A Review on Effects of Lubricant Formulations on Tribological Performance and Boundary Lubrication Mechanisms of Non-Doped DLC/DLC Contacts

Tribological efficiency of industrial applications involving boundary lubrication regime can be improved to an appreciable extent by the deposition of hard coatings on interacting surfaces. Among such coatings, diamond-like carbon (DLC) coatings are considered to be one of the most suitable ones for the said role. DLC coatings possess a unique combination of physical, chemical, and material properties due to which they can help in minimizing friction-induced energy and material losses even under starved lubrication conditions. Since commercial lubricants are optimized for steel surfaces, therefore, a lot of experimental investigations were carried out to analyze the tribological compatibility of these lubricants with various DLC coatings. However, there is still a lack of understanding about how DLC coatings interact with conventional lubricant additives. Some researchers reported tribologically beneficial interactions between DLC coatings and formulated lubricants while others observed no such behavior. To address these inconsistencies, there is a need to rearrange the published data in a more apprehensible and organized manner with a special emphasis on the mechanisms responsible for a particular tribological behavior. In this way, it can be determined whether synergistic or antagonistic correlation exists between a particular DLC-lubricant combination and research on DLC coatings can be continued in a logical way. In this article, most widely investigated non-doped DLC coatings (ta-C, a-C:H, a-C, and ta-C:H) are tribologically analyzed. Average values of friction and wear coefficients are calculated for various DLC-lubricant combinations using already published data and compared to quantify the effectiveness of a particular lubricant additive in enhancing tribological characteristics of symmetrical non-doped DLC contacts. Moreover, tribological performance parameters of non-doped DLC coatings are compared with those of doped-DLC coatings to understand differences in their tribological behavior in combination with additives.     

A brief review on the wear mechanisms and interfaces of carbon based materials

Abstract

The demand for reducing wear and friction has become the chief aim in the automotive industry nowadays. The usage of lubricant is not considered enough as there is still room for improvements. As a solution, much research has arisen towards what we called self-lubricating ideas, in order to reduce friction better than lubricant. This paper presents an overview wear mechanism and the interface of carbon-based materials. This paper will also discuss the interfaces by carbon as substrate and coating layer. The findings show that for metals, the predominant wear mechanisms were abrasion and fatigue. Meanwhile, for polymers and coating (DLC), they were abrasive along with adhesive wear. The surface roughness of the substrate plays a crucial role in increasing the excellent performance of the DLC coating. The interfaces of carbon elements definitely give huge impact on both self-lubricant materials and coatings where the coefficient of friction and wear rate changes drastically even with 1 wt.% addition. Nevertheless, a clear understanding of the factors that affect the tribological performance is very essential in performance improvement for potential applications.     

A Critical Review on Physical Vapor Deposition Coatings Applied on Different Engine Components

Friction and wear in different engine components have crucial effects on the engine performance, combustion efficiency, oil consumption and lifetime of the internal combustion (IC) engine. Under certain loads, speeds, and temperatures, the metallic components of the IC engine, especially the piston and valve system suffer from a higher friction. Thin film coating is one of the novel techniques to reduce the frictional forces and improve the mechanical properties of engine components. Due to some versatile tribological properties, increasing attention has been paid to the physical vapor deposition (PVD) technology in the recent decade to deposit thin film coating on engine components. This article presents a comprehensive literature review on thin film coatings for IC engine components deposited by PVD technique. Issues related to tribological properties (wear and coefficient of friction) and mechanical properties (hardness and roughness) are also highlighted. Scientific improvements are presented in the light of literature. It is revealed that PVD coating is significantly effective on wear resistance, scuffling resistance, surface roughness, and friction of the components in IC engine. Laboratory test and data from actual service so far suggest that the plasma-activated electron beam evaporation coating is perhaps one of the best choices for smooth surface finishing with improved mechanical and tribological properties. However, there are still some problems in its practical usage. This compressive review paper presents the major shortcomings of PVD coatings on IC engine components and the possible solutions if any. Finally, a number of issues have been reported which need to be encountered for further studies.     

Surface-modified Pd nanoparticles as a superior additive for lubrication

The tribological performance of lubricants is favourably altered by adding small amounts of nanoparticles which provide reduced wear and low friction. However, one of the main difficulties of using nanoparticles as additives is their dispersion or dissolution in lubricant oils, typically of hydrocarbon nature. With the surface modification of nanoparticles through long chain high molecular weight hydrocarbons, stable dispersions in lubricant oils become feasible. Here we show that using surface-modified Pd nanoparticles (2 nm size) with tetraalkylammonium chains, stable dispersions in lubricant oils become feasible with excellent tribological properties (friction 0.07, wear resistance 10⁻¹⁰ mm³/Nm). Electrical contact measurements were also used to monitor the conductivity of the contact during sliding. The use of these nanoparticles made decrease the electrical resistance of the contact a percentage of 97 to 99.5% in comparison with the initial value measured for the base oil alone. To understand these phenomena the contact surfaces and Pd nanoparticles were studied after friction by scanning electron microscopy (SEM) combined with energy dispersive X-ray analysis (EDX) and transmission electron microscopy (TEM), respectively. The outstanding performance is attributed to a combination of factors as metallic character of palladium, nanometric size, and replenishment of Pd nanoparticles onto the contact forming a transfer layer. This discovery opens new perspectives of using metallic nanoparticles as lubricant additives for small contacts and connectors applications.     

Defect effect on tribological behavior of diamond-like carbon films deposited with hydrogen diluted benzene gas in aqueous environment

This study examined the friction and wear behavior of diamond-like carbon (DLC) films deposited from a radio frequency glow discharge using a hydrogen diluted benzene gas mixture. The DLC films were deposited on Si (1 0 0) and polished stainless steel substrates by radio frequency plasma-assisted chemical vapor deposition (r.f.-PACVD) at hydrogen to benzene ratios, or the hydrogen dilution ratio, ranging from 0 to 2.0. The wear test was carried out in both ambient and aqueous environments using a homemade ball-on-disk type wear rig. The stability of the DLC coating in an aqueous environment was improved by diluting the benzene precursor gas with hydrogen, suggesting that hydrogen dilution during the deposition of DLC films suppressed the initiation of defects in the film and improved the adhesion of the coating to the interface.     

多层石墨烯作为液体石蜡添加剂的摩擦学性能

以膨胀石墨为原料,采用不同溶剂,通过液相超声直接剥离法制备多层石墨烯,利用透射电子显微镜、原子力学显微镜对其形貌进行了表征,在多功能往复摩擦磨损试验仪上研究了石墨烯石蜡分散体系的摩擦学性能。通过扫描电镜、能谱仪分析了磨痕形貌及表面元素组成。结果表明:多层石墨烯作为液体石蜡添加剂表现出良好的减摩抗磨性能,主要是因为多层石墨烯在磨损表面形成的物理吸附膜与摩擦化学反应膜的共同作用。     

The microstructure, mechanical and friction properties of protective diamond like carbon films on magnesium alloy

Protective hard coatings deposited on magnesium alloys are believed to be effective for overcoming their poor wear properties. In this work, diamond-like carbon (DLC) films as hard protective films were deposited on AZ91 magnesium alloy by arc ion plating under negative pulse bias voltages ranging from 0 to −200 V. The microstructure, composition and mechanical properties of the DLC films were analyzed by scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy and nanoindentation. The tribological behavior of uncoated and coated AZ91 magnesium alloy was investigated using a ball-on-disk tribotester. The results show that the negative pulse bias voltage used for film deposition has a significant effect on the sp³ carbon content and mechanical properties of the deposited DLC films. A maximum sp³ content of 33.3% was obtained at −100 V, resulting in a high hardness of 28.6 GPa and elastic modulus of 300.0 GPa. The DLC films showed very good adhesion to the AZ91 magnesium alloy with no observable cracks and delamination even during friction testing. Compared with the uncoated AZ91 magnesium alloy, the magnesium alloy coated with DLC films exhibits a low friction coefficient and a narrow, shallow wear track. The wear resistance and surface hardness of AZ91 magnesium alloy can be significantly improved by coating a layer of DLC protective film due to its high hardness and low friction coefficient.     

Influence of sulfidation treatment on the structure and tribological properties of nitrogen-doped diamond-like carbon films

The nitrogen-doped diamond-like carbon (DLC) films were deposited on high speed steel (HSS) substrates in the direct current unbalanced magnetron sputtering system. Sulphurized layer was formed on the surface of DLC films by means of liquid sulfidation in the intermixture of urea and thiourea solution in order to improve the tribological properties of DLC films. The influence of sulfidation treatment on the structure and tribological properties of DLC films was investigated in this work. The structure and wear surface morphology of DLC films were analyzed by Raman spectroscopy, XPS and SEM, respectively. It reveals that the treated films are smooth and uniform; and sulfur atoms are bonded chemically. The treated films have broader distribution of Raman spectra in the range of 1000-1800 cm⁻¹ and higher I_D/I_G ratio than the untreated films as a result of the appearance of the crystalline graphite structure after the sulfidation treatment. It is showed that the sp² relative content increase in the treated films from the XPS measurement. The Raman results are consistent with the XPS results. The tribological properties of DLC films were investigated using a ball-on-disk rotating friction and wear tester under dry friction conditions. It is found that the sulfidation concentration plays an important part in the tribological properties of the treated DLC films. The results showed the treated films with low sulfidation concentration have a lower friction coefficient (0.1) than the treated films with high sulfidation concentration (0.26) and the untreated films (0.27) under the same friction testing conditions, which can be attributed to both the presence of sulfur-containing materials and the forming of the mechanical alloyed layer on the wear surface. Adding the dry nitrogen to the sliding surface in the testing system helps the friction coefficient of the treated films with low sulfidation concentration to decrease to 0.04 further in this work. On the basis of the experimental results, it is indicated that the liquid sulfidation technique, which is low-cost, non-polluting and convenience, would be an appropriate method for the surface treatment of DLC films.     

Tribological behavior of diamond-like carbon film with different tribo-pairs: A size effect study

A friction force microscope (FFM) with different probes and a ball-on-disk (BOD) tribo-meter were used to investigate the tribological properties of diamond-like carbon (DLC) films. DLC films were prepared by chemical vapor deposition (CVD) method by altering the deposition parameters, and their morphologies and structural information were examined with an atomic force microscope (AFM) and the Raman spectrum. The wear traces of the DLC films after frictional tests were analyzed by an optical microscope. It is found that surface roughness and adhesion play important roles in characterizing the tribological properties of DLC films using FFM. Moreover, the debris accumulation is another significant factor affecting the frictional behavior of DLC films, especially for the sharp tip. The difference in coefficients of friction (COFs) obtained by the BOD method among different DLC films under water lubrication is much smaller than the case without water lubrication. The variation trends in COF for the flat tip and the BOD test are similar in comparison with the result obtained with the sharp tip. The wear traces after frictional tests suggest that DLC films under water lubrication are prone to be damaged more readily.     

Control of tribological properties of diamond-like carbon films with femtosecond-laser-induced nanostructuring

This paper reports tribological properties of diamond-like carbon (DLC) films nanostructured by femtosecond (fs) laser ablation. The nanostructure was formed in an area of more than 15 mm × 15 mm on the DLC surface, using a precise target-scan system developed for the fs-laser processing. The frictional properties of the DLC film are greatly improved by coating a MoS₂ layer on the nanostructured surface, while the friction coefficient can be increased by surface texturing of the nanostructured zone in a net-like patterning. The results demonstrate that the tribological properties of a DLC surface can be controlled using fs-laser-induced nanostructuring.     

Tribochemical investigation of DLC coating in water using stable isotopic tracers

Tribochemical reaction of DLC coating in water was investigated by using a stable isotopic tracer, ¹⁸O labeled water (H₂¹⁸O), to carry out the friction test of DLC coating and 440C ball pair, and using ToF-SIMS to analyze the worn surfaces. The result showed that DLC coating tribochemically reacted with water to form hydrophilic hydroxyl and carboxyl groups on surface, and suggested that the formed hydroxyl mainly combined with the secondary or tertiary carbons on the surface. The surface layer on the counter ball mainly consisted of C from the coating, Cr, Fe from the ball and ¹⁸O from water, and was rich in ¹⁸OH. It is thought that the hydrophilic groups formed at the interfaces play an important role in low friction and wear behaviors of DLC coating and the counter part in a water environment. Comparing with that obtained from the test in D₂O, the result also suggests that hydrogen/deuterium exchange is easy to occur between the products containing OD on the mated ball and some adsorbates in an ambient air environment.     

First-order phase transition between the liquidlike and solidlike structures of a boundary lubricant

A thermodynamic model for characterization of the first-order phase transition between the structural states of a boundary lubricant is suggested. It is shown that melting of the lubricant is due both to a rise in its temperature and to shear experienced by friction surfaces when elastic strains (stresses) exceed a critical value. A phase diagram with regions of dry and sliding friction is constructed. Using a mechanical analogue of the tribological system, the dependence of the friction force on the lubricant temperature and relative shear rate of the friction surfaces is analyzed. The observed conditions of stick-slip friction, which is the main reason for friction parts wear, are described. Reasons for stick-slip friction are revealed.     

The influence of a cross-linking agent and C60 fullerene on the properties of a solid lubricant

The influence of a cross-linking agent, diamine, and C₆₀ fullerene on the antifriction and wear properties of a solid lubricant made of trifluorochloroethylene-vinylidene fluoride copolymer was studied for steel-to-steel sliding friction. The wear characteristics are improved in the whole range of loads investigated, while the antifriction properties, only at small loads. A qualitative wear test method is proposed in which the test-period-averaged friction coefficient of a hybrid specimen (coating plus metal substrate) is measured with a standard friction machine. A model that considers the combined interaction of the substrate and the coating with the roller was used to calculate the linear wear rate of steel and the probabilistic parameter of wear.     

Formation of a protective film on a copper friction surface in the presence of fullerene C60

The influence of C₆₀ additive in industrial oil on the structure of the friction surface of copper foil in a steel-copper sliding friction pair is investigated by wide-angle x-ray diffraction, scanning electron microscopy, and hardness testing. The presence of C₆₀ in the lubricant leads to the formation of a thin film (of thickness <1000 Å) on the friction surface of the copper, where it protects the surface layers of the latter against major structural changes and helps to improve the tribological characteristics.     

Tribological effect of iron oxide residual on the DLC film surface under seawater and saline solutions

This paper discusses the seawater and saline solutions effects on the tribological behavior of diamond-like carbon (DLC) films. The adsorption of Fe on DLC surface is one of the mechanisms that is believed to be the cause of the decrease in dispersive component of the surface energy and increase of the I_D/I_G ratio leading to low friction coefficient and wear rate under corrosive environments. Tribological behaviors DLC films were experimentally evaluated under corrosive environments by using steel ball and DLC coated steel flat under rotational sliding conditions. The DLC films were prepared on 440 stainless steel disks by DC-pulsed PECVD using methane as a precursor gas. Two different set of tribological system was assembled, one when the liquids and the pairs were put inside of a stainless steel vessel and others inside of a PTFE. Every tribological test was performed under 10 N normal load120 mms^? 1 of sliding speed. The friction coefficients were evaluated during 1000 cycles.     

掺硅类金刚石薄膜摩擦过程的分子动力学模拟

掺硅类金刚石(Si-DLC) 薄膜表现出优异的摩擦学性能, 在潮湿空气和高温中显示出极低的摩擦系数和很好的耐磨性, 但是许多实验表明Si-DLC膜的摩擦性能受其硅含量的影响很大. 因此, 本文采用分子动力学模拟的方法分别研究干摩擦和油润滑两种情况下不同硅含量的Si-DLC膜的摩擦过程. 滑移结果表明干摩擦时DLC膜和掺硅DLC膜之间生成了一层转移膜, 而油润滑时则为边界膜. 因此干摩擦时的摩擦力明显大于油润滑时的摩擦力. 少量添加硅确实能降低DLC膜的摩擦力, 但是硅含量大于20%后对DLC膜的摩擦行为几乎无影响. 干摩擦时硅含量对转移膜内键的数量影响很大, 转移膜内CC键和CSi键都先增加后减少, 滑移结束时几乎不含CSi键.     

Surface restoration induced by lubricant additive of natural minerals

The effect of a new-fashioned lubricant additive is studied. The additive is prepared out of natural minerals containing flaky silicate, schungite and some other catalyzers. Applications of the additive obviously improve the surface mechanics properties of steel-steel friction pairs, and the nanohardness and the modulus of the friction surface are increased by 67 and 90%, respectively. The friction surface is especially examined with the high resolution transmission electron microscope (HRTEM), and an amorphous restoration film mostly made up of C with some Si or Si-O amorphous structure doped was found. Considering all research results about the restoration film, this study suggests the film is a sort of diamond-like carbon film (DLC film).     

Atmospheric effects on the adhesion and friction between non-hydrogenated diamond-like carbon (DLC) coating and aluminum - A first principles investigation

Experimentally, non-hydrogenated DLC coatings were tested against 319 Al alloy in the nitrogen, hydrogen, dry air (0% RH), and ambient air (40% RH) environments using a vacuum pin-on-disc tribometer. The average coefficient of friction (COF) and the material transfer changed dramatically depending on the test environment. Density functional theory (DFT) calculations were performed to investigate the interaction of diamond surface, to represent non-hydrogenated DLC, with N₂, H₂, and H₂O molecules. These calculations suggested that hydrogen and water would dissociate and be chemically adsorbed at a diamond surface whereas the dissociation of nitrogen is very unlikely to happen. Therefore, the diamond/DLC surface is passivated by -H termination in hydrogen and by -OH termination in water vapor, but not passivated in nitrogen. The calculated work of separation for Al with non-passivated and reacted diamond surfaces indicated the same tendency of adhesive transfer as observed in the pin-on-disc tests. The calculated work of separation at the interfaces formed after material transfer has the same trend with the measured COF. Therefore, DFT calculations successfully explained the atmospheric dependency of the tribological behavior of non-hydrogenated DLC coatings.     

环烷酸铅和烷基水杨酸铅的微波原位合成及其摩擦学性能

在液体石蜡中采用微波技术原位合成了油溶性环烷酸铅（LN）和十二烷基水杨酸铅（LAS）,在高速低负荷（r=1500&#177;10rpm,P=196-392N)和低速高负荷（r=300&#177;10rpm,P=800N)两种条件下,用四球摩擦磨损试验对LN,LAS和对应的羧酸进行了摩擦学性能评价,用往复式摩试验机考察了LN和LAS抗磨减摩性能,结果表明：LN具有良好的抗磨减磨性能和中等的极压性能,且各项摩擦学性能指标均好于LAS。为弄清其作用机理,从分子结构分析了产生摩擦学性能差异的原因,并用SEM及XPS研究了磨斑表面,结果发现：摩擦过程中,LN和LAS都能在摩擦副表面形成吸附膜且部分吸附膜发生摩擦化学反应产生了铅氧化物转化膜,但所形成的吸附膜和转化膜厚度不同。     

Surface-modification in situ of nano-SiO2 and its structure and tribological properties

The preparation of a series of dispersible nano-SiO₂ by surface-modification in situ was described in this paper. It is found that some silane coupling agents can be combined with nano-SiO₂ by covalent bonds, which change the nanoparticle's surface properties and make nano-SiO₂ disperse well and steadily in many organic mediums. The structure of nanoparticles was characterized by transmission electron microscopy (TEM), infrared spectrum (IR), X-ray photoelectron spectra (XPS) and thermogravimetric analysis (TG). The dispersivity of these nanoparticles in organic solvents was measured by light transmittance. Considering such superior dispersion in oily solvents and very small size, we primarily investigated their tribological behaviors as additive in lubricant on wear testers. The results show that they can evidently increase anti-wear ability and reduce the friction coefficient of lubricant.