ion-plasma energy was about 70 eV. The impact of doping elements (Cu, Zr, Ti, Al, F(Cl), N) on the characteristics of DLC films deposited on metal and silicon substrates was studied aiming at the choice of the optimum coating for low friction couples. The microhardness of thick (≥20 μm) DLC films was studied by Knoop and Vickers indentations, medium thick DLC films (1–3 μm) were investigated using a ‘Fischerscope’, and Young's module of thin films (20–70 nm) was studied by laser induced surface acoustic waves. The bonds in DLC films were investigated by electron energy loss spectroscopy (EELS), X-ray excited Auger electron spectroscopy (XAES), and X-ray photoelectron spectroscopy (XPS). The adhesion of DLC films was defined by the scratch test and Rockwell indentation. The coefficient of friction of the Patinor DLC film was measured by a rubbing cylinders test and by a pin-on-disk test in laboratory air at about 20% humidity and room temperature. The microhardness of the Patinor DLC film was up to 100 GPa and the density of the film was 3.43–3.65 g/cm³. The specific wear rate of the Patinor DLC film is comparable to that of other carbon films.     

A study of hard diamond-like carbon films in mid-frequency dual-magnetron sputtering

A series of hydrogen-free diamond-like carbon (DLC) films were deposited by a mid-frequency dual-magnetron sputtering under basic conditions of Cr and C target power density between 6 and 18 W/cm², bias voltage in a range of − 100 V to − 200 V, and a pure argon atmosphere. Microstructure, microhardness, adhesion, friction and wear properties were investigated for the DLC films to be used as protective films on cutting tools and forming dies, etc. The DLC films exhibited some combined superior properties: high hardness of 30–46 GPa, good adhesion of critical load of 50–65 N, and friction coefficient about 0.1 in air condition. Properties of the magnetron-sputtered carbon films showed a strong dependence on flux and energy of ion bombardment during growth of the films.     

Influence of a hard transition layer on the microstructure and properties of diamond-like carbon/hydroxyapatite composite coating prepared by magnetron sputtering

The nanostructured diamond-like carbon/hydroxyapatite composite coating (DLC/HA) was deposited using magnetron sputtering technique with a densely packed columnar cross-sectional structure and a uniform granular surface morphology. After heat treatment, the amorphous structure of the coating was transformed into a crystal structure. Nanohardness and scratch tests results demonstrated the DLC transition layer significantly enhanced the nanohardness of Ti6Al4V substrates from 4.8 GPa to 10.4 GPa, and increased critical load from 16.6 N (pure HA layer) to 26.5 N (DLC layer) without obvious brittle fracture, flaking and delamination. Electrochemical and immersion tests results demonstrated that DLC/HA composite coatings with a dense gradient transition interlayer had better corrosion resistance and could prevent harmful metal ions being released into the SBF solution more effectively than single HA coatings. Furthermore, active Ca²⁺ ions can be rapidly released from the coating surface during initial immersion in the SBF solution, and facilitated the formation of bone-like apatite.     

Mechanical and tribological properties of diamond-like carbon films prepared on steel by ECR-CVD process

Diamond-like carbon (DLC) films were prepared on AISI 440C steel substrates at room temperature by the electron cyclotron resonance chemical vapor deposition (ECR-CVD) process in C₂H₂/Ar plasma under different conditions. In order to prevent the inter-diffusion of carbon and improve the adhesion strength of DLC films, functionally gradient Ti/TiN/TiCN/TiC supporting underlayers were deposited on the steel substrates in advance. Using the designed interfacial transition layers, relatively thick DLC films (1–2 μm) were successfully prepared on the steel substrates without delamination. By optimizing the deposition parameters, DLC films with hardness up to 28 GPa and friction coefficients lower than 0.15 against the 100Cr6 steel ball were obtained. In addition, the specific wear rates of the films were found to be extremely low (∼10⁻¹⁷ m³/Nm). The friction-induced graphitization mechanism of DLC was confirmed by micro-Raman analysis.     

Wear-corrosion behavior of ultra-thin diamond-like carbon nitride films on aluminum alloy

Diamond-like carbon films exhibit high hardness, high wear resistance and a low friction coefficient. They are extensively utilized in the mechanical, electronic and biomedical industries. This work evaluates the effect of the thickness of ultra-thin diamond-like carbon nitride films on their corrosion properties and their wear-corrosion resistance in a mixed 1 M NaCl + 1 M H₂SO₄ solution using electrochemical methods. The corrosion current density and weight loss of all films during and after wear-corrosion test are also recorded. This work employs ion beam-assisted deposition (IBAD) to deposit DLC nitride films of various thicknesses (1.5, 2.0, 2.5 and 3.0 nm), containing 60% nitrogen gas in the form of a gaseous mixture of C₂H₂ + 60%N₂. The thickness of the films was measured using a transmission electron microscope (TEM). The atomic bonding structures of these DLC nitride films are analyzed using a Raman spectrometer and by electron spectroscopy for chemical analysis (ESCA). A scanning electron microscope (SEM) was adopted to elucidate the surface morphologies of the specimens after corrosion and wear-corrosion. The results indicated that all of the nitrogen-containing DLC films excellently protected the 5088 Al–Mg alloy substrate with an electroless plated Ni–P interlayer against corrosion, and that the degree of protection increases with the thickness of the film. In the wear-corrosion tests various potentials were applied during wear in the particular corrosive solution. The results further demonstrated that the wear-corrosion resistance of all the nitrogen-containing DLC films was as effective as corrosion protection, and that the wear-corrosion loss decreased as the film thickness increased.     

Electrochemical behavior of amorphous carbon films: kinetic and impedance-spectroscopy studies

Impedance spectra and potentiodynamic curves of oxidation and reduction reactions in the quinone/hydroquinone and Ce^3+/4+ systems were measured in a 0.5M H₂SO₄ solution on amorphous carbon thin-film electrodes grown by magnetron sputtering or ion source techniques. The electrode equivalent circuit contains a constant phase element. Only narrow-bandgap (“graphitelike”) amorphous carbon is electrochemically active; however, the wider bandgap (“diamondlike”) material also acquires the activity on “doping” it with platinum (ca 10%) in the course of film growth. The admixture of platinum does not effect film conductivity; its action probably is of catalytic character. In its electrochemical activity, the platinum-containing amorphous diamondlike carbon films resemble boron-doped polycrystalline diamond.     

Temperature Dependence of Diamondlike Carbon Film Tribological Characteristics

The tribological characteristics of a diamondlike carbon (DLC) film deposited on high-speed steel were investigated systematically by using a ball-on-flat reciprocating tribometer over a range of temperatures (from −40° to 20°C). The results indicated that the temperature dependence of the DLC film's tribological behavior was associated with the counterpart material. DLC presented favorable tribological behavior while sliding on itself. However, when a steel ball slides against the DLC film, there is evidence that the heat generated has a significant impact on friction and wear. Microanalysis of wear tracks on the films showed that multiple wear mechanisms took place during testing. At higher temperatures, material transfer dominated the wear behavior, while fatigue-induced microcracking was the predominant wear mechanism at low temperatures. Raman analysis indicated that the DLC film was mechanically worn rather than removed by tribochemical interactions between the friction pairs.     

Effect of gold oxide incorporation on electrochemical corrosion resistance of diamond-like carbon

Gold oxide nanoparticles were incorporated into diamond-like carbon (DLC) films in order to improve protection of AISI-1020 from electrochemical corrosion. The AuO_x:DLC films were prepared by plasma enhanced chemical vapor deposition and were subsequently characterized by scanning electron microscopy, Raman spectroscopy and electrochemistry measurements. The electrochemical corrosion performance of the AuO_x:DLC coating was contrasted to AISI-1020 and DLC without AuO_x coating. The electrochemical techniques that were utilized for this investigation were potentiodynamic and electrochemistry impedance spectroscopy. The electrochemical analysis indicated that AuO_x:DLC films presented superior corrosion resistance as compared to DLC. This resulted in 99.8% and 96.8% protection efficiency respectively, when compared to AuO_x:DLC and DLC coatings.     

Microstructure and mechanical properties of CeO2 doped diamond-like carbon films

A kind of rare earth oxide, CeO₂, was doped into the diamond-like carbon (DLC) films with thickness of 180–200 nm, using unbalanced magnetron sputtering. All the adhesion strength of CeO₂ doped DLC films is increased, while the residual compressive stress is obviously decreased compared to pure DLC film. Specially, the residual compressive stress of the deposited films are reduced by 90%, when the CeO₂ content is in the range of 5–7%, from a value of about 4.1 GPa to 0.5 GPa. When the CeO₂ content is increased to 10%, the deposited films possess the highest adhesion strength of 85 mN, 37% higher than that of pure DLC film. The nanohardness and elastic modulus exist a transition point at 8% of CeO₂ content within the DLC film. Before this value, nanohardness and elastic modulus of CeO₂ doped DLC films are lower than those of pure DLC film, and after this value, they are higher or adjacent to those of pure DLC film. Auger electron spectroscopy shows a more widened interface of 6% CeO₂ doped DLC film compared to pure DLC film. The enhancement of adhesion strength is mainly attributed to the widening of the film-substrate interface, as well as the decrease of residual compressive stress.     

Mechanical characterization of ultra-thin fluorocarbon films deposited by R.F. magnetron sputtering

Fluorocarbon films were deposited on silicon substrate by R.F. magnetron sputtering using a polytetrafluoroethylene (PTFE) target. Structure of the deposited films was studied by X-ray photoelectron spectroscopy (XPS). Hardness, elastic modulus and scratch resistance were measured using a nanoindenter with scratch capability. -CF_x (x = 1, 2, 3) and C-C units were found in the deposited fluorocarbon films. The hardness and elastic modulus of the films are strongly dependent on the R.F. power and deposition pressure. The film hardness is in the range from 0.8 GPa to 1.3 GPa while the film elastic modulus is in the range from 8 GPa to 18 GPa. Harder films exhibit higher scratch resistance. Differences in nanoindentation behavior between the deposited fluorocarbon films, diamond-like carbon (DLC) films and PTFE were discussed. The fluorocarbon films should find more applications in the magnetic storage and micro/nanoelectromechanical systems.     

Antibacterial property of DLC film coated on textile material

To evaluate the antibacterial property for diamond-like carbon films (DLC), DLC films were coated on textile material (cotton fibres) using a plasma-based ion implantation (PBII). Raman spectra show the DLC films were successfully coated on the cotton fibres. An antibacterial property of DLC film against two types of bacteria (Staphylococcus aureus, and Klebsiella pneumoniae) was investigated by the standard evaluation technique International Organization for Standardization (ISO) 20743. After incubation for 18 h, the number of cell colonies of the normal cotton fibres increased 100 times more than that of the initial condition. In contrast with the cotton fibres with DLC coating, no active bacteria could be observed after incubation for 18 h. X-ray photoelectron spectroscopy confirms that DLC coating formed C–H bond on cotton surface. Consequently, DLC film coating is a promising method to inhibit the increase of active bacteria. The DLC coatings are expected for biomedical applications with antibacterial property for coating of the commercial items.     

Synthesis and mechanical properties of carbon nanotube/diamond-like carbon composite films

Diamond-like carbon (DLC) coatings were successfully deposited on carbon nanotube (CNT) films with CNT densities of 1 × 10⁹/cm², 3 × 10⁹/cm², and 7 × 10⁹/cm² by a radio frequency plasma-enhanced chemical vapor deposition (CVD). The new composite films consisting of CNT/DLC were synthesized to improve the mechanical properties of DLC coatings especially for toughness. To compare those of the CNT/DLC composite films, the deposition of a DLC coating on a silicon oxide substrate was also carried out. A dynamic ultra micro hardness tester and a ball-on-disk type friction tester were used to investigate the mechanical properties of the CNT/DLC composite films. A scanning electron microscopic (SEM) image of the indentation region of the CNT/DLC composite film showed a triangle shape of the indenter, however, chippings of the DLC coating were observed in the indentation region. This result suggests the improvement of the toughness of the CNT/DLC composite films. The elastic modulus and dynamic hardness of the CNT/DLC composite films decreased linearly with the increase of their CNT density. Friction coefficients of all the CNT/DLC composite films were close to that of the DLC coating.     

Mechanical properties of DLC films prepared in acetylene and methane plasmas using electron cyclotron resonance microwave plasma chemical vapor deposition

Diamond-like carbon (DLC) films were deposited on silicon using methane and acetylene plasma induced by electron cyclotron resonance microwave plasma chemical vapor deposition (ECR-MPCVD). The mechanical properties of DLC films were characterized by micro-Raman system, atomic force microscope, tribometer, nano-indenter used for both hardness and nano-scratch test measurements. The mechanical properties of both DLC films, prepared in methane and acetylene plasmas, respectively, strongly depended on the kinetic energy of impinging particles. The deposition at −120 V substrate bias gave rise to DLC films with the best mechanical properties for both methane and acetylene plasmas. The hardness measurements with variable indentation depth showed the characteristic changes in hardness values implying elastic deformations of supporting substrates. The maximum hardness value of DLC^M films was 20 GPa while that of DLC^A films was 28 GPa. However, the hardness dropped when DLC films were prepared at substrate biases more negative than −120 V due to the thermal graphitization. The improvement in DLC properties usually provided the films with smaller hydrogen content and higher density of sp³ bondings. These parameters were engineered through controlling the deposition parameters. Particularly, the bombardment of growing DLC films by energetic ions showed to be extremely important to yield films with lower internal stress.     

Structural characterization and properties enhancement of diamond-like carbon films synthesized under low energy Ne bombardment

Diamond-like carbon (DLC) films were synthesized by Ar⁺ sputtering graphite with concurrent Ne⁺ bombardment. Transmission electron microscopy diffraction revealed that some diamond crystals were distributed in the amorphous matrix of DLC films synthesized under Ne⁺ bombardment at an energy of 200 eV and ion current density of 0.19 mA cm⁻². X-ray photo electron spectra showed that the valence band of the DLC films was similar to that of diamond, and the binding energy of electrons was 284.9 eV. The DLC films possessed a high hardness of 42.14 GPa and excellent wear resistance. It was confirmed that the wide atomic intermixed film-substrate interface meant that the DLC films would improve greatly the wear-resistant properties of AISI 52100 steel if the DLC films were coated on its surface.