The influence of the surface texture of hydrogen-free tetrahedral amorphous carbon films on their wear performance

Hydrogen-free and predominantly tetrahedrally bonded amorphous carbon thin films (ta-C) are excellent coatings to protect surfaces from wear due to their low coefficient of friction and high hardness. Since these coatings may be several times harder than common engineering materials counterpart wear can be significant. Therefore the surface texture of the ta-C coating is critical to wear applications. While the surface roughness is an important factor, the paper shows that other surface texture parameters have to be considered as well to predict the wear performance of the coating. Wear data are compared of as deposited, polished and brushed ta-C coatings. The results show that typically referenced average values for the surface roughness such as R_a and R_z may prove insufficient to reliably predict the wear behavior of the coating. Additional parameters describing the surface texture such as the “Skewness” (R_sk) and “Kurtosis” (R_ku) can provide relevant information. For example, a brushed ta-C surface with an average roughness of R_a = 31 nm showed a tenfold improved wear performance over a polished ta-C surface with an average roughness of R_a = 10 nm. This phenomenon is explained by analyzing the R_sk and R_ku data, which prove to more closely capture the post-treatment specific changes to the surface texture of the coatings.     

Synthesis and mechanical wear studies of ultra smooth nanostructured diamond (USND) coatings deposited by microwave plasma chemical vapor deposition with He/H2/CH4/N2 mixtures

Ultra smooth nanostructured diamond (USND) coatings were deposited by microwave plasma chemical vapor deposition (MPCVD) technique using He/H₂/CH₄/N₂ gas mixture. The RMS surface roughness as low as 4 nm (2 micron square area) and grain size of 5–6 nm diamond coatings were achieved on medical grade titanium alloy. Previously it was demonstrated that the C₂ species in the plasma is responsible for the production of nanocrystalline diamond coatings in the Ar/H₂/CH₄ gas mixture. In this work we have found that CN species is responsible for the production of USND coatings in He/H₂/CH₄/N₂ plasma. It was found that diamond coatings deposited with higher CN species concentration (normalized by Balmer H_α line) in the plasma produced smoother and highly nanostructured diamond coatings. The correlation between CN/H_α ratios with the coating roughness and grain size were also confirmed with different set of gas flows/ plasma parameters. It is suggested that the presence of CN species could be responsible for producing nanocrystallinity in the growth of USND coatings using He/H₂/CH₄/N₂ gas mixture. The RMS roughness of 4 nm and grain size of 5–6 nm were calculated from the deposited diamond coatings using the gas mixture which produced the highest CN/H_α species in the plasma. Wear tests were performed on the OrthoPOD®, a six station pin-on-disk apparatus with ultra-high molecular weight polyethylene (UHMWPE) pins articulating on USND disks and CoCrMo alloy disk. Wear of the UHMWPE was found to be lower for the polyethylene on USND than that of polyethylene on CoCrMo alloy.     

A new elegant technique for polishing CVD diamond films

It is well known that the columnar growth nature of CVD diamond results in a very rough growth surface and the surface roughness steeply increases with film thickness, especially for thick CVD diamond films. In this paper, we report the successful implementation of a new elegant technique for polishing thick polycrystalline CVD diamond films at high polishing rate of up to 10 μm/h. This technique involves polishing the as-grown polycrystalline diamond films with another thick as-grown polycrystalline diamond film, which acts as a polishing abrasive. Two types of diamond films were prepared using microwave plasma CVD and then polished for 2 h using the new polishing technique. A stylus profilometer, scanning electron microscopy and Fourier transform infrared spectroscopy were used to measure the surface roughness, characterize morphology and optical transmission of the samples before and after polishing, respectively. By polishing, thickness of 20–30 μm was removed from the top surface, and the mean surface roughness R_a of the films reduced significantly, e.g. for one film R_a reduced initially from 5.2 to 1.35 μm and the other from 3.2 to 0.55 μm. The principal advantages of this new polishing technique are simplicity, flexibility and time saving. This simple method can serve as ‘rough chipping’ to quickly remove the rough top surface and then combine with conventional polishing methods for precision machining to further reduce the surface roughness to a specific desired degree.     

Deposition and structural analyses of molybdenum-disulfide (MoS2)–amorphous hydrogenated carbon (a-C:H) composite coatings

In this study we developed composite coatings consisting of amorphous hydrogenated carbon (a-C:H) and molybdenum-disulfide (MoS₂), and clarified their microstructure. In addition, we interpreted the tribological properties of the composite coatings in the viewpoint of a deposition-induced microstructural modification. The coatings were produced by the hybrid deposition technique of RF-generated methane and argon plasma and DC magnetron co-sputtering of MoS₂ target. The deposition parameter investigated in this study was methane flow rate. Structural analyses were performed using a transmission electron microscope (TEM) and an atomic force microscope (AFM). Friction tests were conducted using a ball-on-disk type tribometer. From an electron micrograph, it was confirmed that nano-clusters were embedded into an amorphous carbon host matrix. Surface roughness of the composite coating was ～ 0.25 nm in R_a compared to 5.0 nm in R_a of sputtered MoS₂. The concentration measurements were performed, and the results show that the sulfur and molybdenum concentration ratio, [S]/[Mo], is ～ 0.9, which indicates that the amount of sulfur was reduced due to the discharged plasma. In friction tests, composite coatings showed high friction in a vacuum condition. It was considered that lubricant MoS₂ lamellar structures showing super-low friction in a vacuum condition during friction could not be formed between ball and coating during friction because of the lack of sulfur in embedded clusters.     

Tribological properties of DLC films deposited on steel substrate with various surface roughness

Tribological properties of diamond-like carbon (DLC) films in water were investigated concerning with the influence of surface roughness and various mating materials. The DLC films were deposited by pulsed-bias CVD method on AISI630 stainless steel. The substrate roughness (R_a) is in the range of 1.4–740 nm. AISI 440C, AISI 304 stainless steel and brass balls were used as a mating ball. The friction coefficients of DLC films against with AISI 440C stainless steel ball indicated under 0.1 irrespective of the roughness. The film having smooth surface (R_a=1.4 nm) had severe damage at a load of 9.4 N. However, the film having rough surface (R_a=263 nm) had no damage at the same load. The specific wear rate of the steel ball increased with increase of roughness of the surface. In the case of AISI 304 stainless steel ball, the specific wear rate of the ball showed similar tendency. The friction with brass ball showed relatively high friction coefficient in the range of 0.12–0.25. However, the damage on the films could not be observed after friction test. It is considered that the roughness of the surface is important factor for the rupture of the film in water environment.     

Machining behaviour of silicon nitride tools coated with micro-, submicro- and nanometric HFCVD diamond crystallite sizes

Very smooth CVD diamond films are used as direct coatings on Si₃N₄ tool substrates. By adjusting deposition parameters, namely Ar/H₂ and CH₄/H₂ gas ratios, and substrate temperature, nano- (27 nm) and submicrometric (43 nm) crystallite sized grades were produced in a hot filament reactor. Also, a conventional 5 and 12 μm micrometric grain size types were produced for comparison. Normalized coated inserts were tested for dry turning of WC–25 wt.% Co hardmetal. All the CVD diamond grades endured the hardmetal turning showing slight cratering, having the flank wear as the main wear mode. Their turning performance was distinct, as a consequence of morphology and surface roughness characteristics. Among all the tested tools, the more even surface and the submicrometric grade presented the best behaviour regarding cutting forces, tool wear and workpiece surface finishing. For this coating, the depth-of-cut force attained the lowest value, 150 N, the best combination of wear types (KM = 30 μm, KT = 2 μm and VB = 110 μm) and workpiece surface finishing (Ra = 0.2 μm).     

Optical characterization of surface roughness of diamond by spectroscopic ellipsometry

Vacuum ultraviolet spectroscopic ellipsometry (SE) was performed on high-temperature and high-pressure (HPHT) synthesized Ib diamond samples with different polishing grades of different surface roughness, R_a [nm], which was measured by atomic force scanning microscopy (AFM). Observations showed that SE spectra systematically changed as a function of surface roughness. From this experimental result, we estimated the ideal dielectric function (DF) of diamond with a flat surface. Using this estimated DF, the optical thickness of a roughness layer was evaluated only from the SE data. It was shown that SE is an effective means of evaluating the thickness of a roughness layer and also the degree of surface modification without damaging the diamond surface, unlike the tip scanning of AFM measurements.     

Enhanced performance of HFCVD nanocrystalline diamond self-mated tribosystems by plasma pretreatments on silicon nitride substrates

Nanocrystalline diamond (NCD) coatings were grown by the hot-filament chemical vapour deposition (HFCVD) method on hydrogen plasma pretreated silicon nitride (Si₃N₄) substrates. The friction and wear behaviour of self-mated NCD films, submitted to unlubricated sliding and high applied loads (up to 90 N), was assessed using an oscillating ball-on-flat configuration in ambient atmosphere. The reciprocating tests revealed an initially high friction coefficient peak, associated to the starting surface roughness of NCD coatings (R_q = 50 nm). Subsequently, a steady-state regime with low friction coefficient values (0.01–0.04) sets in, related to a smoother (R_q = 17 nm) tribologically modified surface. A polishing wear mechanism governing the material loss was responsible for mild wear coefficients (k  10^− 7 mm³ N^− 1 m^− 1). The hydrogen etching procedure notably increased the film adhesion with respect to untreated surfaces as demonstrated by the high threshold loads (60 N; 3.5 GPa) prior to film delamination.     

Wettability studies of reactive brazing alloys on CVD diamond plates

Wettability of both the diamond and the insert surfaces by the filler metal in CVD diamond brazed-on cutting tools is a key condition for good brazing strength. The brazing process of CVD diamond thick plates still has to be improved, namely on the influence of the brazing alloy composition and of the substrate surface finishing quality in wettability. In this study, contact angle measurements were performed in a dedicated high vacuum furnace coupled with a video recording system. Diamond films with different thickness (75<t<300 μm), and thus having distinct grain sizes and roughness, were grown with fixed conditions by the MPCVD technique on Si substrates and chemically detached for wettability experiments. Roughness parameters were evaluated by profilometry and AFM, which was used to observe the grown diamond surfaces of the self-standing films. The reactive Ag–Cu–Ti brazing system was investigated. Results showed a very good wettability in the temperature range 800–850°C, namely for the diamond surface where a minimal contact angle of 10° was reached. A Ti-rich thin reaction layer (0.5–0.8 μm) was detected at the drop side of the substrate/brazing alloy interface in both substrate materials, proving the affinity of Ti to carbon. The influence of the diamond roughness on the contact angle θ_R is notable, obeying a linear dependence of the type cosθ_R=cosθ₀+k cosθ₀·(R_a/G)², where R_a and G, the grain size, are related to asperity height and width, respectively. This relationship is based on the well-known Wenzel equation that correlates the real contact angle to the surface area increasing with roughness.     

Biomimetic Zirconia with Cactus-Inspired Meso-Scale Spikes and Nano-Trabeculae for Enhanced Bone Integration

Biomimetic design provides novel opportunities for enhancing and functionalizing biomaterials. Here we created a zirconia surface with cactus-inspired meso-scale spikes and bone-inspired nano-scale trabecular architecture and examined its biological activity in bone generation and integration. Crisscrossing laser etching successfully engraved 60 μm wide, cactus-inspired spikes on yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) with 200–300 nm trabecular bone-inspired interwoven structures on the entire surface. The height of the spikes was varied from 20 to 80 μm for optimization. Average roughness (Sa) increased from 0.10 μm (polished smooth surface) to 18.14 μm (80 μm-high spikes), while the surface area increased by up to 4.43 times. The measured dimensions of the spikes almost perfectly correlated with their estimated dimensions (R² = 0.998). The dimensional error of forming the architecture was 1% as a coefficient of variation. Bone marrow-derived osteoblasts were cultured on a polished surface and on meso- and nano-scale hybrid textured surfaces with different spike heights. The osteoblastic differentiation was significantly promoted on the hybrid-textured surfaces compared with the polished surface, and among them the hybrid-textured surface with 40 μm-high spikes showed unparalleled performance. In vivo bone-implant integration also peaked when the hybrid-textured surface had 40 μm-high spikes. The relationships between the spike height and measures of osteoblast differentiation and the strength of bone and implant integration were non-linear. The controllable creation of meso- and nano-scale hybrid biomimetic surfaces established in this study may provide a novel technological platform and design strategy for future development of biomaterial surfaces to improve bone integration and regeneration.     

Three-dimensional diamond growth film simulations: correlations between nucleation and surface parameters

The development of a three-dimensional simulation of the diamond nucleation and growth presented in a previous paper has been used in this study to determine surface parameters such as the roughness, R_a, and porosity (filling factor Q) of diamond film, according to the crystal size (via the radius R) and the nucleation density N. Evolutions of these surface parameters are compared to values obtained by a statistical treatment (Poisson's law) based on the random nucleation and subsequent growth of hemispheres. In particular, we study the roughness variations with the parameter λ=πR²N, which seems to be the key variable in the case of coatings whose nucleation and growth are in agreement with the Volmer–Weber mechanism. From these results, it is possible to calculate some surface parameters that are useful for tribological and optical applications and whose evolutions with synthesis time have not been reported to our knowledge.     

Effect of the surface roughness of sulfuric acid-anodized aluminum mold on the interfacial crystallization behavior of isotactic polypropylene

The influence of the surface topography of aluminum alloy (Al) on the heterogeneous nucleation of isotactic polypropylene (iPP) at the iPP/Al interface has been investigated using a polarized optical microscope (POM) with a hot stage. Different textures of the Al surface were prepared by electrochemical processes, including polishing and anodizing, and utilized to induce interfacial nucleation upon supercooling. This process enabled the topological features of the aluminum surface to be controlled without altering their chemical composition by such a procedure. The pretreated surfaces were investigated by scanning electron microscopy and quantitatively characterized by a surface texture instrument in terms of RMS roughness (R _a). The Al surface with a higher surface roughness induced more nuclei of iPP and led to a transcrystalline layer (TCL) in the interfacial region upon supercooling over the temperature range 128°C < T _c < 154°C. Based on the theory of heterogeneous nucleation, it was found that the induction time correlates well with the nucleation rate in determining the interfacial free energy difference function Δσ of iPP. The ratio of Δσ at the interface to that in the bulk matrix (ΔσTCL/Δσ _bulk) for the polished surface (R _a = 0.38 μm) is 4.45, implying that transcrystallization growth is unfavorable from a thermodynamic point of view. On the other hand, the Δσ _TCL/Δσ _bulk ratio decreases as the current density for anodizing increases, indicating that transcrystallization growth becomes favorable. The induction times and nucleation rates were also measured to characterize quantitatively the nucleating ability of various Al surfaces. The oxide porosity was filled in when sealing treatment by hydration was carried out. This resulted in Δσ _TCL/Δσ _bulk being slightly higher as the surface roughness decreased.     

Effect of surface roughness and surface modification of indium tin oxide electrode on its potential response to tryptophan

The effect of surface modification of indium tin oxide (ITO) electrode on its potential response to tryptophan was investigated for ITO substrates with different surface roughness. It was found that a small difference in surface roughness, between ∼1 and ∼2 nm of R_a evaluated by atomic force microscopy, affects the rest potential of ITO electrode in the electrolyte. A slight difference in In:Sn ratio at the near surface of the ITO substrates, measured by angle-resolved X-ray photoelectron spectrometry and Auger electron spectroscopy is remarkable, and considered to relate with surface roughness. Interestingly, successive modification of the ITO surface with aminopropylsilane and disuccinimidyl suberate, of which essentiality to the potential response to indole compounds we previously reported, improved the stability of the rest potential and enabled the electrodes to respond to tryptophan in case of specimens with R_a values ranging between ∼2 and ∼3 nm but not for those with R_a of ∼1 nm. It was suggested that there are optimum values of effective work function of ITO for specific potential response to tryptophan, which can be obtained by the successive modification of ITO surface.     

Fabrication of diamond MISFET with micron-sized gate length on boron-doped (111) surface

A hydrogenated surface conductive layer of B-doped diamond on (111) was employed to fabricate a metal insulator semiconductor field effect transistor (MISFET) using a CaF₂ and Cu stacked gate. The carrier mobility and concentration of the hydrogenated surface on (111) before FET processing were 35 cm²/V s and 10¹³/cm², respectively, when bulk carrier concentration and film thickness of the B-doped underlaying diamond was 3 × 10¹⁵/cm³ and 1.5 μm, respectively. The DC characteristics of the gate with 1.1 μm length and 50 μm width showed that the maximum measured drain current was 240 mA/mm at − 3.0 V gate voltage, and the maximum transconductance (g_m) was 70 mS/mm. The cut-off frequency of 4 GHz was obtained, which is one of the best values for the RF characteristics of a diamond homoepitaxial (111) MISFET.     

Influence of acidity level in acetonitrile on Hammett–Zuman type correlations on the reduction of α-hydroxyquinones

In this work the voltammetric study in acetonitrile was carried out of a quinones family containing α-hydroxy group, anilineperezones (APZs; 2-(1,5-dimethyl-4-hexenyl)-3-hydroxy-5-methyl-6-[4′-(R₂-phenyl)amine]-1,4-benzoquinones) as well as their comparison with their methylated derivatives (APZms; 2-(1,5-dimethyl-4-hexenyl)-3-methoxy-5-methyl-6-[4′-(R₂-phenyl)amine]-1,4-benzoquinones) where R₂ is MeO, Me, H, Br and CN. Through a systemic study that modified the type of electron transfer coupled reactions of the two quinoid systems, linear Hammett–Zuman type variations were found, ΔE_pc=E_pc(R₂=X)−E_pc(R₂=H)=ρ_πσ_p+a, with a≠0. Therefore, we suggest that the Hammett–Zuman equation simultaneously considers the substituent effect, not only in the electron transfer but also in chemically coupled reactions. Furthermore, we suggest that the magnitude of a of Hammett–Zuman type correlations shows the presence of chemical reactions coupled to the electron transfer, so that a apparently depends on the substituent effect on this type of reactions.     

Influence of CAD-CAM milling on the flexural strength of Y-TZP dental ceramics

In this work, the influence of milling strategy and cutter wear on the flexural strength of sintered Y-TZP ceramics machined in a CAD-CAM system, was investigated. Pre-sintered Y-TZP blocks were machined with tungsten carbide (WC) milling cutters and divided into three groups: a) samples machined with New Cutting Tools (NCT); b) samples machined with End-of-life cutting tools (ELCT); and c) samples machined and subsequently polished. The samples were machined parallel and perpendicularly to the diameter of pre-sintered Y-TZP blocks aiming to evaluate the effect of the machining orientation on roughness. After cutting, the specimens were sintered at 1530?°C for 2?h and characterized. After sintering, dense Y-TZP samples presenting grain size average of 0.81?±?0.23?μm, hardness of 1205?±?12 HV, K_C of 7.7?±?0.4 MPam^1/2 and flexural strength of 1207?±?199?MPa were obtained. Furthermore, the control roughness (polished surfaces) presented R_a?=?0.058?±?0.011?μm. The surface roughness of the samples was influenced by the machining methodology using NCT mills, with R_a?=?0.386?±?0.149?μm and R_a?=?0.292?±?0.105?μm for samples machined parallel and perpendicularly to the pre-sintered Y-TZP blocks, respectively. The use of ELCT led to a roughness increasing (R_a?=?0.582?±?0.183?μm for samples milled perpendicularly, and R_a?=?0.919?±?0.164?μm for samples cut parallel to the pre-sintered blocks. The flexural strength of the sintered Y-TZP decreases with use of ELCT as consequence of surface roughness increasing, resulting from wear of WC mills, which presented chippings with sizes ranging from 30 to 340?μm in the cutting edge.     

The interrelation between structure and mechanical properties of CNx (0 ≤ x ≤ 0.5) coatings obtained by graphite arc sputtering

Hardness, elastic modulus, internal stresses and friction coefficients were measured in CN_{0 ≤ x ≤ 0.5} coatings (1–3 μm). The dependence of these parameters on nitrogen concentration can be applied in the practical coatings. The structure investigations show that the domain amorphous matrix mixture consists of CN_{x ≤ 0.1} and CN_0.5. Such structure allows understanding the dependence of the CN_{0 ≤ x ≤ 0.5} coatings properties on nitrogen concentration. Through the structure, the coating properties of CN_{0 ≤ x ≤ 0.5}, depend on the nitrogen concentration.     

Tribological properties of NCD coated cemented carbides in contact with wood

Cemented carbides coated with diamond layers are promising materials for mills in the wood industry. Therefore, a study of the tribological properties of the contact between this material and wood is interesting and important. Wood is a specific material with a highly anisotropic structure, which causes roughness of its surface. For example, the friction coefficient (μ) of wood in contact with polished steel coated with a smooth DLC layer, has a relatively high value of μ=0.2–0.5. Cemented carbides, as manufactured for tools for wood milling purposes with roughness R_z=0.66 μm, have been modified with a nanocrystalline diamond film (NCD) using the RF PACVD method. The surface of the NCD coating showed ‘sharp hills’ morphology, but the surface roughness of cemented carbide decreased slightly after coating. The friction was very high (μ=0.7–0.8 at v=1 m/s; F_N=60 N) and it depended on the species of wood. When examining oak and poplar using carbides coated with the thickest NCD layer and a DLC film on top, this value decreased by 30% with respect to that of uncoated carbides. For fibreboard against NCD, the value was increased. Comparing the friction of NCD against wood to its friction against steel, titanium and aluminium alloys, we could see that the roughness of wood was the main factor which determined its tribological behaviour. Prime novelty: the tribological properties of a NCD layer deposited on cemented carbides with wood.     

Zeolites in biomedical application: Zn-exchanged clinoptilolite-rich rock as active carrier for antibiotics in anti-acne topical therapy

A clinoptilolite-rich rock was evaluated as inorganic Zn²⁺ releasing carrier for antibiotic erythromycin. The perspective is its use in the topical treatment of acne, a diffused skin pathology, given the efficacy of zinc-erythromycin combination against resistant Propionibacterium strains. The tested rock is an ash-rich epiclastite collected in Northern–Central part of Sardinia island (Italy). ICP chemical analyses of the bulk rock evidenced a composition compatible with topical applications. A 66 wt.% of clinoptilolite content was determined by means of XRD analysis (reference intensity ratio [RIR] technique). EDS chemical analyses of zeolite crystals were performed on polished thin section. The CEC of the rock is 1.45±0.08 meq/g. Using a specific exchange method, the material was previously Na-conditioned then Zn-conditioned. A substantially complete Zn-form was obtained, as demonstrated by AAS analyses. A back-exchange reaction toward Na-form was performed in the same conditions (65 °C in 1 M NaCl solution): zinc release was fast and almost complete (94%). Zn-conditioned powder was then micronized to achieve a volume/surface ratio suitable for a topical therapy. After micronization, the specific surface area, determined by BET gas adsorption, was 30.2 m²/g, and 92% of the powdered rock was lower than 30 μm in size (measured by a Coulter Counter apparatus); the so-called “volume-surface diameter” was 6.48 μm, compatible with the intended topical application. Zn²⁺ release was measured on micronized rock at 37 °C both in physiologic solution as in 0.05 M KH₂PO₄/Na₂HPO₄ buffer. Also in these conditions, a prompt and significant zinc release was recorded: after 30 min, 68% and 60%, respectively. Erythromycin was charged onto the micronized material using a solvent evaporation method. HPLC determinations showed that 85% of the drug contacted with the carrier was loaded. The simultaneous release of zinc and erythromycin were evaluated in phosphate buffer. Eighty-two percent of the loaded antibiotic was released after 30 min. Zinc exchange is substantially unaffected by the contemporary drug release. The request to file an international patent for this pharmaceutical application has been accepted by the European International Preliminary Examination Office.     

Deposition of diamond film on silicon and quartz substrates located near DC plasma

Deposition of diamond films on to both Si and quartz substrates was succeeded by means of locating the substrate near plasma, and their microstructures were investigated by using SEM and Raman spectroscopy. The plasma was generated by intermittent DC discharge in H₂–CH₄ gas mixture at high gas pressure. The deposition rate of the film was remarkably increased when distance (D) between the substrate and the plasma (discharge electrodes) decreased. When the gas pressure (P_g) was increased from 100 to 250 Torr, the deposition rate was extremely increased and the crystalline quality of the film was improved. The deposition rate, when P_g = 200 Torr and D = 5 mm, was about 2.1 and 1.7 μm/h for Si and quartz substrate, respectively.