Phase Behavior and Lubricity of Aqueous PEO-PPO-PEO and PPO-PEO-PPO Triblock Copolymer Solutions

Aqueous triblock copolymer solutions are potential low-cost, eco-friendly lubricants. However, as a solution, their phase changes with copolymer concentration and solution temperature, raising the question, “Does the phase change affect the formation of adsorbed layer and the lubrication performance?” This article studies the copolymer solution phase behavior and lubricity in response to the copolymer structure, concentration, and solution temperature. Four different triblock copolymers, two normal PEO-PPO-PEO and two reverse PPO-PEO-PPO composed of PEO poly(ethylene oxide) and PPO poly(propylene oxide), have been investigated. From cloud point and surface tension measurements, phase change and micellization are shown to depend on copolymer type, number of hydrophilic PEO blocks, and temperature. Furthermore it is found that the phase and the presence of micelles lead to significant variation in adsorbed copolymer mass and lubricity. Based on the observed phase behaviors, the lubricity of copolymer solutions is discussed with regard to aggregation and adsorption on the solid–liquid interface.     

Thickness and scratch resistance of adsorbed film formed by triblock symmetrical copolymer solutions

The thickness and scratch resistance of adsorbed films formed on mild steel samples (MS1020), which have been immersed in water copolymer solutions, are reported. The effects of bulk temperature and the copolymer structures, normal, poly(ethylene oxide)_m‐poly(propylene oxide)_n‐poly(ethylene oxide)_m, and reverse, poly(propylene oxide)_n‐poly(ethylene oxide)_m‐poly(propylene oxide)_n, are elucidated. The films' thicknesses are independent of structure but not of temperature. The adsorbed films of above cloud point solutions are thicker than below cloud point. However, nanoscratch experiments carried out to measure the scratch resistance of the films reveal that despite of thicker film formed by above cloud point solutions, it is relatively more prone to being detached than the thinner films of below cloud point solutions. The effect of extreme pressure additive, alkyl phosphate ester (APE), is also investigated suggesting the normal copolymer has comparable scratch resistance with APE when used at below the cloud point. Copyright © 2016 John Wiley & Sons, Ltd.     

Fundamental Understanding of Environmental Effects on Adhesion and Friction: Alcohol and Water Adsorption Cases

Layers of adsorbed vapor molecules have profound impacts on adhesion and friction. This article reviews fundamental aspects of alcohol and water adsorption effects on adhesion and friction. Capillary force, a component of adhesion force which arises from the liquid meniscus that forms between contacting surfaces, shows a strong vapor partial pressure dependence that is not explained by theory which neglects the adsorbed layer. Theoretical calculations accounting for the adsorbed layer give good agreement with experimentally measured adhesion forces at the nanoscale. Nanoscale friction measurements are also strongly affected by the meniscus and adsorbed layer. Conventional contact mechanics theory could not fully explain the load dependence of nanoscale friction, especially at vapor partial pressures below saturation. However, when the effect of the meniscus is included in theoretical analysis of experimental data, it is found that the friction depends on the shear strength change in the contract area and the dragging of the meniscus formed around the contact. The meniscus dragging term is dominant at low loads but becomes inconsequential at higher loads. When the adsorbed layer assumes structural ordering or causes tribochemical reactions, their adhesion and friction behaviors are further complicated and deviated from simple contact mechanics.     

Adsorption and lubricating properties of HFBII hydrophobins and diblock copolymer poly(methyl methacrylate-b-sodium acrylate) additives in water-lubricated copper vs. a-C:H contacts

In a metal forming process the adhesion between the workpiece and the tool needs to be minimised, which can be achieved by use of lubricants and coatings. Here adsorption and lubrication properties of HFBII hydrophobins and diblock copolymer poly(methyl methacrylate-b-sodium acrylate) in water-lubricated copper vs. a-C:H coating contacts were studied by Surface Plasmon Resonance (SPR) and by a pin-on-disc (POD) tribometer. Hydrophobins formed a dense monolayer film on a-C:H surface and reduced friction by 13–30% but increased the wear of copper compared to pure water lubrication. Poly(methyl methacrylate-b-sodium acrylate) formed a sparse lubricating layer compared to HFBII lubricated contacts, but the friction coefficient was lower. HFBII molecules prevented copper oxide tribofilm formation on the copper pin.     

Morphology and protein adsorption characteristics of block copolymer surfaces

Biocompatible polymers are known to act as scaffolds for the regeneration and growth of bone. Block copolymers are of interest as scaffold materials because novel, structurally diverse polymers can be synthesized from biocompatible blocks. Block copolymer nanostructure and surface morphology is easily tunable with synthetic techniques and the diverse nanostructures can be used to affect cell and tissue behaviour. In this paper, we present atomic force microscopy studies on the morphology and corresponding protein adsorption behaviour of a novel class of methyl methacrylate and acrylic acid diblock and triblock copolymers. The topography, phase angle and adhesion maps were obtained to study the morphology. Atomic force microscopy imaging reveals that the diblock and triblock copolymers present distinct nanomorphologies, although their chemical composition is the same. This has implications on the role of nanomorphology in cell-polymer interactions independent of chemical composition. Protein adsorption on a biomaterial surface is critical to understanding its biocompatibility and bovine serum albumin was used to model that behaviour on the block copolymer surfaces. An increase in the adhesive force of the surface was observed to correlate with the adsorption of bovine serum albumin on the block copolymer surfaces investigated.     

耐候钢表面保护性锈层与基体结合强度的研究

耐候钢曝晒4a后，表面生成了致密锈层，降低了基体的大气腐蚀速率。基于锈层／基体界面结合强度对基体的保护作用有直接影响，通过界面在承受压载时的受力分析，建立数学模型，计算出界面结合强度。结果表明：曝晒3a后锈层与基体的结合强度最好。     

An ESCA study of the effectiveness of antiwear and extreme‐pressure additives based on substituted phosphorodithioate derivatives,and a comparison with ZDDP

Ashless substituted dithiophosphoric acid derivatives (ADPs) are a new generation of multifunctional additives with promising antiwear (AW) and extreme‐pressure (EP) characteristics. Three such additives synthesised in the authors' laboratory have been evaluated for their AW and EP properties by standard four‐ball friction and wear tests. The friction‐reducing properties of these additives were compared with those of a commercial zinc dialkyldithiophosphate (ZDDP). It was found that the phosphorodithioate compounds studied here possessed excellent AW/EP properties. Their AW characteristics were found to be comparable to those of ZDDP at low loads. However, at higher loads they show inferior AW characteristics in comparison to ZDDP. Nevertheless, ADP derived from cashew nut shell oil had a higher load‐carrying capacity than ZDDP. The mechanism of the AW and EP behaviour exhibited by the different additives was investigated using X‐ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and scanning electron microscopy (SEM) of the worn surfaces formed during friction. XPS and AES analyses of the worn surfaces reveal that the tribochemical film formed on the ADP‐tested surfaces consisted mainly of metal phosphates and only a small amount of metal sulphides, even though the ADPs contained twice the number of sulphur atoms than phosphorus atoms. The ZDDP‐tested surface showed a mixture of metal sulphides and metal phosphates. Alkylamino substitution appeared to have no significant effect on the AW/EP properties of the additive. XPS and AES analyses also revealed that the tribochemical film formed on an ADP‐tested surface was thicker than that present on the ZDDP‐tested surface at low loads, whereas at higher loads the reverse was true. The higher weld load obtained for the blend containing cashew nut shell oil‐derived ADP is attributed to the thicker adsorbed reaction film formed on the surface due to the long alkyl groups present in the original additive structure. Short‐chain alkyl groups, however, form only a thin adsorbed layer, which may get rubbed off during the friction at high load. The low sulphide formation on ADP‐tested surfaces was attributed to the absence of any metal atom in the additive, which would help in the formation of metal sulphides during tribofragmentation and further tribochemical reactions.     

钢/玻璃的摩擦磨损性能动态观测研究

本实验在自行设计的摩擦磨损动态观测实验机进行,摩擦副之间的接触采用球一盘式接触。研究表明：当以较低速度滑动时,钢球表面的氧化物起到抗磨作用;滑动速度达到一定值时,氧化膜的生成速度小于氧化膜的磨损速度,摩擦表面为粘着磨损;当滑动速度继续升高时,摩擦表面的活化能增加,氧化加速．又出现氧化磨损;而滑动速度过高时,粘着磨损成为主要磨损形式,同时由于磨粒的作用,表面也发生疲劳磨损和磨料磨损．致使磨损急剧增加;表面层在摩擦热导致的高温条件下,氧化膜的生成速度又有所增加,氧化磨损为主要形式。     

Mechanical and Tribological Properties of Ca/P-Doped Titanium Dioxide Layer Produced by Plasma Electrolytic Oxidation: Effects of Applied Voltage and Heat Treatment

Plasma electrolytic oxidation (PEO) is a technique that produces a hard oxide layer on the titanium surface where its properties can be tailored by changing the process parameters or by a posterior heat treatment (HT). In this work, a TiO₂ layer with different crystallinity was produced by PEO with different applied voltages (250 to 400 V) and post-HT at 600°C. Our aim was to evaluate the influence of the PEO voltage and HT on the mechanical and tribological properties of anodized Ti. There is an increase in pore size, oxide thickness, and Ca/P ratio for the oxide layer with the applied voltage during the PEO process. X-ray diffraction (XRD) results indicated an increase in the crystalline rutile phase in the oxide layer with voltage and HT. Nanoindentation shows an increase in the oxide hardness and elastic modulus with increased voltage and HT, leading to an improvement in the wear resistance.     

Surface and Tribological Chemistry of Water and Carbon Dioxide on Copper Surfaces

The tribological chemistry of carbon dioxide and water vapor is studied on copper surfaces at high pressures, with a view to understand the gas-phase lubrication of copper–copper sliding contacts. The adsorption and film formation properties are studied on vapor-deposited copper films in an ultrahigh vacuum chamber using a quartz crystal microbalance. The nature of the reactively formed film is studied after reaction by ex situ X-ray photoelectron spectroscopy (XPS). Carbon dioxide adsorbs reversibly on copper, while water vapor adsorbs both reversibly and irreversibly, where XPS reveals that the irreversibly formed film consists of a mixture of cuprous oxide/hydroxide. Measuring the thickness of the cuprous oxide/hydroxide film as a function of water vapor pressure and temperature reveals that its thickness varies between about 6 and 14 Å and is proportional to the total amount of water adsorbed on the surface. This results in a cuprous oxide/hydroxide film that is thinner at higher temperatures. Measurements of the friction coefficient as a function of temperature and pressure in the presence of water vapor shows that it correlates with film thickness, reaching a limiting value of ~0.35 for thicker films.     

A study of structure and properties of molecularly thin methanol film using the modified surface forces apparatus

A novel approach for studying the adsorption and evaporation processes of molecularly thin methanol film by the modified surface forces apparatus (M‐SFA) is reported. This method can be used precisely to measure the thickness, morphology, and mechanical properties of the film confined between two mica surfaces in a real‐time manner at gas atmosphere. By observing the adsorption and evaporation processes of the methanol molecule, it is found that the first adsorbed layer of the methanol film on the mica surface behaves as a solid‐like structure. The thickness of this layer is measured to be about 3.2 Å, approximately equal to the diameter of a methanol molecule. Besides, this first adsorbed layer can carry normalized loads of more than 5.6 atm due to the carrying capacity conserved by the bond of mica‐OH. The outer layers of the methanol film are further adsorbed with the increase of the exposure time, which are liquid‐like and can be easily eliminated out from the substrate. The present study suggests that the interacting mode between hydroxy and mica is of great potential in material science and biomedical systems. Microsc. Res. Tech. 77:851–856, 2014. © 2014 Wiley Periodicals, Inc.     

Influence of ionic strength on the tribological properties of pre-adsorbed salivary films

We have studied tribological properties of pre-adsorbed salivary films formed in vitro on compliant hydrophobic surfaces. The adsorbed salivary film significantly decreases boundary friction under physiological ionic strength, which is related to a hydrophilic character of the adsorbed film and its structure. Decrease in the ionic strength below physiological conditions affects film’s structure, but it does not significantly affect boundary lubrication at low loads. Applications of high loads led to a gradual loss of lubrication due to shear-induced wear of the films. The wear became more extensive as the ionic strength of the solvent was lowered below physiological conditions.     

Anti-oxidant mechanism of TiAlN/SiN decorative films on borosilicate glass by magnetron sputtering

The black TiAlN decorative film was prepared on the borosilicate glass by the magnetron sputtering in equipment with multiple vacuum chambers. The transparent SiN protective layer was deposited on the surface of the TiAlN film to keep the black color invariant at the high temperature. The structure of the TiAlN/SiN film was characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HRTEM). The coating adhesion was measured by scratch tester. The TiAlN film has a columnar crystal structure with a thickness of 200 nm, and the top SiN layer is amorphous with a thickness of 100 nm. The coated borosilicate glass with the TiAlN/SiN films still retains the black color after oxidation at 600 °C in atmosphere. While the oxidation temperature elevates to 700 °C, the color of the TiAlN/SiN films begins to change. The top SiN layer plays a role as the barrier against oxygen diffusion into the inner TiAlN layer. The thin self-formed aluminum oxide layer was generated on the surface of the SiN layer and it contributes to the improvement of anti-oxidant property of the inner TiAlN layer. However, the thick self-formed aluminum oxide layer leads to the color change of the black TiAlN film. The thermal oxidation benefits the improvement of the adhesion for the TiAlN/SiN films with glass substrate.     

Reaction layer formation on bronze with an S-P extreme pressure additive in boundary lubrication under increasing load: I

An extreme pressure film formed on a phosphor bronze sliding against hardened ball-bearing steel with an S-P compound in mineral oil was examined. Film formation under boundary lubrication with continuously increasing load was observed using surface analytical methods. The concentration of tin in the reaction layer was found to be more enhanced than that of other elements. The segregation of phosphorus and tin showed good correlation but the sulphur distribution in the film was distinctly different. The film formed was often thick, up to 20 μm. Such a film had poor lubricity and weak strength against shearing.     

Thin-Film Properties of Some Functionalized Perfluoropolyether Boundary Lubricants Based on the n-Perfluoropropylene Oxide Monomer Unit

The thin-film properties of some perfluoropolyether boundary lubricants based on hydroxyl-termination of the n-perfluoropropylene oxide monomer units are investigated as a function of molecular polarity. The n-perfluoropropylene oxide monomer units provide a stiffer main chain than perfluoropolyethers comprised of a copolymer of perfluoro-methylene oxide and -ethylene oxide monomer units. Terraced flow and bonding kinetics show that the stiffer main chain reduces lubricant mobility on the disk surface but provides a lower profile lubricant film. The lack of mobility attributed to the main chain can be compensated for by decreasing the number of OH end groups. The Hamaker constants, derived from surface energy vs. thickness measurements are larger than the corresponding flexible main chains, suggesting an increased adhesion to the underlying carbon surface.     

高结合力工模具TiN涂层的制备

本文分析了电弧离子镀TiN涂层各工艺参数的相互关系,提出了以镀膜温度为主控参数的工艺设计思路;探讨了TiN涂层膜/基结合强度与涂层组织结构的关系和制备高结合力涂层的技术方法。     

Speed‐ and topography‐dependent boundary friction characteristics of steel

A novel tribometer that undergoes significant changes at ultra‐slow (>5.0 µm s⁻¹) to moderate (<20 cm s⁻¹) sliding speeds was developed in order to study the friction‐speed characteristics of steel lubricated with oil. Three different surface topographies were applied to the specimens, and the friction characteristics with an additive‐free base oil (MO91) and a stearic acid‐formulated oil (StA/MO91) were studied to understand the effects of surface textures on the lubrication performance of an adsorbed molecular layer formed by StA. Friction reduction behaviour of the adsorbed layer observed in the transverse direction was attributed to microscopic hydrodynamic action that maintained the load‐carrying performance of the adsorbed layer. Copyright © 2010 John Wiley & Sons, Ltd.     

Tribological performance of sulfonamide derivatives as lubricating oil additives in the diester

The load‐carrying capacity, anti‐wear and friction reduction properties of two sulfonamide derivatives added to a synthetic lubricant (diester) were evaluated using a four‐ball test machine. The results indicate that both additives possess good load‐carrying capacities and excellent anti‐wear and friction reduction properties. The surface topography of the rubbed surface was investigated by scanning electron microscopy, and the chemical nature of the anti‐wear films generated on the steel counter‐face was investigated by X‐ray photoelectron spectroscopy. Surface analysis results show that a stable lubricating film consisting of the reaction layer and adsorption layer was formed on the worn surface. Copyright © 2006 John Wiley & Sons, Ltd.     

Intermetallic formation and its relation to interface mass loss and tribology in die casting dies

Due to high metal injection velocities typical of die casting process, oxide film on die surface breaks exposing virgin steel surface to liquid aluminum at 680 °C. This paper describes in detail the fundamental tribochemical basis for the soldering and mass loss phenomena related to this steel-cast metal interaction. Cylindrical plain H13 coupons are dipped in hot liquid aluminum, kept for predetermined times, cleaned and characterized for surface and substrate changes. The thermodynamics behind the formation of intermetallic compounds based on Gibb’s free energy calculations are presented. Adhesive strength of soldering layer is determined through pull tests on casting solidified around the test pin. From these results, a dissolution–adhesion wear model is proposed for the growth and dissolution of intermetallics and soldering. In addition, this paper includes the soldering and adhesion behavior of nitrided surfaces. It is seen that the diffusion barrier treatment prevents soldering formation and provides for reduced friction and adhesion at the interface.     

20G钢在高含Cl~-乙二醇溶液中的腐蚀机理研究

通过高压釜试验研究了20G钢在高含Cl-乙二醇溶液中的腐蚀行为,用能谱(EDS)及X射线光电子能谱(XPS)对腐蚀产物膜进行成分分析,试验结果表明:20G在乙二醇溶液中生成的钝化膜较薄,其主要成分为Fe2O3,FeOOH。在溶液中水的作用下,由于氧化膜溶解,形成阳离子层促使钝化膜形成。在闭塞区,当孔内溶解的电流密度大于溶解产物由孔内向孔外的传质速度,腐蚀性加强。