A comparison of oxidation and oxygen substitution in MoS2 solid film lubricants

Significant advancements in the production of low friction, long wear life, sputter-deposited MoS₂ lubricant coatings have been made in the last decade. The introduction of multi-layered coatings, the establishment of careful controls on doping during DC and magnetron sputter deposition, and the implementation of ion assisted deposition have resulted in lubricants with substantially longer wear lives (up to a factor of ten greater than in the early 1980s) and lower sliding friction coefficients. A major research effort, designed to improve the performance of solid lubricants, involved a number of laboratories during this time period, resulting in these major breakthroughs. However, even with this concentrated effort, the typical investigation involved making an educated guess, based on previous experience, of the deposition conditions, target compositions, or post treatments that might be expected to provide improved performance of resulting coatings. One notable discovery during this time period was that typical MoS₂ films contain large quantities (up to 20 atom %) of oxygen substituted for sulfur in individual crystal lattices. In this paper we will compare the effects of this oxygen substitution with the effects of oxidation which involves a change in the oxidation number of the central molybdenum atoms within the crystals. A discussion of the relationship(s) between chemistry and coating structure and tribological performance will be presented with emphasis on defect chemistry and multiple phase interactions. Speculations on the role of coating chemistry in determining coating performance in applications such as in ball bearings will be presented.     

单层MoS2和WS2的太赫兹近场显微成像研究

采用太赫兹散射式扫描近场光学显微镜(THz s-SNOM)研究了化学气相沉积法制备的单层MoS₂和WS₂晶粒的太赫兹近场响应。在没有可见光激发时,未探测到可分辨的太赫兹近场响应,说明晶粒具有较低的掺杂载流子浓度。有可见光激发时,由于光生载流子的太赫兹近场响应,能够测得与晶粒轮廓完全吻合的太赫兹近场显微图。在相同的光激发条件下,MoS₂的太赫兹近场响应强于WS₂,反映了两者之间载流子浓度或迁移率的差异。研究结果表明,THz s-SNOM兼具超高的空间分辨率和对光生载流子的灵敏探测能力,对二维半导体材料和器件光电特性的微观机理研究具有独特的优势。     

Super-low friction of MoS2 coatings in various environments

The ultra-low friction coefficient (typically in the 10⁻² range) of MoS₂-based coatings is generally associated with the friction-induced orientation of ‘easy-shear’ planes of the lamellar structure parallel to the sliding direction, particularly in the absence of environmental reactive gases and with moderate normal loads. We used and AES/XPS ultra-high vacuum tribometer coupled to a preparation chamber, thus allowing the deposition of oxygen-free MoS₂ PVD coatings and the performance of friction tests in various controlled atmospheres. Friction of oxygen-free stoichiometric MoS₂ coatings deposited on AISI 52100 steel was studied in ultra-high vacuum (UHV: 5 × 10⁻⁸ Pa), high vacuum (HV: 10⁻³ Pa), dry nitrogen (10⁵ Pa) and ambient air (10⁵ Pa). ‘Super-low’ friction coefficients below 0.004 were recorded in UHV and dry nitrogen, corresponding to a calculated interfacial shear strength in the range of 1 MPa, about ten times lower than for standard coatings. Low friction coefficients of about 0.013–0.015 were recorded in HV, with interfacial shear strength in the range of 5 MPa. Friction in ambient air leads to higher friction coefficients in the range of 0.2. Surface analysis performed inside the wear scars by Auger electron spectroscopy shows no trace of contaminant, except after friction in ambient air where oxygen and carbon contaminants are observed. In the light of already published results, the ‘super-low’ friction behaviour (10⁻³ range) can be attributed to superlubricity, obtained for a particular combination of cystallographic orientation and the absence of contaminants, leading to a considerable decrease in the interfacial shear strength.     

Residual stresses in TiN, DLC and MoS2 coated surfaces with regard to their tribological fracture behaviour

Thin hard coatings on components and tools are used increasingly due to the rapid development in deposition techniques, tribological performance and application skills. The residual stresses in a coated surface are crucial for its tribological performance. Compressive residual stresses in PVD deposited TiN and DLC coatings were measured to be in the range of 0.03-4 GPa on steel substrate and 0.1-1.3 GPa on silicon. MoS₂ coatings had tensional stresses in the range of 0.8-1.3 on steel and 0.16 GPa compressive stresses on silicon. The fracture pattern of coatings deposited on steel substrate were analysed both in bend testing and scratch testing. A micro-scale finite element method (FEM) modelling and stress simulation of a 2 μm TiN-coated steel surface was carried out and showed a reduction of the generated tensile buckling stresses in front of the sliding tip when compressive residual stresses of 1 GPa were included in the model. However, this reduction is not similarly observed in the scratch groove behind the tip, possibly due to sliding contact-induced stress relaxation. Scratch and bending tests allowed calculation of the fracture toughness of the three coated surfaces, based on both empirical crack pattern observations and FEM stress calculation, which resulted in highest values for TiN coating followed by MoS₂ and DLC coatings, being K_C = 4-11, about 2, and 1-2 MPa m^1/2, respectively. Higher compressive residual stresses in the coating and higher elastic modulus of the coating correlated to increased fracture toughness of the coated surface.     

Tribological properties of ZrO2 (Y2O3)-Mo-BaF2/CaF2 composites at high temperatures

ZrO₂ (Y₂O₃) with different contents of BaF₂/CaF₂ and Mo were fabricated by hot pressed sintering, and the tribological behavior of the composites against SiC ceramic was investigated from room temperature to 1000 °C. It was found that the ZrO₂ (Y₂O₃)-5BaF₂/CaF₂-10Mo composite possessed excellent self-lubricating and anti-wear properties. The low friction and wear were attributed to enhanced matrix and BaMoO₄ formed on the worn surfaces.     

Study on the tribological properties of surfactant-modified MoS2 micrometer spheres as an additive in liquid paraffin

Tribological properties of MoS₂ micrometer spheres modified by self-prepared surfactant as an additive in liquid paraffin (LP) are studied and compared with those of the commercial colloidal MoS₂ on a four-ball tester and an Optimol SRV oscillating friction and wear tester. The worn surfaces are examined with SEM and XPS, respectively. Results show that MoS₂ micrometer sphere is a much better extreme-pressure additive and anti-wear and friction-reducing additive in LP than the commercial colloidal MoS₂. The boundary lubrication mechanism can be deduced as an effective chemical adsorption protective film formed by the long chain alkyl and active elements (S and N) in the prepared surfactant and tribochemical reaction film composed of the tribochemical reaction products of the additive. Moreover, sliding and rolling frictions exist simultaneously in the MoS₂ micrometer spheres /LP lubricating system, which also do more contributions to the good tribological properties.     

Study on rotational fretting wear of bonded MoS2 solid lubricant coating prepared on medium carbon steel

The rotational fretting wear behaviors of the bonded MoS₂ solid lubricant coating and its substrate steel were comparatively studied under varied angular displacement amplitudes, constant normal load, and rotational speed. Dynamic analysis in combination with microscopic examinations was performed through SEM, EDX, XPS, optical microscope, and surface profilometer. The experimental results showed MoS₂ changed the fretting running regimes of substrate. The friction coefficients of MoS₂ were lower than those of the substrate. For MoS₂, the damage in partial slip regime was very slight. The damage mechanism of the coating in slip regime was main abrasive wear, delamination, and tribo-oxidation.     

Sliding wear characteristics of plasma-sprayed Al2O3 and Cr2O3 coatings against copper alloy under severe conditions

Al₂O₃ and Cr₂O₃ coatings were deposited by atmospheric plasma spraying and their tribological properties dry sliding against copper alloy were evaluated using a block-on-ring configuration at room temperature. It was found that the wear resistance of Al₂O₃ coating was superior to that of the Cr₂O₃ coating under the conditions used in the present study. This mainly attributed to its better thermal conductivity of Al₂O₃ coating, which was considered to effectively facilitate the dissipation of tribological heat and alleviate the reduction of hardness due to the accumulated tribological heat. As for the Al₂O₃ coating, the wear mechanism was plastic deformation along with some micro-abrasion and fatigue-induced brittle fracture, while the failure of Cr₂O₃ coating was predominantly the crack propagation-induced detachment of transferred films and splats spallation.     

Tribological properties of Ni3Al-Cr7C3 composite coating under water lubrication

The tribological properties of Ni₃Al-Cr₇C₃ composite coating under water lubrication were examined by using a ball-on-disc reciprocating tribotester. The effects of load and sliding speed on wear rate of the coating were investigated. The worn surface of the coating was analyzed using electron probe microscopy analysis (EPMA) and X-ray photoelectron spectroscopy (XPS). The results show the friction coefficient of the coating is decreased under water lubrication. The wear rate of the coating linearly increases with the load. At high sliding speed, the wear rate of the coating is dramatically increased and a large amount of the counterpart material is transferred to the coating worn surface. The low friction of the coating under water lubrication is due to the oxidizing of the worn surface in the wear. The wear mechanism of the coating is plastic deformation at low normal load and sliding speed. However, the wear mechanism transforms to microfracture and microploughing at high load with low sliding speed, and oxidation wear at high sliding speed. It is concluded that the contribution of the sliding speed to an increase in the coating wear is larger than that of the normal load.     

Tribological behaviour and wear mechanism of MoS2–Cr coatings sliding against various counterbody

MoS₂–Cr coatings with different Cr contents have been deposited on high speed steel substrates by closed field unbalanced magnetron (CFUBM) sputtering. The tribological properties of the coatings have been tested against different counterbodies under dry conditions using an oscillating friction and wear tester. The coating microstructures, mechanical properties and wear resistance vary according to the Cr metal-content. MoS₂ tribological properties are improved with a Cr metal dopant in the MoS₂ matrix. The optimum Cr content varies with different counterbodies. Showing especially good tribological properties were MoS₂–Cr8% coating sliding against either AISI 1045 steel or AA 6061 aluminum alloy, and MoS₂–Cr5% coating sliding against bronze. Enhanced tribological behavior included low wear depth on coating, low wear width on counterbody, low friction coefficients and long durability.     

Modelling particulate erosion–corrosion regime transitions for Al/Al2O3 and Cu/Al2O3 MMCs in aqueous conditions

Very little research effort has been directed at development of models of erosion–corrosion of composite materials. This is because, in part, the understanding of the erosion–corrosion mechanisms of such materials is poor. In addition, although there has been a significant degree of effort in the development of models for erosion of MMCs, there are still difficulties in applying such models to the laboratory trends on erosion rate.In this paper, the methodology for mapping erosion–corrosion processes in aqueous slurries was extended to particulate composites. An inverse rule of mixtures was used for the construction of the erosion model for the particulate MMCs. The corrosion rate calculation was evaluated with reference to the matrix material.The erosion–corrosion maps for composites showed significant dependency on pH and applied potential. In addition, the corrosion resistance of the matrix material was observed to affect the regime boundaries. Materials maps were generated based on the results to show the optimum composite composition for exposure to the environment.     

一种纤维锌矿结构CuInS2纳米化合物的合成方法

CuInS2(CIS)是重要的三元Ⅰ-Ⅲ-Ⅵ族直接带隙半导体化合物光伏材料。纤维锌矿CIS的铜和铟原子共享一个晶格,因此其在化学计量比调控方面更加灵活,对高效太阳能电池具有重要意义。在低温条件下,通过简单高效的热注入法合成了在常温下能稳定存在的纤维锌矿CIS纳米化合物,并通过X射线衍射仪(XRD)、扫描电子显微镜(SEM)、X射线光谱仪(EDX)和紫外可见分光光度计(UV)分别对其晶相、形貌、化学计量比和能带值进行了分析。结果表明:合成的CIS纳米化合物呈纤维锌矿结构;能带值为1.47eV,非常接近最佳能带值;呈六边形纳米盘状,纳米盘厚度约为10nm,直径约为100nm;Cu∶In∶S的化学计量比为1.70∶1∶2.94。     

Influence of Al2O3 reinforcement on the abrasive wear characteristic of Al2O3/PA1010 composite coatings

In the present study, the abrasive wear characteristics of Al₂O₃/PA1010 composite coatings were tested on the turnplate abrasive wear testing machine. Steel 45 (quenched and low-temperature tempered) was used as a reference material. The experimental results showed that when the Al₂O₃ particles have been treated with a silane coupling agent (γ-aminopropyl-triethoxysilane), the abrasive wear resistance of Al₂O₃/PA1010 composite coatings has a good linear relationship with the volume fraction of Al₂O₃ particles in Al₂O₃/PA1010 composite coatings and the linear correlation coefficient is 0.979. Under the experimental conditions, the size of Al₂O₃ particles (40.5-161.0 μm) has little influence on the abrasive wear resistance of Al₂O₃/PA1010 composite coatings. By treating the surface of Al₂O₃ particles with the silane coupling agent, the distribution of Al₂O₃ particles in PA1010 matrix is more homogeneous and the bonding state between Al₂O₃ particles and PA1010 matrix is better. Therefore, the Al₂O₃ particles make the Al₂O₃/PA1010 composite coatings have better abrasive wear resistance than PA1010 coating. The wear resistance of Al₂O₃/PA1010 composite coatings is about 45% compared with that of steel 45.     

Tribological properties of molybdenum disulfide nanosheets by monolayer restacking process as additive in liquid paraffin

Molybdenum disulfide nanosheets were prepared by monolayer restacking process. Results of transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and scanning electron microscopy (SEM) showed that the obtained MoS₂ nanosheets had a thickness about 30-70 nm. The tribological properties of the so-prepared MoS₂ nanosheets were investigated on a MQ-800 four-ball tribometer. The results showed the base oil with MoS₂ nanosheets had better friction reduction, wear resistance and extreme pressure than those with commercial micro-MoS₂. The good tribological properties of MoS₂ nanosheets were mainly ascribed to the surface effect and the dimension effect of nanoparticles. Moreover, the formation of MoO₃ and FeSO₄ complex film on the rubbed surface also played an important role in friction reduction and wear resistance.     

High-temperature tribological properties of spark-plasma-sintered Al2O3 composites containing barite-type structure sulfates

Al₂O₃–50BaSO₄–20Ag, Al₂O₃–50BaSO₄–10SiO₂, Al₂O₃–50(mass%)SrSO₄, Al₂O₃–50PbSO₄–5SiO₂, Al₂O₃–50BaSO₄ and Al₂O₃–50BaCrO₄ composites (mass%) were prepared by spark plasma sintering and their microstructure and high-temperature tribological properties were evaluated. Al₂O₃–50BaSO₄–20Ag composites (mass%) showed the lowest friction coefficients at the temperature ranging from 473 to 1073 K. Thin Ag film was observed on the wear tracks of the composites above 473 K. In addition, the friction coefficients of Al₂O₃ composites containing SrSO₄ and PbSO₄ were as low as those of Al₂O₃–BaSO₄ and Al₂O₃–BaCrO₄ composites at the temperatures up to 1073 K. The thin films formed on the wear tracks of the Al₂O₃–SrSO₄ composites were composed of Al₂O₃ and SrSO₄ phases, while the films formed on the wear tracks of the Al₂O₃–PbSO₄–SiO₂ composites consisted of Al₂O₃, PbSO₄ and SiO₂ phases.     

钙硼硅系LTCC生瓷带在收/发组件中的应用

低温共烧陶瓷(LTCC)技术是实现机载、星载、舰载相控阵雷达收/发组件小型化、轻量化、高性能、高可靠的有效手段。由于技术落后,国内缺少商品化的微波LTCC材料,严重制约了LTCC技术的发展。文中对国产钙硼硅系LTCC生瓷带在X波段收/发组件中的应用进行了深入研究,分析了钙硼硅系LTCC生瓷带的工艺性能、浆料匹配性能以及微波性能,并采用国产钙硼硅系LTCC生瓷带研制了X波段收/发组件,性能指标满足相控阵雷达技术要求,为微波LTCC材料的国产化进行了有益的探索。     

Tribological performance of MoS2---B2O3 compacts

A recent investigation suggests that selected oxides perform well as additives in molybdenum disulphide (MoS₂) because of their ability to soften at asperity contacts with the result that the solid lubricant can attain and retain a preferred tribological orientation.This research determined the effectiveness of boric oxide (B₂O₃), when used as an additive in MoS₂, for substrate temperatures ranging from 21°C to 316°C. This range was used to allow the asperity contact temperature to vary below and above the softening point of B₂O₃. It was found that a moderate friction coefficient and high wear, which is attributed to the additive acting abrasively, occurred when the asperity contact temperature was well below the softening point of the oxide. When the asperity contact temperature neared the softening point of the oxide, the friction coefficient increased dramatically and wear volume was reduced. It is postulated that B₂O₃ acted adhesively at the interface resulting in a higher coefficient of friction, and wear decreased due to an attainment of a preferred orientation by the MoS₂. For asperity contact temperatures significantly above the softening point of B₂O₃, the friction coefficient returned to about the same value as for temperatures below the softening point. It is speculated that wear continued to increase moderately because of localized melting of the B₂O₃, permitting the MoS₂ to be removed from the interface. These observations support a hypothesis that an additive, such as boric oxide, can soften as the asperity contact temperature approaches the softening point temperature of the additive so that the overall tribological conditions may be improved resulting in reduced interfacial wear. Significant changes in temperature, load or sliding velocity would, of course, dramatically alter the wear characteristics observed at the interface.     

Characterization of nanoscale recording mark on Ge2Sb2Te5 film

We have fabricated nanoscale recording marks on Ge₂Sb₂Te₅ (GST) films with conductive atomic force microscope (AFM). GST films were deposited on glass or polyimide film with thickness of 150–200 nm by the rf–sputtering method. Through current–voltage (I–V) spectroscopy, good cantilevers for fabrication and characterization of nanoscale marks on GST were selected. A fresh and highly conductive tip showed voltage-switching characteristic in the I–V curve, where the threshold voltage was 1.6 V. Nanoscale dot and wire arrays of crystalline phases were successfully obtained by varying sample bias voltage from −10 to 10 V. With highly conductive tips, nanowires having full-width at half-maximum of 20 nm could be fabricated, whereas nanowires could not be fabricated with bias voltage below −2 V. The width of the nanoscale mark was increased by repetition of AFM lithography even with same applied voltage and lithography speed. For a thicker nanowire, the width measured in current-image (C-image) was observed to be 2 times of that measured in topography-image (T-image). This result supports that current sensing provides an image of phase-changed GST area with higher resolution than topography sensing.     

Preparation of TiO2 nanowire gas nanosensor by AFM anode oxidation

Applications of atomic force microscopy (AFM) to the fabrication of chemical nanosensors are presented in this paper. Using AFM cantilever as cathode, the surface of Ti thin film is oxidized to form a few tens of nanometers wide oxidized metal semiconductor wire, which works as a nanowire-based hydrogen sensor. The reaction mechanism is proposed. The AFM observations of fabrication of a TiO₂ nanowire are carried out. The sensitive characteristic of such TiO₂ nanowires to hydrogen is investigated.     

Tribological properties of spark-plasma-sintered ZrO2(Y2O3)-CaF2-Ag composites at elevated temperatures

Spark-plasma sintering is employed to synthesize self-lubricating ZrO₂(Y₂O₃) matrix composites with different additives of CaF₂ and Ag as solid lubricants by tailoring the composition and by adjusting the sintering temperature. The friction and wear behavior of ZrO₂(Y₂O₃) matrix composites have been investigated in dry sliding against an alumina ball from room temperature to 800 °C. The effective self-lubrication at different temperatures depends mainly on the content of various solid lubricants in the composites. The addition of 35 wt.% Ag and 30 wt.% CaF₂ in the ZrO₂(Y₂O₃) matrix can promote the formation of a well-covered lubricating film, and effectively reduce the friction and wear over the entire temperature range studied. The friction coefficients at low temperatures were at a minimum value for the composite containing 35 wt.% of silver. At this silver concentration, low and intermediate temperature lubricating properties are greatly improved without affecting high-temperature lubrication by the calcium fluoride in ZrO₂(Y₂O₃) matrix composites. The worn surfaces and transfer films formed during wear process have been characterized to identify the synergistic lubrication behavior of CaF₂ and Ag lubricants at different temperatures.