Characterization of micro- to macroscopic deformation behavior of amorphous polymer with heterogeneous distribution of microstructures

In the present study, we clarify the micro- to macroscopic deformation behavior of an amorphous polymer with a slightly heterogeneous distribution of molecular chains; in other words, the distribution of the initial shear strength of the polymer. The micro- to macroscopic deformation behaviors of polymer under macroscopically uniform tension and shearing, uniaxial extension of a plane strain block and surface deformation of the plane strain block under compression were investigated by means of computational simulation with the nonaffine molecular chain network model. The results revealed the onset of microscopic shear bands emanating from slightly weak points and their evolution, and the interaction and percolation of new shear bands. The effects of distribution patterns and standard deviation of initial shear strength on the deformation, the interaction of weak points, the transition from microscopic shear band formation to macroscopic neck propagation and the evolution of surface undulation under compression have been demonstrated.     

OCP粘度指数改进剂分子结构对剪切安定性能的影响

采用高温高剪切仪和超声波剪切仪对OCP粘度指数改进剂的剪切安定性能进行了测试,并将分析结果与粘度指数改进剂的分子结构进行了关联,发现随着分子量的增加,剪切安定性能下降,随着分子量分布增宽和高分子链中丙基序列的增加,高温高剪切条件下的剪切安定性能下降,而超声波剪切条件下的剪切安定性能增加.从高分子的立体化学结构层次进行了结构与性能关系的分析.     

Experiment and computer simulation of particulate suspensions under shear flow

In this paper is described the role of molecular simulation as a useful quasi-‘experimental’ tool to help in understanding the interplay between molecular structure under shear flow and the manifested tribology/rheology. The development of non-equilibrium molecular simulation techniques are discussed, from the molecular dynamics approach through to the modelling of dispersions by brownian dynamics. Recent advances and extensions of the technique to weakly flocculated systems, such as electro-rheological fluids, are described.     

Double-Newtonian rheology in a model piston-ring cylinder-wall contact

In automotive engines, lubricants have undergone important changes over the last decades. Oil companies have added more and more additives to ensure correct performance of specific engine contacts, whilst increasing engine performance. Polymer additives are amongst these, used to increase viscosity at high temperatures and thus to flatten the viscosity temperature curve. This viscosity increase occurs at low shear rates, but at high shear rates the viscosity diminishes and tends to a lower value.This viscosity reduction at high shear rate is due to the distortion and alignment of the polymer molecules, and their breakage for extreme shear rates.This paper analyses the influence of the double Newtonian rheology on friction and load carrying capacity in a model piston ring cylinder wall contact. It is found that the friction coefficient changes with increasing shear rate, as the contact goes through the non-Newtonian transition.     

Energy Efficient Siloxane Lubricants Utilizing Temporary Shear-Thinning

This study investigates the rheologic properties, elastohydrodynamic film, and friction coefficients of several siloxane-based lubricants to assess their shear stability and their potential for energy efficient lubrication. Several siloxane-based polymers with alkyl, aryl, and alkyl-aryl branches were synthesized in order to examine the relationship between their molecular structures and tribological performance. Nuclear magnetic resonance spectroscopy and gel permeation chromatography were used to characterize the molecular structures and masses, respectively. Density, viscosity, elastohydrodynamic film thickness, and friction measurements were measured from 303 to 398 K. Film thickness and friction measurements were made at loads and speeds that cover the boundary, mixed, and full film lubrication regimes. These results illustrate that the shear characteristics of siloxane lubricants vary significantly with polymer length as well as branch structure and content. The findings provide quantitative insight into the features of siloxane molecular structure conducive to optimum film formation with minimum wear and elastohydrodynamic friction to enhance energy efficiency.     

半流体脂的流变性与润滑机理研究

半流体脂由于其独特的流变性，兼具有润滑油与脂的优点而获得越来越广泛的应用。本文利用毛细管粘度计和ＲＶ２型流变仪研究了半流体脂的弹流润滑机理。     

Dependence of the friction process on the molecular structure and architecture of thin polymer films

The frictional properties of a homologous series of poly(n-alkyl methacrylates) (PnAMA) and a series of poly(methyl methacrylate) (PMMA) films, cast from a variety of solvents, are characterized. The choice of polymer film was driven by the consideration of the possible mechanisms for the accommodation of a macroscopically applied shear stress by molecular entities. Two possible mechanisms are proposed: (i) the relative flexibility of the polymer backbone chain. For this purpose the PnAMAs have been chosen. By varying the length of the substituent chain, the relative molecular freedom around the backbone chain is altered. These molecular differences are sensed in the frictional properties at the macroscopic level, and (ii) the molecular organization is also proposed to be a factor in determining the friction response of a particular polymer film. For this purpose, the frictional properties of PMMA films cast from different solvents are investigated. There is observed to be a strong influence of the molecular organization on the frictional properties of the solvent cast PMMA films. The molecular probe employed to characterize the molecular environment is vibrational spectroscopy. Conformationally sensitive vibrational modes are used to determine the relative flexibility of the backbone chain and the organization of the chain network.     

Study of Permanent Shear Thinning of VM Polymer Solutions

The ultrashear viscometer (USV) has been adapted and employed to investigate the permanent shear thinning of polystyrene solutions in a series of phthalate ester base fluids. The permanent shear stability index based on viscosities measured at 10⁶ s^?1, PSSI(10⁶), has been found to be a convenient way to express the magnitude of permanent shear thinning. When comparing permanent shear thinning at various shear rates in the USV, it is very important to take account of the different times of shear that are present at different shear rates. The PSSI(10⁶) value divided by the total time of shear is then a useful way of quantifying and comparing permanent shear thinning rates. Tests using polystyrene in different viscosity base fluids have shown that this rate of permanent shear thinning depends on shear stress and not shear rate and varies linearly with polymer concentration. The rate of permanent shear thinning also varies exponentially with shear stress, suggestive of a stress-promoted polymer breakdown process. By using a small volume of test fluid in the USV and solvent extraction after a test, it has proved possible to obtain molecular weight distributions of polymer after shear using gel permeation chromatography (GPC). This indicates that the polymer breakdown process is different at low and high polymer concentrations, with molecule fragmentation at low polymer concentration but mid-chain scission at high concentration. A key feature of the USV is that, unlike other methods currently used to measure permanent shear thinning behaviour of engine oils, it subjects the test fluid to well-defined, controllable high shear conditions. Coupled with the use of GPC, this makes it possible for the first time to relate quantitatively the permanent shear thinning of engine oils to shear conditions and to polymer degradation response.     

碳纳米管直径对丁腈橡胶复合材料性能影响的分子模拟

利用分子动力学模拟研究碳纳米管(CNTs)直径改变时对丁腈橡胶(NBR)基体力学及摩擦学性能的影响。采用恒应变法考察不同复合材料模型的力学性能，结果表明复合材料力学性能随着NBR基体中CNTs直径增大呈现先增加后减小的趋势。剪切模拟结果表明，剪切后复合材料基体中分子链发生了不同程度的断裂，出现了聚合物分子链向摩擦界面聚集的现象，其中较大直径CNTs增强NBR复合材料中分子链相对完整连续，摩擦学性能改善效果更好。较大直径CNTs对NBR基体具有显著的增强效果，限制了NBR分子链的活动能力，更多的分子链聚集在CNTs周围，复合材料体系致密性及稳定性提高，从而改善了CNTs/NBR复合材料力学及摩擦学性能。其中直径(6,6)CNTs增强NBR复合材料具有更高的剪切模量，力学性能优异，表现出了更好的摩擦磨损性能。     

Bio‐lubricant flow behaviour in mini‐channels

One of the most common causes of failures in total joint replacements is the generation of wear particles within the joint. This contributes to bone lost and aseptic loosening of the implant, eventually requiring its replacement. Many studies have been carried out to improve the wear characteristics of bearing surfaces in total joint replacement. From the lubrication point of view, the friction behaviour of surfaces and rheology of the joint lubricant (synovial fluid) have been extensively studied. However, little attention has been paid to the interaction between the lubricant and the bearing surfaces. The aim of this study is to develop a methodology for studying the behaviour of bio‐based lubricant in mini‐channels. For this purpose, micro‐particle image velocimetry was used in order to characterise the lubricant behaviour. Channels made of relevant materials such as ultra‐high molecular weight polyethylene, cobalt–chromium–molybdenum alloy and titanium–aluminium–vanadium alloy with 1 and 1.5 mm width, 45 mm length and 2 mm depth were experimentally investigated. Results suggested that the used polymeric solution interaction with solid surfaces is very sensitive to the polymer concentration in the lubricant. Moreover, it was observed that there exist differences between water (Newtonian reference fluid) and the polymeric solution behaviour even at very simple movements; although usually, the properties of this lubricant at high shear rates are estimated by water properties. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of viscosity index improver,molecular weight,and base oil on thickening,shear stability,and evaporation losses of multigrade oils

Some SAE 15W‐40 multigrade oils were formulated, using polymethacrylate (PMA) viscosity index improvers of different molecular weights, with a mixture of N 150 and N 500 as the base oil. Kinematic and dynamic viscosities, borderline pumping temperatures, pour points, shear stability, and evaporation losses were measured. The results confirm that viscometric properties as well as shear stability depend strongly on the polymer concentration and molecular weight of the VI improvers. However, evaporation losses are dominated by the volatility properties of the base oil.     

Investigation of the Tribological Behaviors of Polymer Molecular Deposition Films by Tribometer Based on Interferometer

The polymer molecular deposition films including polyelectrolyte molecular deposition (PEMD) film and nanoparticles composite molecular deposition (NPs/MD) film have been prepared using the molecular deposition method and the in situ synthesize method. The polymer molecular deposition films were characterized by atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). The tribological behaviors of the substrate and polymer molecular deposition films were investigated by a tribometer based on interferometer. It is found that the NPs/MD film has a lower friction force and a better anti-wear property than the PEMD film under the dry friction. The poly alpha olefin (PAO2) and water films confined between samples and steel ball surfaces have been investigated using thin film interferometry. The friction force of substrate was lower than the polymer molecular deposition films under PAO2 lubrication. The friction forces alteration of PEMD film and NPs/MD film were similar and consistent, and lower than that for substrate under water lubrication.     

Structures,solvation forces and shear of molecular films in a rough nano-confinement

Investigations of surface roughness effects on the structure, dynamics and rheology of a molecular fluid (hexadecane) confined between solid (gold) surfaces, through the use of large-scale molecular dynamics simulations, reveal a remarkable sensitivity to the confining surface morphology. A most significant reduction of the ordering propensity is found in films confined by stationary rough surfaces with a consequent strong suppression of solvation forces and the development of liquid-like dynamic and response characteristics. When the rough-surface boundaries are set in motion at a high shear rate, the interfacial layers of the film stick to the adjacent solid boundaries, resulting in partial slip inside the film with the development of shear stress in the viscous molecular fluid, unlike the case of atomically flat crystalline boundaries where slip of the confined film at the boundaries is accompanied by vanishingly small shear stress in the film. These results are discussed in the context of the effect of roughness on the boundary conditions used in modeling fluid flow past surfaces, and they suggest that morphological patterning of surfaces could provide ways for controlled modifications of frictional processes in thin-film lubricated nanotribological systems.     

Tribology of confined Fomblin-Z perfluoropolyalkylethers: molecular weight dependence and comparison between unfunctionalized and telechelic chains

The dynamic shear properties of molecularly-thin films of unfunctionalized and end-functionalized (telechelic) Fomblin-Z perfluoropolyalkylether (PFPAE) melts with number-average molecular weight M _n≈ 3000−4000 g,mol^-1 have been studied at shear rates of 10^-2−10⁵ s^-1 at normal pressures of 1 and 3 MPa. The shear responses are compared to measurements on end-functionalized polymers of the same chemical composition but lower molecular weight, M _n≈ 2000 g,mol^-1. The predominantly elastic response and high shear moduli of the confined film of unfunctionalized polymer, Fomblin Z03, suggest that it forms a structure likely to solidify already at low pressure. Its lubricating properties are less favorable than the ones found for hydroxyl- (DOL) and piperonyl-terminated Fomblin-Z (AM2001, AM3001), where associated molecules form a structure less prone to solidification under confinement. The thickness of the compressed films of the end-functionalized polymers increased more strongly with molecular weight than as M _n ^0.5 . The shear moduli were found to be larger, the higher the molecular weight, indicating slower relaxations. At a normal pressure of 3 MPa, these films solidified and displayed stick–slip as seen already at 1 MPa in the Z03 film. The limiting shear stress of the unfunctionalized Z03, σ > 3 MPa, exceeded by an order of magnitude the limiting shear stress of all of the end-functionalized polymers. The limiting shear stress of the hydroxyl-terminated polymer was larger than that of the piperonyl-terminated polymer. This revised version was published online in August 2006 with corrections to the Cover Date.     

Lubricant oils additivated with polymers in EHD contacts: Part 1. Rheological behaviour

This paper reports on the influence of a polymer additive on the traction behaviour of a mineral oil investigated using a two‐disc machine at different temperatures and contact pressures. A semi‐empirical approach was used for determining the effective lubricant rheological parameters ‐ the elastic shear modulus, the viscosity of the lubricant, and the limiting and Eyring stresses ‐ in elastohydrodynamic contacts. Using this approach, the effect of polymer concentration on the rheological parameters that appear in both the Johnson‐Tevaarwerk and Bair‐Winer models was quantified. The influence of operating conditions, such as pressure, oil temperature, and polymer concentration, on the traction coefficient, limiting shear stress (from the Bair‐Winer model), Eyring stress (from the Johnson‐Tevaarwerk model), shear modulus, and apparent viscosity was also investigated.     

Lubrication properties of non-adsorbing polymer solutions in soft elastohydrodynamic (EHD) contacts

The in-use performance and processing of many consumer products in the food, home and personal care industries are dependent on their tribological properties. A major component of these products is often a high molecular weight polymer, which is typically used to thicken aqueous systems. Polymer solutions tend to be non-Newtonian, and in particular their viscosity varies with shear rate, such that it is difficult to predict their friction or hydrodynamic film-forming behaviour. The present work relates the tribology of aqueous polymer solutions to their rheological properties in thin films in ‘soft’ contacts at high shear rates. The friction properties of three types of polymers in aqueous solution, polyethylene oxide, PEO; xanthan gum, XG; and guar gum, GG, have been studied as a function of polymer concentration over a wide range of entrainment speeds in a point contact formed between silicone rubber and steel. This has enabled the boundary lubrication and isoviscous-elastic lubrication properties of the solutions to be investigated using both hydrophilic and hydrophobic silicone surfaces.It is found that the friction vs. entrainment speed dependence follows the shape of a classical Stribeck curve. In general, a lower friction is observed with increasing polymer concentration in the mixed-regime. Using scaling factors for the entrainment speed, we have shown that this decrease in friction is likely to be due to viscous effects and that the scaling factors represent effective high shear rate viscosities. In the case of PEO and XG, and GG at low concentrations, a good correlation is found between this effective viscosity and the apparent viscosity measured at the highest shear rates attainable with the available rheometer. However, for GG at concentrations above 0.2%, the effective viscosity decreases with increasing polymer content.The three polymers do not significantly reduce friction in the boundary regime and in general give essentially the same response as water when an effective viscosity is taken into account. However, a slight increase in friction in comparison to pure water has been observed for XG and GG on hydrophobic surfaces. It is suspected that this may be due to a blocking of fluid entrainment, or possibly exclusion of polymer from the contact, due to the large hydrodynamic volume and rigid nature of the two biopolymers. Finally, for PEO solutions with full-film elastohydrodynamic conditions were reached, the measured friction coefficient of the film correlated quite well with the value calculated from the effective viscosity.     

New Insight into the Relationship Between Molecular Effects and the Rheological Behavior of Polymer-Thickened Lubricants Under High Pressure

The effects of temperature, pressure and shear stress on the viscosity of simplified automotive lubricants—polymer-thickened base oil solutions—were investigated. Various polymers—with different molecular weights and conformations (comb, linear and star)—were used at low concentration (1.2 % w/w) in a hydrocracked mineral base oil: a poly(alkylmethacrylate), an olefin copolymer and a poly(isoprene-styrene hydrogenated). Their rheological behavior was studied and modeled with a Vogel-Tamman and Fulcher equation, a modified Williams-Landel-Ferry-Yasutomi relationship and a Carreau-Yasuda-like formula. Then, the Einstein’s law was used to rapidly and simply determine the hydrodynamic radii of polymers as a function of temperature and pressure. Calculations from Flory equations, intrinsic viscosities and direct measurements confirmed the relevance of this methodology. Finally, molecular considerations allowed a good understanding of the rheological response of polymer solutions.     

Thixo forging process of wrought aluminum alloy fabricated by rotational helical shape stirrer

The manufacture of rheology materials from wrought and casting aluminum alloys using controlling solid fraction and crystal grain is demonstrated in this paper. The equipment to form the rheology material was designed so that shear force and applied pressure could be carefully and simultaneously applied using a mechanical stirrer. The problems caused by using this method with the thixo forging process were studied by investigating the mechanical properties of a sample that had a controlled solid fraction of 45–50 %.     

Nanotribological behavior of tethered reinforced polymer nanolayer coatings

We fabricated molecularly thick thermoplastic elastomeric films with organized microdomain structure and intriguing nanotribological properties. Molecular films from poly[styrene-b-(ethylene-co-butylene)-b-styrene] (SEBS) were obtained by a melt/solution grafting to a functionalized silicon surface modified with epoxy-terminated self-assembling monolayers. We varied the thickness of grafted block–polymer films from 1.35 nm (disordered polymer layer) to 9 nm (well defined nanophase structure) and tested their friction, adhesion, shear and wearing properties on a microscale with scanning probe microscopy. Tethered SEBS monolayers, composed of a rubber matrix reinforced by a two-dimensional net of glassy polystyrene (PS) microdomains, possess a friction coefficient as low as 0.02 and shear strength in the range 0.15–1.5 GPa. Chemically tethered SEBS monomolecular films are much more stable under shear stresses than conventional molecular coatings.     

The role of viscous deformation in the machining of polymers

This study aims to evaluate the machinability of typical thermoplastic and thermosetting polymers and understand the effect of their viscous properties on surface integrity, chip formation and machining forces. The interaction between the strain rate and temperature during machining was particularly addressed. It was found that the viscous deformation of a polymer plays a decisive role in determining the quality of a machined surface. To minimize the surface roughness, for instance, the machining conditions must be selected in such a way that the material removal deformation falls in the regime without visco-plastic scaling/tearing and brittle cracking. The optimal machining condition must be based on the polymer properties, such as the glass transition temperature, fracture toughness and molecular mobility. The shear stress in the shear plane of chipping is a good measure of the coupled effect of strain rate and temperature rise. In addition, the study discovered two new types of chips whose deformation and curling were in close relation to the surface integrity of the machined components.