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Artificial cardiovascular implants are now made mainly from extruded polytetrafluroethylene (PTFE). However, the limited haemocompatibility of PTFE causes blood clotting and results in early replacement. Many techniques are being developed to improve the haemocompatibility of such devices. One of the most promising techniques is to coat the devices with nitrogen-doped diamond-like carbon (NDLC) thin films. However, the structure of NDLC and its effect on the haemocompatibility of the coated devices have not been fully investigated as required for practical applications. In this thesis, ion beam deposited DLC and Nitrogen doped thin films on PTFE were investigated in order to have a better understanding of the relationships between the structure and biomedical properties of the DLC thin films.<p> DLC and NDLC thin films were synthesized using ion beam deposition. Commercially available PTFE sheets, which are similar to the material used for vascular grafts, were used as substrates for the DLC thin films. Silicon wafers were also utilized as substrates for condition optimization and property comparison. Raman spectroscopy, atomic force microscopy, X-ray photo emission spectroscopy and scanning electron microscopy were used to study the structural and morphological properties of the coated surface. The results show that the ion beam deposited thin films have a very smooth surface and exhibit low coefficient of friction and high adhesion to the substrate. Low concentration of nitrogen doping in DLC improved surface hardness and reduced surface roughness. Higher concentration of sp3 hybridized bonds was observed in the DLC thin films on Si than those on PTFE. DLC coating decreased the surface energy and improved the wettability of PTFE films.<p> The haemocompatibility of the pristine and DLC coated PTFE sheets were evaluated by platelet adhesion technique. The platelet adhesion results showed that the haemocompatibility of DLC coated PTFE, especially NDLC coated PTFE, was considerably improved as compared with uncoated PTFE. SEM observations showed that the platelet reaction on the coated PTFE was minimized as the platelets were much less aggregated and activated.

Artificial cardiovascular implants are now made mainly from extruded polytetrafluroethylene (PTFE). However, the limited haemocompatibility of PTFE causes blood clotting and results in early replacement. Many techniques are being developed to improve the haemocompatibility of such devices. One of the most promising techniques is to coat the devices with nitrogen-doped diamond-like carbon (NDLC) thin films. However, the structure of NDLC and its effect on the haemocompatibility of the coated devices have not been fully investigated as required for practical applications. In this thesis, ion beam deposited DLC and Nitrogen doped thin films on PTFE were investigated in order to have a better understanding of the relationships between the structure and biomedical properties of the DLC thin films.<p> DLC and NDLC thin films were synthesized using ion beam deposition. Commercially available PTFE sheets, which are similar to the material used for vascular grafts, were used as substrates for the DLC thin films. Silicon wafers were also utilized as substrates for condition optimization and property comparison. Raman spectroscopy, atomic force microscopy, X-ray photo emission spectroscopy and scanning electron microscopy were used to study the structural and morphological properties of the coated surface. The results show that the ion beam deposited thin films have a very smooth surface and exhibit low coefficient of friction and high adhesion to the substrate. Low concentration of nitrogen doping in DLC improved surface hardness and reduced surface roughness. Higher concentration of sp3 hybridized bonds was observed in the DLC thin films on Si than those on PTFE. DLC coating decreased the surface energy and improved the wettability of PTFE films.<p> The haemocompatibility of the pristine and DLC coated PTFE sheets were evaluated by platelet adhesion technique. The platelet adhesion results showed that the haemocompatibility of DLC coated PTFE, especially NDLC coated PTFE, was considerably improved as compared with uncoated PTFE. SEM observations showed that the platelet reaction on the coated PTFE was minimized as the platelets were much less aggregated and activated.

Prosthetic cardiac valve surgery is a well-established technique, but the search continues for engineering materials with sup..e rior mechanical characteristics in order to extend the service life of the implant. The introduction of pyrolytic carbon was seen as a breakthrough in the development of wear resistant, non-thrombogenic materials for such applications. However, thrombo-embolic phenomena and the need for anticoagulation treatment following valve insertion remain the main problems associated with artificial materials in this application. The work carried out in this research has studied the haemocompatibility of a commercially available, wear resistant TiffiN/TiCfDLC multilayer structure, and a second TiN coating deposited by RF reactive sputtering of a titanium target in a ArIN2 environment, as candidate materials for a heart valve prosthesis. The structure of the RF deposited tiN coating was assessed as a function of deposition conditions, and was seen to develop a particular preferred crystallographic orientation. The nature of this texture was influenced by the condition of the underlying substrate. The effect of substrate condition on the biocompatibility of the tiN coating was studied by assessment of fibroblast attachment and spreading, and by haemolytic analysis of released haemoglobin. The results showed that the initial attachment and orientation of fibroblast cells was influenced by the substrate condition, but no influence on the degree of spreading and haemolytic nature was observed. Characterisation of the TiN coating and the components of the multilayer structure was carried out by Atomic Force Microscopy (AFM), X-ray Photoelectron Spectroscopy (XPS), stylus profilometry and contact angle measurement. Haemocompatibility was studied by the interaction of the surfaces with plasma proteins, blood platelets and red blood ceUs. Cytotoxicity was studied using the MTT test. The degree of platelet activation on the surfaces correlated with their surface energy. The greatest degree of platelet spreading was observed on the more hydrophilic coatings. The lack of platelet activation seen on the DLC coating is attributed to its smooth surface and hydrophobic nature, resulting in higher levels of adsorption of anticoagulation proteins. The RF sputtered TiN coating caused significant levels of haemolysis and fibroblast cell death. None of the components of the multilayer structure caused such effects, although thrombus formation was observed to a degree on the Ti, TiN and TiC components of this structure. The toxic nature of the RF deposited TiN coating was not attributed to surface chemistry or roughness, but rather to a combination of the hydrophilic nature and the defect state of the surface.

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Abstract Cr-containing diamond-like carbon coatings (Cr-DLC) with gradient interlayers were studied to elucidate the effects of Cr content and substrate bias on the mechanical properties and microstructure of the deposited coatings. The coatings were deposited with a closed field unbalanced magnetron sputtering (CFUBMS) system. The Cr content and substrate bias were varied from 5 at.% to 30 at.% and -22 V to -60 V, respectively. Mechanical properties of the coatings were evaluated with nano-indenter, scratch tester, ball-on-disk tribo-tester and ball crater. Microstructures of the films were characterized by SEM, TEM, and Raman spectroscopy. Experimental results show that an increases in Cr content from 5 at.% to 30 at.% for the Cr-DLC coatings deposited at substrate bias of ¡V40V results in the increase of the hardness, Young¡¦s modulus, adhesion and friction coefficient, and the decrease of the deposition rate. A minimum abrasive wear rate was found at about 10 ~ 15 at.% Cr content. An increase in substrate bias from -22 V to -60 V for the Cr-DLC a of 10 at% Cr content results in a maximum hardness, Young¡¦s modulus and adhesion, and a minimum friction coefficient and abrasive wear rate at a substrate bias of -50 V, the although the deposition rate is decreased. TEM analysis revealed layered structure of about 35 nm period and fine CrC crystallite nanometer in size on the top layer of the Cr-DLC coatings.

In the present thesis, diamond-like carbon thin films were deposited on Si(100) and LiNbO3 substrates by a planar capacitor plasma-enhence-chemical-vapor-deposition system. The reaction gases were C2H2,CH4,O2 and mixed with Ar (95¢M) and H2(5¢M).The influence of the growth of the thin film from different substrates and three different source gases flow ratios have been studied. The bi-layers structure of SAW(Surface Acoustic Wave) device was then fabricated. The interdigital transducers (IDTs) were fabricated on the bi-layers structure. The conditions of the DLC thin film of the bi-layers structure was varied in order to discuss its effects on SAW devices. In addition to Raman analyses, SEM and AFM have been employed to characterize the DLC thin film quality. From the experimental results of Raman spectrum analysis reveals that the DLC film has wide and flat spectrum region at wavelength of 1585~1600cm-1 of G-band and 1390cm-1 of D-band .It indicates that the DLC film contains much graphite sp2 bonds and a small part of amorphous DLC sp3 bonds. The optimal deposition conditions of the DLC film have been found for the reaction gas of C2H2 and Ar, from which the insertion loss of the SAW filter shows the quality better than from the others. SEM and AFM analyses shows that the roughness of the DLC film is below 10 nm and the faces of the DLC films are flat to be made into devices.

DLC exhibits an extreme hardness, chemical stability and optical transparency properties, which are, to a certain extent, similar to those of diamond and thus of technological importance. In the case of amorphous hydrogenated carbon (a-C:H) films they can be interpreted as intermediate between diamond, graphite, and polymer-like carbon sites. The most important intrinsic hardness is protection of tools or machine parts against wear. Most modifications have been used on DLC to enhanced mechanical properties, such as reducing its internal compressive stress (N, Si, and metal incorporation), or to reduce its surface energy for further lowering of its already low friction coefficient with 0.1. Among various deposition techniques, microwave generated discharges, especially electron cyclotron resonance (ECR) plasmas, develop excellent a high degree of ionization, high ions densities. In this work, a novel hybrid technique for diamond-like carbon (DLC) film deposition has been developed, which combines the microwave ECR plasma discharging C2H2 and metallic magnetron sputtering. The effects of negative bias voltage and hydrocarbon flow rate for the deposition of a-C:H films on high speed steel were examined by Raman spectra, and their hardness was investigated by the Rockwell method. The Raman spectra show that at different hydrocarbon flow rate, the variation of the G line peak and width, and the integrated intensity ratio ID/IG of DLC and graphic, correlate well with the film hardness. Consequently, we suggest a deposition mechanism of DLC for this combined method.

Titanium (Ti) and its alloys have been widely used in aerospace, biomedical, chemical processing, marine facilities, and sports equipment because of their low density, very high tensile strength and toughness, and high corrosion resistance. However, the poor tribological properties has been a major problem and limited their widespread applications. Deposition of wear/corrosion resistant diamond-like carbon (DLC) coatings on Ti alloys is promising to significantly enhance the durability and service performances of these materials. However, the adhesion between DLC coatings and Ti alloy substrates is too weak to meet the application requirements. Up to now, approaches including optimization of deposition conditions, surface treatment of the substrate, deposition of an interlayer, and incorporation of metallic or nonmetallic elements have been used for adhesion enhancement of DLC on Ti alloys. In this research, a new method, nanodiamond particles incorporation, was developed for adhesion enhancement of DLC coatings on Ti alloys. In order to achieve high diamond nucleation without damaging the Ti alloy, nucleation enhancement of diamond on Ti alloys by nanodiamond seeding, tungsten (W) interlayers, and high methane concentration were studied. Diamond, DLC and W deposition were carried out by microwave assisted chemical vapor deposition, direct ion beam deposition and hot filament assisted chemical vapor deposition, respectively. Scanning electron microscopy, Atomic force microscopy, X-ray diffraction, Raman spectroscopy and synchrotron-based near edge extended X-ray absorption fine structure spectroscopy were used to characterize the microstructure and chemical bonding of the as-deposited particles and films, and indentation testing was used to evaluate the adhesion of the as-deposited coatings. By nanodiamond seeding or applying a W interlayer, significantly enhanced diamond nucleation has been obtained on Ti alloys, and consequently high quality nanocrystalline diamond thin films have been obtained on Ti alloys at decreased deposition temperature and reduced deposition time, which mitigates the deterioration of Ti alloy substrates due to hydrogen diffusion during diamond deposition and also enhances the adhesion of diamond on Ti alloys. Based on these results, nanodiamond particles (NDP) with high nucleation density and high adhesion were deposited on Ti alloys initially to enhance the adhesion of DLC films on Ti alloys. Results show that the pre-deposited NDP can significantly increase the adhesion of DLC on Ti6Al4V, probably due to the increased interfacial bonding, mechanical interlocking, and stress relief by the incorporation of NDP into DLC to form NDP/DLC composite films.