Wear Of Diamond-like Carbon Research Articles

Environment-dependent tribochemical reaction and wear mechanisms of Diamond-like carbon: A reactive molecular dynamics study

Diamond-like carbon (DLC) is widely utilized in various fields as a promising solid lubricating material. However, the lubricity and wear behaviors of DLC are highly sensitive to the environment, and the relevant mechanisms are hidden by complex tribochemical reactions at the friction interface. In this study, we performed reactive molecular dynamics (RMD) simulations of DLC to clarify the wear mechanisms in various environments (vacuum, water, and oxygen environments). Two types of tribochemical reaction-induced wear were observed: chemical wear induced by the triboemission of CxHy and CxHyOz compounds and mechanical wear induced by the formation of interfacial C–C bonds. Moreover, the results revealed that the environment affects the tribological behavior of DLC primarily through its impact on the surface chemical state, that is, the quantity and type of surface terminations. In terms of the number of surface terminations, the more surface terminations there are, the more chemical wear and less mechanical wear they cause. In particular, oxygen-containing terminations (e.g., C–OH and C=O) are more resistant than H terminations to interfacial bond formation and mechanical wear. The present work provides important insights into the wear mechanisms of DLC, aiding in the reduction of DLC wear by controlling the environment.

In Vitro and In Vivo Evaluation of Toxicity of Structurally Different Diamond-Like Carbon Wear Debris in Joint Replacements.

Diamond-like carbon (DLC) wear debris, which is often composed of different types of structures, is generated from DLC-modified artificial joints in the human body, and its biocompatibility evaluation is especially important to prevent wear-debris-induced implant failure. Here, RAW 264.7 macrophages (inflammatory-reaction assay) and primary mouse osteoblasts (osteoblastogenesis assay) were employed to investigate the toxicity of DLC wear particles (DWPs) by evaluation of cell viability and morphology, enzyme-linked immunosorbent assays, and quantitative reverse-transcription polymerase chain reaction (PCR). Relevant histopathological analysis of rat joints was also performed in vivo. We found that DWPs with a relatively high sp2/sp3 ratio (graphite-phase tendency) manifested a higher cytotoxicity and significant inhibition of osteoblastogenesis. DWPs with a relatively low sp2/sp3 ratio (diamond-phase tendency) showed good biocompatibility in vivo. The DWPs exhibiting a low sp2/sp3 ratio demonstrated reduced secretion of TNF-α and IL-6, along with increased secretion of TIMP-1, resulting in the downregulation of MMP-2 and MMP-9 and upregulation of interleukin-10 (IL-10), thereby attenuating the inflammatory response. Moreover, coculturing osteoblasts with DWPs exhibiting a low sp2/sp3 ratio resulted in an elevated OPG/RANKL ratio and increased expression of OPG mRNA. Because of the absence of electrostatic repulsion, DWPs with a relatively low sp2/sp3 ratio enhanced bovine serum albumin adsorption, which favored cellular activities. Cytotoxicity assessment of DWPs can help establish an evaluation system for particle-related joint disease and can facilitate the clinical application of DLC-coated prostheses.

Designing hydrogen-free diamond like multilayer carbon coatings for superior mechanical and tribological performance

Diamond like carbon (DLC) coatings are extensively employed for their outstanding mechanical and tribological properties. To overcome the inherent high residual stress, therefore brittleness, DLC coatings with multilayer architecture were developed in the form of stacking alternate hard and soft layers to avoid premature failure under severe loading conditions. The current study was designed to investigate the impact of bilayer thickness (hard & soft) on wear of multilayer DLC particularly at high contact stress (2.0 GPa, 2.7 GPa, 3.0 GPa, 3.4 GPa). Seven DLC multilayer (1:1 bilayer ratio) samples with 1, 2, 5, 10, 20, 40, 80 bilayers were deposited on 440C steel and the overall coating thickness was mainatined at ∼1 µm. Moreover, the bilayer thickness effect was determined on mechanical, scratch adhesion and structural properties. Transmission electron microscope (TEM) was used to visualize discrete hard and soft layers in 80 bilayers (∼6 nm thin layer). G peak suppression and ID/IG increment were observed with reduction in bilayer thickness. Hardness, modulus, elastic strain to failure (H/E), plastic deformation resistance (H3/E2) and residual stresses showed an inverse relation with bilayer thickness. Furthermore, micro scratch adhesion decreases with layer thickness reduction. Only 100 nm and above bilayer thickness samples (1, 2, 5, 10 bilayers) could survive under high contact stress while the other three (20, 40, 80 bilayers) showed brittle failure using pin-on-disc tribometer. Additionally, 10 bilayers (100 nm thickness) produced the minimum wear (∼7.9 ×10−8 mm3/Nm) at 80 N.

Synergistic tribological effect between polyisobutylene succinimide-modified molybdenum oxide nanoparticle and zinc dialkyldithiophosphate for reducing friction and wear of diamond-like carbon coating under boundary lubrication

Organic molybdenum lubricant additive like molybdenum dialkyl dithiocarbamate (MoDTC) can cause wear acceleration of diamond-like carbon (DLC) coating coupled with steel under boundary lubrication, which hinders its industrial application. Therefore, polyisobutylene succinimide (PIBS), an organo molybdenum amide, was adopted to modify molybdenum oxide affording molybdenum polyisobutylene succinimide-molybdenum oxide nanoparticles (MPIBS-MONPs) with potential to prevent the wear acceleration of DLC coating. The thermal stability of MPIBS-MONPs was evaluated by thermogravimetric analysis. Their tribological properties as the additives in di-isooctyl sebacate (DIOS) were evaluated with MoDTC as a control; and their tribomechanism was investigated in relation to their tribochemical reactions and synergistic tribological effect with zinc dialkyldithiophosphate (ZDDP) as well as worn surface characterizations. Findings indicate that MPIBS-MONPs/ZDDP added in DIOS can significantly reduce the friction and wear of DLC coating, being much superior to MoDTC. This is because MPIBS-MONPs and ZDDP jointly take part in tribochemical reactions to form a composite tribofilm that can increase the wear resistance of DLC coating. Namely, the molybdenum amide on MPIBS-MONPs surface can react with ZDDP to form MoS2 film with excellent friction-reducing ability; and MPIBS-MONPs can release molybdenum oxide nanoparticle to form deposited lubrication layer on worn surfaces. The as-formed composite tribofilm consisting of molybdenum oxide nanocrystal, amorphous polyphosphate, and molybdenum disulfide as well as a small amount of Mo2C accounts for the increase in the wear resistance of DLC coating under boundary lubrication.

Evaluation of Wear Measurement with Radioactive Isotopes for DLC Coatings Affected by Abrasive Particles

Diamond-like carbon (DLC) coatings protect engine parts from wear and provide low-friction. Unfortunately, the nature of DLC coatings does not allow progressing wear measurement using conventional methods. Therefore, we applied a radioactive isotope-based wear measurement method (RIC method). A tribometer with oscillating contact and one with sliding contact were used to provide different loading conditions. The RIC method was evaluated for DLC coatings, and the DLC wear was investigated regarding the presence of abrasive particles. The results indicate that an increase in abrasive particle concentration leads to an increase of DLC wear rate and a decrease in usage-time until wear-off.

Stress-dependent adhesion and sliding-induced nanoscale wear of diamond-like carbon studied using in situ TEM nanoindentation

We present the first in situ transmission electron microscope (TEM) study of extended sliding of diamond-like carbon (DLC) on diamond. We show how the tribological properties of amorphous carbon (a-C) reach their limit by exploring the onset of wear for the harsh condition of sliding against diamond in vacuum. A particularly hard, hydrogen-free member of the DLC family, a-C is of wide technological interest, but the mechanisms by which damage occurs during tribological contact are not well understood. Real-time TEM imaging of the nanoscale contact area provides insight into wear mechanisms and damage. We show that at high normal stresses with full sliding contributing to additional shear stress, the initially low adhesion of the a-C-diamond interface rapidly increases at a rate greater than is seen in similar silicon-diamond contact studies. We propose that high contact stresses wear away a relatively low surface energy sp2-rich layer on the outer a-C surface, exposing sp3-rich sub-layers which can form covalent bonds that require more tensile force to be broken, leading to higher adhesion and an acceleration of wear.

Laser Surface Texturing to Realize Micro-grids on DLC Coating: Effect of Marking Speed, Power, and Loop Cycle

In the present study, laser surface texturing was tested with the aim of improving the tribological properties of a diamond-like carbon (DLC) coating. Two experimental campaigns were designed to realize different micro-grids, and to study the effect of marking speed, laser power, and loop cycle. The grid profiles obtained were analyzed using a digital microscope and a laser probe system to measure the track cross section. At the end of the experiments, the authors identified a good-quality track obtained by imposing a marking speed of 300 mm/s, a power of 0.5 W, and one loop cycle. For the identified condition, the presence of defects (such as cracks) on both the coated surface and at the substrate/coating interface was analyzed. Furthermore, the coating nanohardness, adhesion to the substrate, and wear behavior in dry condition were investigated. The results underline how laser texturing can improve the DLC wear behavior (wear tracks lower than 30%) without considerably affecting the other tested coating properties.

Reactive Molecular Dynamics Simulations of Wear and Tribochemical Reactions of Diamond like Carbon Interfaces with Nanoscale Asperities under H2 Gas: Implications for Solid Lubricant Coatings

Diamond like carbon (DLC) is an excellent solid lubricant coating used in various nanoscale applications such as nanoelectromechanical systems and atomic force microscopy. Reducing the wear of DLC ...

Triboemission of hydrocarbon molecules from diamond-like carbon friction interface induces atomic-scale wear.

Understanding atomic-scale wear is crucial to avoid device failure. Atomic-scale wear differs from macroscale wear because chemical reactions and interactions at the friction interface are dominant in atomic-scale tribological behaviors, instead of macroscale properties, such as material strength and hardness. It is particularly challenging to reveal interfacial reactions and atomic-scale wear mechanisms. Here, our operando friction experiments with hydrogenated diamond-like carbon (DLC) in vacuum demonstrate the triboemission of various hydrocarbon molecules from the DLC friction interface, indicating its atomic-scale chemical wear. Furthermore, our reactive molecular dynamics simulations reveal that this triboemission of hydrocarbon molecules induces the atomic-scale mechanical wear of DLC. As the hydrogen concentration in hydrogenated DLC increases, the chemical wear increases while mechanical wear decreases, indicating an opposite effect of hydrogen concentration on chemical and mechanical wear. Consequently, the total wear shows a concave hydrogen concentration dependence, with an optimal hydrogen concentration for wear reduction of around 20%.

Theoretical method for nanoscale wear of diamond-like carbon with frictional heat

The aim of this paper is to develop an efficient theoretical method to analyze the nanoscale wear process of diamond-like carbon considering frictional heat. The wear process is divided into burnishing of outlying asperity phase and atomistic wear phase. The governing equation for atomistic wear rate is derived by stress assisted reaction kinetics. Considering the influence of interfacial temperature, the temperature-dependent activation parameters that significantly determine wear resistance are firstly obtained using Piecewise Linear Method. The study shows that the activation energy linearly increases with the increasing of temperature. This explains how wear resistance can remain stable. It is also found that wear rate will increase as interfacial stress and curvature of protrusion increase. The study provides new insights on nanoscale wear considering temperature effect.

Wear behavior of Diamond-like Carbon Deposited on Ti6Al4V Prepared with Surface Mechanical Attrition Treatment

Surface modification by deposition of hard coatings is a way to overpass the poor wear resistance of some metallic materials and one potential material is the Diamond-Like Carbon (DLC). We investigated the wear behavior, and the adhesion of the DLC deposited on a Ti6Al4V (Ti64) alloy after Surface Mechanical Attrition Treatment (SMAT). The SMAT was applied using 100Cr6 steel balls, and the DLC was deposited through the sputtering method. The nano-hardness was evaluated using a MTS Nano Indenter XP. The adhesion of the DLC was evaluated using a CSM Revetest, and the wear tests was performed in a reciprocating linear tribometer from CSM Instruments. The mean wear rate for the Ti64 was 437x10-6 mm3/N/m against 5x10-6 mm3/N/m for the Ti64+SMAT+DLC. The SMAT reduced the wear rate of the DLC coating, showing that the SMAT might be a viable treatment with promising results regarding the DLC wear resistance.

Tribochemical Wear of Diamond-Like Carbon-Coated Atomic Force Microscope Tips.

Nanoscale wear is a critical issue that limits the performance of tip-based nanomanufacturing and nanometrology processes based on atomic force microscopy (AFM). Yet, a full scientific understanding of nanoscale wear processes remains in its infancy. It is therefore important to quantitatively understand the wear behavior of AFM tips. Tip wear is complex to understand due to adhesive forces and contact stresses that change substantially as the contact geometry evolves due to wear. Here, we present systematic characterization of the wear of commercial Si AFM tips coated with thin diamond-like carbon (DLC) coatings. Wear of DLC was measured as a function of external loading and sliding distance. Transmission electron microscopy imaging, AFM-based adhesion measurements, and tip geometry estimation via inverse imaging were used to assess nanoscale wear and the contact conditions over the course of the wear tests. Gradual wear of DLC with sliding was observed in the experiments, and the tips evolved from initial paraboloidal shapes to flattened geometries. The wear rate is observed to increase with the average contact stress, but does not follow the classical wear law of Archard. A wear model based on the transition state theory, which gives an Arrhenius relationship between wear rate and normal stress, fits the experimental data well for low mean contact stresses (<0.3 GPa), yet it fails to describe the wear at higher stresses. The wear behavior over the full range of stresses is well described by a recently proposed multibond wear model that exhibits a change from Archard-like behavior at high stresses to a transition state theory description at lower stresses.

Multiscale characterisation of 3D surface topography of DLC coated and uncoated surfaces by directional blanket covering (DBC) method

Diamond-like carbon (DLC) coated surfaces exhibit anisotropic and multi-scale characteristics, i.e., their roughness change with both scale and direction. However, most currently used standard surface characterisation parameters and methods work well only with isotropic surfaces at a single scale. This problem can be overcome by variance orientation transform (VOT) and directional blanket covering (DBC) methods. Both methods calculate fractal signatures (FSs) in different directions allowing for detailed measurement of roughness of anisotropic and multiscale surfaces. FS is a set of fractal dimensions (FDs) at individual scales, and FD is a measure of surface roughness. High FD values mean rougher surfaces. Unlike other directional FSs methods, e.g., VOT, the DBC method automatically selects scales of calculations. In this study, the DBC method was used to analyse surface topography images of DLC coated and uncoated bearing steel discs of increasing roughness. Its ability to differentiate between two groups of surfaces is evaluated. The results obtained showed that the DBC method can detect differences in roughness at different scales and directions between the DLC coated and uncoated surfaces. This work could lead to applications of the DBC method in modelling of wear and friction behaviour of DLC coated and uncoated surfaces at different scales.

Evaluation of the Size-Dependent Cytotoxicity of DLC (Diamondlike Carbon) Wear Debris in Arthroplasty Applications.

Patients with DLC (diamond like carbon)-coated artificial joints may be exposed to a wide size range of DLC wear debris (DW). In this study, the cytotoxicity of DW of different size ranges (0-0.22, 0.22-0.65, 0.65-1.0, and 1.0-5.0 μm) was evaluated. The microstructure and physical characteristics of DW were investigated by Raman spectroscopy, transmission electron microscopy (TEM), scanning electron microscope (SEM), and dynamic light scattering (DLS). Macrophages, osteoblasts, and fibroblasts were incubated with DW of different size ranges respectively followed by cytotoxicity evaluations of inflammatory cytokines, alkaline phosphatase (ALP) assays, and related signal protein expression analysis. The results showed that, except for the size range of 0-0.22 μm, DW cytotoxicity showed a size-dependent (0.22-5.0 μm) decrease with increasing size. Within the range of 0.22-5.0 μm, DW of larger size resulted in lessened inflammatory response and enhanced osteoblastogenesis and fibrogenesis, with increased viability of cells (macrophages, osteoblasts, and fibroblasts), better morphology, less release of pro-inflammatory factors and more release of anti-inflammatory factors. The results demonstrated that DW sizes below 0.22 μm had less negative effects on cell adhesion and growth because of the BSA (bovine serum albumin) encapsulation effect. These findings provide valuable knowledge about the comprehensive mechanism of promotion of inflammatory response and inhibition of osteoblastogenesis and fibrogenesis induced by DW. In conclusion, an effective system of biocompatibility evaluation for different sizes of DW was derived.

In vitro cytotoxicity evaluation of nano-carbon particles with different sp2/sp3 ratios

Graphitization occurs during the long-term service of a diamond-like carbon (DLC) modified artificial joint. Then, DLC wear debris, which are carbon particles with different sp2/sp3 ratios and sizes ranging from the nano- to micro-meter scale produced. In this paper, to promote the application of DLC coating for artificial joint modification, the cytotoxicity of DLC debris (nano-carbon particles, NCs) with different sp2/sp3 ratios was studied. The microstructure and physical characteristics of NCs with different sp2/sp3 ratios were investigated by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Transmission Electron Microscope (TEM) and Dynamic Light Scattering (DLS). Meanwhile, osteoblasts and macrophages were applied to characterize the cytotoxicity of the NCs. In vitro cytotoxicity assay results indicated that cells incubated with NCs of different sp2/sp3 ratios had greater osteogenic capacity, and these particles caused a weaker immune response in comparison with CoCrMo particles. Taken together, the results indicated that NCs with different sp2/sp3 ratios presented a good cytocompatibility than CoCrMo particles. But no significant differences were observed among NCs with different sp2/sp3 ratios. The better cytocompatibility of NCs is mainly attributable to their surface charge.

Comparative Analysis of Wear Rates of Microcrystalline Diamond and Diamond-Like Carbon Coatings Deposited on WС-Co Substrates

The study investigates the wear of microcrystalline diamond (MCD) and diamond-like carbon (DLC) coatings. The MCD and DLC coatings were grown by plasma enhanced chemical vapor deposition (PECVD) method on WC-Co substrates. The sliding wear tests were performed on the ball-on-plate type of tribometer in reciprocating mode. The ball-cratering wear tests were carried out using Calo tester. The mechanical profilometer, optical and scanning electron microscopes (SEM) were used for investigation of the surface morphology of the wear scars. The wear of DLC coating is more intense in comparison to the MCD coating. In contrast to the MCD coating, no evidence of the DLC coating deflection was found.

The effect of hydrogen on the tribological behavior of diamond like carbon (DLC) coatings sliding against Al2O3 in water environment

The tribological behavior of hydrogenated and hydrogen free diamond like carbon (DLC) coatings sliding against Al2O3 in air and pure water was investigated by ball-on-disc reciprocation wear test, and the effect of hydrogen was discussed. The results showed that in air environment, the Al2O3 slide against DLC under solid lubrication condition, and the wear of DLC coatings was mainly affected by coating mechanical properties. The hydrogen lowered the coating hardness and brought more DLC wear in air environment. In water environment, the solid lubrication effect is weak, the hydrogen began to play an important role in DLC wear. The hydrogenated DLC coating with saturated ‐CH bonds showed better wear resistance even though its hardness is lower. The hydrogenated DLC coating with unsaturated ‐CH bonds was easy to graphitize and generate massive wear no matter in water or in air environment.

Wear Mechanisms of Hydrogenated DLC in Oils Containing MoDTC

Diamond-Like Carbon (DLC) coatings are well known for offering excellent tribological properties. They have been shown to offer low friction and outstanding wear performance in both dry and lubricated conditions. Application of these coatings for automotive components is considered as a promising strategy to cope with the emerging requirements regarding fuel economy and durability. Commercially available oils are generally optimised to work on conventional ferrous surfaces and are not necessarily effective in lubricating non-ferrous surfaces. Recently, the adverse effect of the Molybdenum DialkyldithioCarbamate (MoDTC) friction modifier additive on the wear performance of the hydrogenated DLC has been reported. However, the mechanisms by which MoDTC imposes this high wear to DLC are not yet well understood. A better understanding of DLC wear may potentially lead to better compatibility between DLC surfaces and current additive technology being achieved. In this work, the wear properties of DLC coatings in the DLC/cast iron (CI) system under boundary lubrication conditions have been investigated to try to understand what appears to be a tribocorrosion-type process. A pin-on-plate tribotester was used to run the experiments using High Speed Steel (HSS) plates coated with 15 at.% hydrogenated DLC (a-C:15H) sliding against CI pins or ceramic balls. The lubricants used in this study are typical examples of the same fully formulated oil with and without ZDDP. The friction and wear responses of the fully formulated oils are discussed in detail. Furthermore, Optical Microscopy (OM) and Scanning Electron Microscopy (SEM), Energy-Dispersive X-ray spectroscopy (EDX), Focused Ion Beam (FIB) and Transmission Electron Microscopy (TEM) were used to observe the wear scar and propose wear mechanisms. The X-ray Photoelectron Spectroscopy (XPS) analysis was performed on the tribofilms to understand the tribochemical interactions between oil additives and the DLC coating. Nano-indentation analysis was conducted to assess potential structural modifications of the DLC coating. Coating hardness data could provide a better insight into the wear mode and failure mechanism of such hard coatings. Given the obtained results, the wear behaviour of the hydrogenated DLC coating was found to depend not only on the presence of ZDDP in the oil formulation but also on the counterpart type. This study revealed that the steel counterpart is a critical component of the tribocouple leading to MoDTC-induced wear of the hydrogenated DLC.

Tribological behavior of diamond like carbon film sliding against CoCrMo or Al2O3 in air and water environment

The effect of counterface material (CoCrMo and Al2O3) on the tribological behavior of hydrogen free diamond like carbon (DLC) film in air and water environment was investigated. The results show CoCrMo causes unstable high friction and high DLC wear in air environment owing to the unstable transfer layer rich in metal oxide. Al2O3 induces less DLC wear than CoCrMo in air due to reduced adhesive wear and solid lubrication. In water environment, CoCrMo brings extremely low wear of DLC film due to the high graphitized transfer material adhering on the counterface and water preventing adhesive wear. For Al2O3 counterpart, relatively high DLC wear is produces in water environment because of the high hardness of Al2O3 and insufficient solid lubrication.

Wear behaviour of hydrogenated DLC in a pin-on-disc model test under lubrication with different diesel fuel types

The wear behaviour of hydrogenated diamond like-carbon (DLC) coating in DLC/steel tribological contact in a pin-on-disc model test under lubrication with two diesel fuels is presented in this work. The first diesel fuel was standard EN590 that contained ester-based antiwear additives. In contrast to EN590, the second diesel fuel, called GDK650, did not contain antiwear additives. It was experimentally observed that the antiwear additives are detrimental to the DLC. The effects of load, speed and temperature on the DLC and steel counterbody wear were investigated. Steel counterbody wear volume was found to be not affected by pressure, temperature, speed and lubricant, whereas the DLC-coating revealed correlation between the parameters and wear rate. Regarding the results of the tribological tests under both diesel lubrications, new mathematical wear laws were developed.