Deposition and mechanical property evaluation of amorphous silicon-containing diamond-like carbon (Si-DLC) coatings on steel

Amorphous silicon-containing diamond-like carbon (Si-DLC) coatings were deposited by Ar⁺ ion beam-assisted physical vapor deposition of tetraphenyl-tetramethyl-trisiloxane (704 Dow Corning diffusion pump oil). The steel substrates studied included AISI 4130, 17-7 PH, 440-C, and 4340 (bare and nitride-precoated) specimens. DLC coating thicknesses ranged from 1.8 to 4.31 μm. Deposition rates increased with increasing beam current density and varied with the steel substrate composition. Nanoindentation measurements of the hardness and elastic modulus at two different depths yielded values of 9-10 GPa and 99-128 GPa, respectively. Film cohesion and adhesion failure loads increased with increasing underlying layer hardness, chromium content in the substrate, or the presence of a titanium nitride precoat. The friction coefficient of a diamond stylus against the coating surface decreased and wear resistance increased with nitride precoating.     

Nanoindentation of diamond,graphite and fullerene films

The recently developed method of nanoindentation is applied to various forms of carbon materials with different mechanical properties, namely diamond, graphite and fullerite films. A diamond indenter was used and its actual shape determined by scanning force microscopy with a calibration grid. Nanoindentation performed on different surfaces of synthetic diamond turned out to be completely elastic with no plastic contributions. From the slope of the force–depth curve the Young's modulus as well as the hardness were obtained reflecting a very large hardness of 95 GPa and 117 GPa for the {100} and {111} crystal surfaces, respectively. Investigation of a layered material such as highly oriented pyrolytic graphite again showed elastic deformation for small indentation depths but as the load increased, the induced stress became sufficient to break the layers after which again an elastic deformation occurred. The Young’s modulus was calculated to be 10.5 GPa for indentation in a direction perpendicular to the layers. Plastic deformation of a thin fullerite film during the indentation process takes place in the softer material of a molecular crystalline solid formed by C₆₀ molecules. The hardness values of 0.24 GPa and 0.21 GPa for these films grown by layer epitaxy and island growth on mica and glass, respectively, vary with the morphology of the C₆₀ films. In addition to the experimental work, molecular dynamics simulations of the indentation process have been performed to see how the tip–crystal interaction turns into an elastic deformation of atomic layers, the creation of defects and nanocracks. The simulations are performed for both graphite and diamond but, because of computing power limitations, for indentation depths an order of magnitude smaller than the experiment and over indentation times several orders of magnitude smaller. The simulations capture the main experimental features of the nanoindentation process showing the elastic deformation that takes place in both materials. However, if the speed of indentation is increased, the simulations indicate that permanent displacements of atoms are possible and permanent deformation of the material takes place.     

Nanoindentation with spherical tips of single crystals of YBCO textured by the Bridgman technique: Determination of indentation stress–strain curves

The mechanical properties of superconductor ceramics are of interest in the manufacture of superconducting devices. The current trend is to produce smaller devices (using, e.g., thin films), and the correct characterization of small volumes of material is critical. Nanoindentation is used to assess mechanical parameters, and several studies determine hardness and Young's modulus by sharp indentation. However, studies on the elasto-plastic transition with spherical indentation are scare. Here we used, spherical diamond tip indenter experiments to explore the elasto-plastic transition and to measure the yield strength of the orthorhombic phase of YBa₂Cu₃O_7?δ (YBCO or Y-123) at room temperature. The study was carried out for a range of monodomains on the (1 0 1)-plane for Bridgman samples. Inspection of the load–unload curves for penetration depths lower than 200 nm allows for observation of the elasto-plastic transitions. Focused ion beam (FIB) trenches showed no cracking due to the indentation, although oxygenation cracks were apparent. The mean pressure for the onset of elasto-plastic deformation is 3.5 GPa, and the elastic modulus, E, calculated using the Hertzian equations is 123.5 ± 3.4 GPa.     

Diamond-like carbon overcoat for TFMH using filtered cathodic arc system with Ar-assisted arc discharge

The deposition system described for sub-30 Å and thicker carbon (ta-C) overcoat that includes two RF ion beam guns and Filtered Cathodic Arc (FCA) module mounted on a single vacuum chamber. The system is capable of flattening the Thin Film Magnetic Heads (TFMH) surface by ion beam etching; smoothing scratches, trenches, steps on boundaries of different materials, and enhancing the adhesion by ion assisted ion beam sputtering. It provides the highly controllable deposition of carbon using an FCA module with Ar-assisted arc discharge. Low-level particulates are achieved on the deposited film surface (< 5/cm² ). It was shown that crucial impact on filtering the particles with size < 1 μm has the electrostatic field distribution across the plasma guide that can be controlled by duct bias. Mechanical and electrical properties, optical and Raman spectra of ta-C films were investigated as a function of Ar flow in the arc discharge area. At Ar flow rates 0–12 sccm, stress of the films was varied in a range 2.9–7.5 GPa while hardness and Young's Modulus stayed in ranges of 45–60 GPa, and 230–300 GPa, respectively. Density of the obtained films was greater than 2.8 g/cm³. Optical absorption and electrical conductivity of ta-C films showed a significant rise while stress came down with Ar flow. Raman G-peak was higher for ta-C films with lower stress and shifted to lower energy. The low stress films versus high stress films showed a few orders reduced electrical resistance and anisotropy of specific resistance with respect to substrate plane: ρ_⊥ ≫ ρ_∥. In situ ellipsometric control of growing film thickness was implemented on the system. Run-to-run standard deviation was less than 1 Å for 20–25 Å thick films. High corrosion resistance of FCA coatings was exhibited. The impact of Ar gas–carbon plasma interaction on the deposition conditions and microstructure of ta-C films was discussed.     

Mechanical properties of different types of diamond

The mechanical properties of different types of diamond (synthetic diamonds with different nitrogen impurity concentrations 0.3 and 200 ppm) have been investigated by sclerometry hardness and wear resistance measurements. Diamond (111) and (100) faces in the 〈100〉 and 〈110〉 directions were tested. It was found the synthetic diamond with nitrogen impurity concentration of 0.3 ppm exceeds other diamond types with respect to hardness and wear resistance, and reveals anisotropy of the mechanical properties, different from other diamond types. The hardness measured on the (111) face for synthetic diamond was 175±5 GPa for 0.3 ppm of nitrogen impurities and 151±5 GPa for 200 ppm of nitrogen impurities. The hardness measurements were performed using an ultrahard fullerite indenter exceeding diamond in hardness and the diamond faces were deformed plastically under scratching conditions.     

Tribological behaviors of aligned carbon nanotube/fullerene‐epoxy nanocomposites

The tribological properties of aligned CNT/fullerene‐epoxy nanocomposites were studied by nanoscratch, nanowear, and nano‐indentation tests. Compared with neat epoxy, aligned CNT/fullerene‐epoxy nanocomposites showed lower friction coefficient in scratch tests, a reduction of 38.1 and 26.2%, respectively. In addition, the aligned CNT‐epoxy composite showed better wear resistance and its hardness and Young's modulus increased by 29.4 and 16.8%, respectively. In contrast, for a fullerene‐epoxy nanocomposite with 10 wt% fullerenes, the hardness decreased by 50% and the Young's modulus decreased by more than 60% when compared with the neat epoxy. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Structure and properties of ta-C films prepared by vacuum cathodic arc with an unbalanced external electromagnetic field

ta-C thin films were deposited by vacuum cathodic arc technology with an unbalanced external electromagnetic field. The intensity of the magnetic field was adjusted by changing coil current and its effect on structure and properties of ta-C films was studied. FEM simulation results showed that as coil currents increased, the transverse, normal magnetic field and the magnetic intensity from arc cathode to substrates holder gradually increased. The UBM system increases the magnetic field intensity of the entire vacuum chamber by mainly improving the normal magnetic flux density near the arc cathode. The surface morphology, microstructure, tribo-mechanical properties of ta-C films were analyzed by SEM, Raman spectrometer, XPS, 3D surface profiler, Nano-indentation and ball-on-disk tribometer. Results showed that as the coil current increased, the average target voltage increased from 21.14 V to 25.97 V and target power rose from 845 W to 1043 W. Changes of magnetic field affected the plasma in vacuum chamber and the number of ions reaching the substrates, which had significant influences on film structure and properties. With a proper magnetic field (at coil current of 4A), ta-C films perform the highest hardness of 58.8 GPa, and the highest sp³ content of about 71% with the lowest ratio of I_D/I_G (0.38). During the wear process, the transfer layer was formed by oxidation and graphitization of contact surfaces. High hardness provided good support for transfer film, which leads to a low wear rate.     

Friction and wear at nanometer scale: a comparative study of hard carbon films

Tribological properties of nanostructured carbon (ns-C) and tetrahedral amorphous carbon (ta-C) thin films were investigated by friction force microscopy. It was found that the ns-C films have a smaller friction coefficient than ta-C films for relative humidity greater than 30%. In particular, at 40% of humidity, ns-C films have lower friction coefficient (0.11±0.02) than the ta-C films (0.13±0.02), which can be attributed to both the presence of closed graphite nanoparticles and the passivation of the dangling bonds at the ns-C surface. The friction coefficient did not vary as a function of the tip scanning velocity for both films. The nanoscale wear was studied in a very low force regime, in the range of nanonewton, using an atomic force microscope (AFM) with a Si₃N₄ tip and with forces in the range of micronewton with the AFM equipped with a stainless still cantilever and a diamond tip. The ns-C provides better wear resistance compared to ta-C films in the range of forces studied. The sp²-rich ta-C surface layer was easily scratched during the wear test in contrast to the ns-C films. The wear in ta-C in the low forces regime is attributed to the presence of this low density layer at the surface of the film due to subplantation of energetic ions during deposition while the better resistance to wear of ns-C films is attributed to its highly elastic nature.     

Mechanical properties of alternating high-low sp3 content thick non-hydrogenated diamond-like amorphous carbon films

Thick non-hydrogenated DLC films (∼ 1μm), consisting of alternating sub-layers of high/low sp³ content, were deposited onto n++ Si substrates using the filtered cathodic vacuum arc method. These films were systematically studied to determine how the changes in composition of the sub-layers would affect the mechanical properties such as intrinsic stress, hardness, friction coefficient, wear rate and surface roughness. Variations of both the ratio of hard to soft layers (from 1:3 to 3:1) and thickness of individual layers (from 12.5nm to 75nm) were studied in detail. The stress of the film was sufficiently lowered (7.8GPa–2.4GPa) by the multilayer approach. The results indicated that although hardness has some correlations with the internal composition of the film, the reduced Young's modulus is largely not affected. Wear and frictional characterizations also showed that the multilayer was a good candidate for many mechanical applications.     

Nitrogenated carbon films deposited using filtered cathodic arc

Nitrogenated carbon films were deposited on various substrates using filtered cathodic arc. Non-uniformity of the film thickness was less than 5% over a 15 cm diameter area. Mechanical, optical (refraction index, extinction coefficient versus wavelength) and electrical properties were investigated as a function of nitrogen flow rate. Deposited coatings demonstrated high hardness of 40–65 GPa, Young's modulus 200–285 GPa, excellent elastic recovery, high critical pressure for scratch formation, and surface smoothness. While the hardness showed a relatively small decrease with nitrogen flow increase, the stress decrease was more significant (8–3.8 GPa). Extremely low wear rates were observed, even at high contact pressures, and no substantial debris was detected indicating that carbon is oxidized during wear. Clear correlation was found between transparency, electrical resistivity and stress of the films. Transparency and resistivity showed a significant rise with an increase of stress. An explanation of the film properties is based on the assumption that the basic characteristics of the deposited films were determined by the relative proportion of two three dimensional complementary type of bonds; the tetrahedral sp³ bonds leading to stiff networks, and the trigonal sp² arrangments close to fullerene-like, or nanotube-like, structures.     

Nanoindentation study of microplasma sprayed hydroxyapatite coating

The microplasma sprayed (MPS) hydroxyapatite (HAP) coating on surgical grade SS316L, is an emerging material for bio-ceramic based implant application involving higher reliability. For this purpose, a 200 μm thick MPS-HAP coating was developed on SS316L substrate and characterized by XRD, SEM and FE-SEM techniques. The local mechanical properties of the coating, e.g. nano-hardness and Young's modulus were evaluated by nanoindentation technique carried out with a Berkovich indenter at various depths in the range of about 170–3000 nm on a polished top surface. The characteristic values of nano-hardness (1.5–5 GPa) and Young's modulus (∼60–100 GPa) obtained through the application of Weibull statistics to the experimentally measured data revealed a strong indentation size effect (ISE). Attempts were made to explain the genesis of ISE on the basis of some existing and some new concepts.     

Indentation measurements using a dynamic mechanical analyzer

A dynamic mechanical analyzer equipped with a diamond indenter tip was used to measure the elastic modulus of polymeric coatings as well as various bulk materials. A fabricated indenter probe was used to indent bulk samples of aluminum and fused quartz, as well as gelatin and polystyrene films in order to compare the micron-level indentation measurements with sub-micron (nanoindentation) techniques. The measured moduli were in agreement for ductile materials and thick films (>20 μm), but limited displacement resolution, material cracking, and hydrostatic pressure effects led to diverging values for thinner coatings and more brittle materials.     

Mechanical properties of free-standing graphene oxide

The mechanical properties of free-standing graphene oxide (GO) films were investigated using nanoindentation on a dynamic contact module (DCM) system. The Young's modulus, stiffness, and ultimate strength of thin films were evaluated. Nanoindentation measurements were combined with the DCM to evaluate the mechanical properties of thin films and to predict the crack length and critical energy. Electrophoretically deposited GO film, 50 ~ 60 nm in thickness, was found to have a Young's modulus of 695 ± 53 ~ 697 ± 15 GPa. The critical energy values for 50- and 60-nm-thick films were 0.142 ~ 0.201 and 0.479 ~ 0.596 J/m², respectively. Nanoindentation combined with the DCM can thus be used to obtain the mechanical properties and critical energy of thin films.     

Evaluation of mechanical properties and hydrophobicity of room-temperature,moisture-curable polysilazane coatings

Polysilazane coatings have a broad need in real-life applications, which require low processing or working temperature. In this work, five commercially available polysilazanes have been spin-coated on polycarbonate substrates and cured in ambient environment and temperature to obtain transparent, crack-free, and dense films. The degree of crosslinking is found to have a significant impact on the hardness and Young's modulus of the polysilazane films but has a minor influence on the film thickness and hydrophobicity. Among all five polysilazane coatings, the inorganic perhydropolysilazane-based coating exhibits the largest hardness (2.05 ± 0.01 GPa) and Young's modulus (10.76 ± 0.03 GPa) after 7 days of curing, while the polyorganosilazane-derived films exhibit higher hydrophobicity. The molecular structure of polysilazanes plays a key role in mechanical properties and hydrophobicity of the associated films, as well as the adhesion of coatings to substrates, providing an intuitive and reliable way for selecting a suitable polysilazane coating material for a specific application.     

Raman scattering,AFM and nanoindentation characterisation of diamond films obtained by hot filament CVD

In this work, structure and mechanical properties of diamond films fabricated by HFCVD on silicon substrates with nanodiamond seeding were investigated. Raman spectroscopy was used to characterise the diamond phase content, crystalline quality and source of stresses in these films. Topography, hardness and Young's modulus were studied by scanning force microscopy (SFM) and nanoindentation methods. It has been ascertained that for the diamond films grown on silicon substrates with nanodiamond seeding hardness and crystalline quality is higher than for films on scratched silicon. The diamond films demonstrate Raman upshift with respect to natural diamond, indicating presence of internal compressive stress. It was shown that various types of impurities and defects induce compressive stresses in the diamond grains.     

Structure and properties of hard carbon films depending on heat treatment temperatures via polymer precursor

Phenylcarbyne polymer films were coated on silicon substrates and heat treated in 1 atm pressure of argon at various temperatures. The structural changes occurring during the heat treatment process of the polymer were investigated by Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The Raman and FTIR spectra features of the polymer showed a dependence on the heat treatment temperatures. At low temperatures (below 400°C), the Raman and IR spectra of the polymer were similar to those of the original polymer. The hardness and Young's modulus of the polymer films were below 1 and 50 GPa, respectively. With increasing temperature (above 400°C), thermal decomposition of the polymer occurred, resulting in structural changes of the polymer from soft amorphous hydrocarbon (400–600°C) phases to hard carbon phases (above 600°C). The hardness and Young's modulus increased from 1.5 and 65 GPa at 600°C to 9 and 120 GPa at 1000°C, respectively. It is assumed that the hard carbon film converted from the polymer might contain sp² and sp³ carbon phases; high temperature of heat treatment resulted in increasing sp² (glassy) carbon phase in the films.     

Improved mechanical properties of SnO2:F thin film by structural modification

This study reports the improvement in the mechanical properties of SnO₂:F (FTO) thin films through the modification of the structure and surface morphology. The FTO thin films are deposited on glass substrates by the atmospheric pressure chemical vapor deposition method on an industrial production line. Both the average grain size and the surface roughness were progressively increased by increasing the flow rate of metal organic monobutyltin trichloride (MBTC). The hardness and Young's modulus of the FTO films increased from 9.01 GPa to 15.08 GPa, and from 125.24 GPa to 206.93 GPa, respectively, according to the nanoindenter results. Post-heat treatment at 650 °C for 10 min resulted in a further increase in the hardness and Young's modulus, reaching maximum values of ~15.89 GPa and ~235.9 GPa, respectively. The enhancement in mechanical properties can be attributed to the reduced grain boundaries and the improved structural densification.     

Heat treatment of tetrahedral amorphous carbon films grown by filtered cathodic vacuum-arc technique

Tetrahedral amorphous carbon (ta-C) is a potential low-cost substitute for diamond in certain applications, but little is known of the temperature range over which its desirable properties are retained. The thermal stability of tetrahedral amorphous carbon (ta-C) films has been investigated by heat treatment of the films at temperatures from room temperature to 450°C in high vacuum, low vacuum and oxygen ambient. It was found that heat treatment in oxygen ambient leads to a much more prominent variation in film thickness, stress and hardness than in both low and high vacuum. Raman studies also show an increase of the G-band frequency to higher values, an increase of the integrated intensity ratio and a narrowing of the G bands for films annealed in oxygen ambient with increasing temperature. By contrast, ta-C films exhibit a high resistance to degradation during treatment in low and high vacuum. They sustain their structure, thickness, stress and hardness for temperatures up to 400°C.     

Structure and properties of cellulose nanocomposite films containing melamine formaldehyde

Films of high Young's modulus and low density are of interest for application as loudspeaker membranes. In the present study nanocomposite films were prepared from microfibrillated cellulose (MFC) and from MFC in combination with melamine formaldehyde (MF). The prepared materials were studied with respect to structure as well as physical and mechanical properties. Studies in SEM and calculation of porosity showed that these materials have a dense paper‐like structure. The moisture sorption isotherms were measured and showed that moisture content decreased in the presence of MF. Mechanical properties were studied by dynamical mechanical thermal measurements as well as by tensile tests. Cellulose films showed an average Young's modulus of 14 GPa while the nanocomposites showed an average Young's modulus as high as 16.6 GPa and average tensile strength as high as 142 MPa. By controlling composition and structure, the range of properties of these materials can extend the property range available for existing materials. The combination of comparatively high mechanical damping and high sound propagation velocity is of technical interest. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007