Preparation and properties of Ni–Co–P/nano‐sized Si3N4 electroless composite coatings

Ni–Co–P/nano‐sized Si₃N₄ composite coating was successfully fabricated on aluminum alloys by electroless plating in this work. The surface and cross‐sectional morphologies, composition, microstructure, microhardness, friction and wear behavior of deposits were investigated with SEM, EDS, XRD, Vickers hardness and high‐speed reciprocating friction, respectively. It was found that a Ni–Co–P/nano‐sized Si₃N₄ composite coating on aluminum alloy substrate is uniform and compact. The existence of nano‐sized Si₃N₄ particles in the Ni–Co–P alloy matrix causes a rougher surface with a granular appearance, and increases the microhardness but decreases the friction coefficients and wear rate of electroless coatings. Meanwhile, the effects of heat treatment at 200, 300, 400 and 500 °C for 1 h on the hardness and tribological properties were researched. It is revealed that both of the microhardness and tribological properties of Ni–Co–P coatings and Ni–Co–P/Si₃N₄ composite coatings increase with the increase of heating temperature in the range of 200–400 °C, but show different behavior for the two coatings after annealing at 500 °C. Copyright © 2011 John Wiley & Sons, Ltd.     

Micro/nanotribological behaviors of ionic liquid nanofilms with different functional cations

Four kinds of molecularly thin films of room temperature ionic liquids (RTILs) with different functional cations were prepared on silicon substrates by dip‐coating method. Thermal stability of the RTILs was evaluated using Mettler thermal gravity analysis (TGA) in a nitrogen atmosphere. Chemical compositions of the RTIL nanofilms were examined by means of multifunctional XPS. Nanoscaled adhesion and friction forces between the films and AFM tip were measured by FFM whereas the morphologies of the films were also investigated. Microscaled friction and wear behaviors between the films and Si₃N₄ ball were further measured by the microtribometer. The micro/nanotribological behaviors of different RTIL films were comparatively investigated and discussed in terms of functional cations of the RTILs molecules. Results in this paper revealed that the functional cations of the RTIL films significantly affected their tribological behaviors both in micro‐ and nanoscales. The corresponding micro/nanotribological mechanism of the tested ultrathin RTIL films under the test conditions was consequently proposed based on the experimental results. Copyright © 2010 John Wiley & Sons, Ltd.     

Effects of UV irradiation on tribological properties of nano‐TiO2 thin films

One‐layer and two‐layer nano‐TiO₂ thin films were prepared on the surface of common glass by sol–gel processing. Water contact angle, surface morphology, tribological properties of the films before and after ultraviolet (UV) irradiation were investigated using DSA100 drop shape analyzer, scanning probe microscopy (SPM), SEM and universal micro‐materials tester (second generation) (UMT‐2MT) friction and wear tester, respectively. The stored films markedly resumed their hydrophilicity after UV irradiation. But UV irradiation worsened tribological properties of the films. After the film was irradiated by UV, the friction coefficient between the film and GCr15 steel ball increased about 10–50% and its wear life shortened about 20–90%. Abrasive wear, brittle break and adherence wear are the failure mechanisms of nano‐TiO₂ thin films. It was believed that UV irradiation increased surface energy of the film and then aggravated adherence wear of the film at initial stage of friction process leading to severe brittle fracture and abrasive wear. Copyright © 2009 John Wiley & Sons, Ltd.     

Sliding friction and wear behaviors of plasma sprayed aluminum–bronze coating in artificial seawater

The friction and wear behaviors of plasma sprayed aluminum–bronze (CuAl) coating sliding against silicon nitride (Si₃N₄) in artificial seawater were investigated and compared with those in pure water and dry sliding. The morphologies of the worn surfaces were analyzed by three‐dimensional non‐contact surface mapping and scanning electron microscopy. Moreover, chemical states of the tribochemical products of CuAl/Si₃N₄ in seawater were characterized by X‐ray photoelectron spectroscopy. Results show that the plasma sprayed CuAl coating possessed a specific wear rate (in order of 10^?7 mm³/Nm) in seawater more than 600 times smaller than that in dry sliding due to the great alleviation in abrasion wear and splats delamination. Besides, the CuAl/Si₃N₄ had a friction coefficient of 0.06 in seawater, significantly lower and more stable than those in pure water and dry sliding. The tribochemical products of CuAl/Si₃N₄ in seawater, which were proved to be silica, alumina, and their hydrates, transformed into a loosened wear‐debris layer under the coagulation effect of the seawater and dominated the excellent lubrication state in artificial seawater. Copyright © 2014 John Wiley & Sons, Ltd.     

Tribological properties of Ti-doped diamond-like carbon coatings under dry friction and PAO oil lubrication

Titanium-doped diamond-like carbon (Ti-DLC) coatings with Ti concentration of 4 at.% (Ti_4at.%-DLC) and 27 at.% (Ti_27at.%-DLC) were prepared by a hybrid ion beam deposition system for comparison. The tribological behaviors of Ti-DLC coatings under dry friction and boundary lubrication conditions were systematically investigated. Results showed that, under dry friction, the Ti_4at.%-DLC coating displayed lower friction coefficient (0.07) and wear rate due to the continuous transfer film formed in the sliding interface, while Ti_27at.%-DLC coating was worn out at initial stage due to severe abrasive wear. And under boundary lubrication, both the Ti_4at.%-DLC and Ti_27at.%-DLC coatings showed excellent tribological properties attributing to the formation of oil film between sliding interface. In particular, Ti_27at.%-DLC performed the lowest wear rate of 1.12 × 10⁻¹⁶ m³ N⁻¹ m⁻¹ in this friction case. In conclusion, compared with Ti_27at.%-DLC coating, Ti_4at.%-DLC coating exhibited better tribological performances both under dry friction and boundary lubrication. The present result provides guidance for the selection of DLC coatings according to the realistic environment of starved-oil and rich-oil conditions.     

The high‐temperature tribological properties of Si‐DLC films

The tribological properties of Silicon‐containing diamond‐like‐carbon (Si‐DLC) films, deposited by magnetron sputtering Si target in methane/argon atmosphere, were studied in comparison with diamond‐like‐carbon (DLC) films. The DLC films disappeared because of the oxidation in the air at 500 °C, whereas the Si‐DLC films still remained, implying that the addition of Si improved significantly the thermal stability of DLC films. Retarded hydrogen release from DLC film at high temperature and silicon oxide on the surface might have contributed to lower friction coefficient of the Si‐DLC films both after annealing treatment and in situ high‐temperature environment. Copyright © 2012 John Wiley & Sons, Ltd.     

The effect of interface electrostatic interaction based on acid–base theory on friction behavior

Fluorine‐containing amorphous carbon films [fluoring‐containing diamond‐like carbon (F‐DLC)] were fabricated on Si wafer by direct current plasma enhanced chemical vapor deposition (dc‐PECVD) technique using CF₄ and Ar as gas sources, confirmed by XPS and Raman analyses. The friction tests were carried out on a rotating ball‐on‐disk apparatus in high vacuum atmosphere (≤5.0 × 10^?4 Pa) at the load of 0.5 N selecting glass (mainly containing silicon–oxygen tetrahedron structure) and Al₂O₃ with the same hardness and surface roughness as the counterpart balls. The results indicate that glass/F‐DLC results in lower friction coefficient of 0.14 than that of the Al₂O₃/F‐DLC (0.20). At the same time, no wear was occurred, and the transfer layer was not formed on the counterpart ball for glass/F‐DLC, while the wear of Al₂O₃/F‐DLC is slightly larger than that of glass/F‐DLC. However, just like the glass ball, there is no formation of transfer layer on the Al₂O₃ ball surface. Furthermore, the chemical state of fluorine in the film after friction, which mainly existed in the form of the C–CF and C–F bonds, did not change compared with the F‐DLC film, while the fluorine content has changed significantly. As a result, it is assumed that interface electrostatic interaction based on acid–base theory plays an extremely important role in the process of friction. Copyright © 2017 John Wiley & Sons, Ltd.     

Oil‐Soluble Polymer Brush Grafted Nanoparticles as Effective Lubricant Additives for Friction and Wear Reduction

The development of high performance lubricants has been driven by increasingly growing industrial demands and environmental concerns. Herein, we demonstrate oil‐soluble polymer brush‐grafted inorganic nanoparticles (hairy NPs) as highly effective lubricant additives for friction and wear reduction. A series of oil‐miscible poly(lauryl methacrylate) brush‐grafted silica and titania NPs were synthesized by surface‐initiated atom transfer radical polymerization. These hairy NPs showed exceptional stability in poly(alphaolefin) (PAO) base oil; no change in transparency was observed after being kept at ?20, 22, and 100 °C for ≥55 days. High‐contact stress ball‐on‐flat reciprocating sliding tribological tests at 100 °C showed that addition of 1 wt % of hairy NPs into PAO led to significant reductions in coefficient of friction (up to ≈40 %) and wear volume (up to ≈90 %). The excellent lubricating properties of hairy NPs were further elucidated by the characterization of the tribofilm formed on the flat. These hairy NPs represent a new type of lubricating oil additives with high efficiency in friction and wear reduction.     

A New Route to High Yield Mesostructure Boron Carbide Powder from SiC/Si3N4 Whiskers

Boric acid/Mg (magnesiothermic or metal sintering aid)/C (activated carbon)/N₂ or Ar (atmosphere)/additives (mesoporous SiO₂ or mesoporous SiC or SiC/Si₃N₄ whiskers) systems were used in the one‐step synthesis of mesostructured B₄C (221.04 m²/g). In this study, a mixture of the active precursors was allowed to react via a self‐sustaining reaction (high‐energy ball milling process). Also, the properties of the samples prepared using powdered activated carbon (PAC) and SiC/Si₃N₄ whiskers (concentration in the range 5–10 wt%) as sources of carbon were investigated. X‐ray diffraction results proved the presence of crystalline boron carbide in the peak positions of B₄C (B₁₂C₃). The advantage of the present route for yielding mesostructured B₄C powder seems to be limited by the growth of carbide crystals. This restriction is believed to be imposed by a lack of whisker additives around the pores where B₄C crystals grow. The results also show that the best mesoporous additive for the synthesis of nanoscale boron carbide is mesoporous SiC. The effect of the concentration of CO (reduction of α‐Fe₂O₃ to Fe by CO) on the B₄C synthesis suggests that, in addition to the concentration of CO, the pressure of the N₂ atmosphere is an important factor in the synthesis of mesostructured B₄C.     

Sol‐Gel‐Process in the Ammono‐System – a Novel Access to Silicon Based Nitrides

Controlled coammonolysis of elementalkylamides in aprotic organic solvents at low temperatures have been shown to result in the formation of polyazanes. The synthetic procedure developed may be addressed as “sol‐gel‐route in the ammono system”. Pyrolysis of these novel polymer precursors gave access to multinary nitrides. For the model systems Si(NHMe)₄/B(NMe₂)₃, Si(NHMe)₄/Ti(NMe₂)₄, and Si(NHMe)₄/Ta(NMe₂)₅ polymeric boro‐, titano and tantalosilazanes were obtained. Pyrolysis in ammonia at 1000 °C yielded amorphous silicon boron nitride, silicon titanium nitride and silicon tantalum nitride powders; further heating of the nitride powders at 1500 °C in nitrogen atmosphere led to the formation of partly crystalline composites of α‐Si₃N₄ and amorphous silicon boron nitride for the Si/B/N system, a composite of finely dispersed TiN and amorphous silicon titanium nitride for the Si/Ti/N system, and crystalline TaN and amorphous silicon nitride for the Si/Ta/N system. Furthermore, the structure and pyrolysis chemistry of the polymeric intermediates, as well as the morphology of the pyrolysis products, were studied by NMR, MAS‐NMR, FT‐IR, DTA‐TG‐MS, XRD, SEM, EDX and elemental analyses.     

Effects of sputtering current on the bonding structure and mechanical properties of diamond‐like carbon films deposited by MFPUMST

Diamond‐like carbon (DLC) films on glass wafers were produced by middle frequency pulsed unbalanced magnetron sputtering technique (MFPUMST) at different sputtering current. The chemical bonding of carbon characterized by Raman spectroscopy and X‐ray photoelectron spectroscopy (XPS) show that the sp³ fraction in DLC films increases with increasing sputtering current from 100 to 300 mA, and then decreases above 300 mA. Mechanical properties like nano‐hardness and elastic recovery for these films under different sputtering currents analyzed by a nano‐indentation technique show the same tendency that nano‐hardness and elastic recovery increase with increasing sputtering current from 100 to 300 mA, and then decrease with increasing sputtering current from 300 to 400 mA. These results indicate that the sp³ fraction in the prepared DLC films is directly related to nano‐hardness and elastic recovery. The results shown above indicate that the parameter of the preparation—sputtering current has a strong influence on the bonding configuration of the deposited DLC films. The mechanism of sputtering current on the sp³ fraction is discussed in this paper. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of methane on magnetron sputtering graphite target deposited films and tribological properties of a-C:H:Ti/a-C:H friction pairs

In this study, we prepared a-C:H films with different nanostructures at different methane flow rates. The effect of the methane flow rate on the tribological properties of 440 steel/a-C:H friction pairs and a-C:H:Ti/a-C:H friction pairs in an atmospheric environment was studied by a reciprocating friction machine. The results show that there is no relationship between the tribological properties of 440 steel/a-C:H friction pair and methane flow rate. The tribological performance of the a-C:H:Ti/a-C:H friction pair was greatly improved. In particular, in the friction pair of a-C:H:Ti/a-C:H with a methane flow rate of 20 sccm, superlubricity is shown, and the wear rate is only 4.04 × 10⁻⁹ mm³/Nm. After tribological experiments, Raman spectroscopy, XPS, and other characterization methods were used to study the relationship between the nanostructure and tribological properties of a-C:H:Ti films and a-C:H prepared with different methane flow rates. This study is great significance to the application of a-C:H:Ti/a-C:H friction pair in mechanical parts under atmospheric environment.     

Comparative study of the effects of nano‐sized and micro‐sized CF and PTFE on the thermal and tribological properties of PEEK composites

The tribological characteristics of PEEK composites fretting against GCr 15 steel were investigated by a SRV‐IV oscillating reciprocating ball‐on‐disk tribometer. In order to clarify the effect of type and size of fillers on the properties of PEEK composites, nano‐sized and micro‐sized CF and PTFE fillers were added to the PEEK matrix. The thermal conductivity, hardness, and fretting wear properties of PEEK composites reinforced by CF or PTFE were comparatively studied. The results showed that the type and size of the fillers have an important effect on both the friction coefficient and wear rate, by affecting their thermal conductivity, hardness, as well as the surface areas of their transfer films. In comparison, the effect on improving the tribological properties of micro‐sized CF was superior to that of nano‐sized CF, while the effect of nano‐sized PTFE was superior to that of micro‐sized PTFE. Considering the acceptable friction coefficient and wear rate of the composite under the fretting wear test, it seemed that 4% nCF, 20% mCF, 2% nPTFE and 10% mPTFE were desired additive proportions. And it also can be found that during the fretting wear test, the abrasive and adhesive wear resulted in accumulative debris at the contacting surface. The transfer films made of debris were formed on the counterfaces.     

Tribological behavior of the low-concentration boric acid and ZDDP lubricating oil mixtures

Zinc dithiophosphate (ZDDP)-free environmental friendly lubricating oil research studies have gained importance due to the governmental regulations over the last decade. In this study, low concentration boric acid-base oil and ZDDP-base oil mixtures were investigated with a ball on flat reciprocating tribometer to evaluate their tribological performances. The tribological performances of 1, 3, and 5% additive and base oil mixtures were evaluated at boundary lubrication condition in three main contexts including wear rates, surface tribochemistry, and friction. Results showed that there was no significant difference between boric acid and ZDDP friction coefficients. However, boric acid showed poor wear resistance when compared with ZDDP and it cannot be an alternative additive alone to ZDDPs.     

The structure and tribological properties of aluminum/carbon nanocomposite thin films synthesized by reactive magnetron sputtering

Hydrogenated nanocomposite aluminum/carbon thin films (Al/a‐C:H) were fabricated on stainless steel and silicon wafer substrates via unbalanced reactive magnetron sputtering from an Al target in CH₄/Ar plasma. The composition and structure of Al/a‐C:H films were investigated by high‐resolution transmission electron microscope (HRTEM), XPS and micro‐Raman spectroscopy. Nanoindenter, interferometer and ball‐on‐disc tribometer were carried out to evaluate the hardness, internal stress and tribological properties of Al/a‐C:H films. HRTEM observations confirmed that the metallic Al nanocrystallites were uniformly dispersed in the amorphous carbon matrix. XPS and Raman analyses indicated that the sp² content increased with the increase of Al content in the films. Nanoindenter and interferometer tests exhibited that the uniform incorporation of Al nanocrystallites can diminish drastically the magnitude of internal stress with maintaining the higher hardness of as‐deposited films. Especially, the ball‐on‐disc tribometer measurements revealed that the nanocomposite film with 2.3 at.% Al content exhibited relatively better wear resistance and self‐lubrication performance with a friction coefficient of 0.06 and wear rate of 3.1 × 10^?16 m³/ N·m under ambient air, which can be attributed to the relatively higher hardness, the formation of continuous graphitized transfer film on counterface and the reduced reaction of oxygen with carbon. Copyright © 2010 John Wiley & Sons, Ltd.     

Preparation and characterization of copper nanoparticles surface‐capped by alkanethiols

Cu nanoparticles surface‐capped by alkanethiols were synthesized using ligand exchange method in a two‐phase system. The effects of synthetic conditions, including the pH value of CuSO₄ solution, the ratio of cetyltrimethyl ammonium bromide to CuSO₄, and reaction temperature, on the size and shape of as‐synthesized Cu nanoparticles were investigated. As‐synthesized Cu nanoparticles surface‐capped by alkanethiols with different chain lengths (C_xS‐Cu) were characterized by means of X‐ray diffraction, transmission electron microscopy, Fourier transform infrared spectrometry, and ultraviolet–visible light spectrometry. The tribological behavior of C_xS‐Cu as an additive in liquid paraffin was evaluated with a four‐ball machine. Results indicate that cetyltrimethyl ammonium bromide plays an important role in controlling the dispersion of Cu nanoparticles before adding modifier octanethiol into the reaction solution. C_xS‐Cu nanoparticles as additive in liquid paraffin possess excellent antiwear and friction‐reduction performance because of the deposition of nano‐Cu with low melting point on worn steel surface leading to the formation of a self‐repairing protective layer thereon. Copyright © 2013 John Wiley & Sons, Ltd.     

The influence of anti‐wear additive ZDDP on doped and undoped diamond‐like carbon coatings

Diamond‐like carbon (DLC) coatings are recognised as a promising way to reduce friction and improve wear performance of automotive engine components. DLC coatings provide new possibilities in the improvement of the tribological performance of automotive components beyond what can be achieved with lubricant design alone. Lubricants are currently designed for metallic surfaces, the tribology of which is well defined and documented. DLC does not share this depth of tribological knowledge; thus, its practical implementation is stymied. In this work, three DLC coatings are tested: an amorphous hydrogenated DLC, a silicone‐doped amorphous hydrogenated DLC and a tungsten‐doped amorphous hydrogenated DLC. The three coatings are tested tribologically on a pin‐on‐reciprocating plate tribometer against a cast iron pin in a group III base oil, and a fully formulated oil that consists of a group III base oil and contains ZDDP, at 100 °C for 6 h and for 20 h in order to determine whether a phosphor‐based tribofilm is formed at the contact. The formation of a tribofilm is characterised using atomic force microscopy and X‐ray photoelectron spectroscopy techniques. The main findings of this study are the formation of a transfer film at the undoped, amorphous hydrogenated DLC surface, and also the tungsten amorphous hydrogenated DLC having a significant wear removal during the testing. The three coatings were found to have differing levels of wear, with the tungsten‐doped DLC showing the highest, the silicon‐doped DLC showing some coating removal and the amorphous hydrogenated DLC showing only minimal signs of wear. Copyright © 2015 John Wiley & Sons, Ltd.     

Electron probe microanalysis of chemical gradients in gas pressure sintered silicon nitride

During gas pressure sintering of silicon nitride (Si₃N₄) — which normally contains oxide additives such as SiO₂, Al₂O₃ and Y₂O₃ — in a resistance heated graphite furnace, a reduction of the Si₃N₄ sample takes place. At high temperatures (>1800°C) this effect is accompanied by decomposition reactions of Si₃N₄. Both lead to chemical gradients in larger components which influence the strength of the sintered article. Electron probe microanalysis (EPMA) has been carried out in order to study the influence of the crucible material [graphite (C), boron nitride (BN)] and the quantity of filling on the gradient formation.     

Preparation of WS2 nanocomposites via mussel-inspired chemistry and their enhanced dispersion stability and tribological performance in polyalkylene glycol

A novel biomimetic surface modification method utilizing mussel-inspired chemistry was used to prepare tungsten disulfide (WS₂) nanocomposites, which enhanced the dispersion stability and tribological performance of WS₂ in polyalkylene glycol (PAG). Herein, WS₂-polydopamine-methoxypolyethylene glycol amine (WS₂-PDA-MPGA) was first synthesized via mussel-inspired chemistry and used as a lubricant additive in PAG. After modification, the dispersion stability of WS₂ nanosheets in PAG was obviously improved. Moreover, the tribological performance of WS₂-PDA-MPGA in PAG at high temperature was evaluated by the oscillating reciprocating tribometer. Compared to pure PAG, the lubricant composition containing WS₂-PDA-MPGA exhibited excellent performance in friction reduction and anti-wear properties at high temperature. The optimal tribological performance could be obtained when the percentage of additives was 0.9?wt%. The tribological results indicate that WS₂-PDA-MPGA, with its good dispersion stability, has better friction reduction and anti-wear properties than does WS₂ in PAG base oil. The chemical composition analysis of the wear surface indicated that a stable protective film had been formed by physical adsorption and tribo-chemical reactions. Therefore, the surface modification strategy is an effective way to improve the dispersion stability of WS₂ in PAG, which can be expanded application of WS₂ in the tribological field.     

Synthesis of nanostructured lanthanum fluoborate modified by oleylamine and evaluation of its tribological properties as a lubricating additive in synthetic ester

Lanthanum fluoborate modified by oleylamine [denoted as La(BF₄)₃‐OA] was synthesized as a potential lubricant additive by direct precipitation method with sodium tetrafluoroborate and lanthanum nitrate [La(NO₃)₃] as the staring materials and oleylamine (OA) as the surface‐modifying agent in distilled water‐ethanol mixed solvent. The effects of reaction temperature, OA to La(NO₃)₃ ratio, and surfactant cetyltrimethyl ammonium bromide on the size and shape of as‐synthesized La(BF₄)₃‐OA were investigated. The crystalline structure and morphology of as‐obtained La(BF₄)₃‐OA were characterized by X‐ray diffraction, transmission electron microscopy, Fourier transform infrared spectrometry, and X‐ray photoelectron spectroscopy. Moreover, the tribological properties of La(BF₄)₃‐OA as an additive in dioctyl sebacate, a synthetic ester, were evaluated with a four‐ball machine, and the worn surfaces of the steel balls were analyzed with a field emission scanning electron microscope equipped with an energy dispersive spectrometer accessory. It was found that the as‐synthesized La(BF₄)₃‐OA exhibits disk‐like nanoflake shape and have a diameter of 10–45 nm, depending on varying synthetic conditions. As‐synthesized La(BF₄)₃‐OA as an additive in DIOS possesses excellent antiwear and friction‐reduction performance for the steel–steel pair, which is because the as‐synthesized additive simultaneously contain tribologically active elements La, B, and F that facilitate the formation of a boundary lubricating and protecting film on sliding steel surfaces thereby avoiding direct contact of the steel–steel pair and significantly reducing the friction and wear. Copyright © 2016 John Wiley & Sons, Ltd.