Poly(l‐lysine)‐graft‐poly(ethylene glycol): a versatile aqueous lubricant additive for tribosystems involving thermoplastics

The adsorption and aqueous lubricating behaviour of poly(l ‐lysine)‐graft‐poly(ethylene glycol) (PLL‐g‐PEG) have been investigated for tribopairs involving thermoplastic materials, including polypropylene, polyamide‐6,6 and polyethylene. A major finding is that PLL‐g‐PEG adsorbs onto both hydrophobic, non‐polar surfaces and hydrophilic, polar (negatively charged) surfaces from aqueous solution, and thus plays as a very unique and effective aqueous boundary lubricant additive for the sliding contact of thermoplastics against themselves as well as against many hydrophilic, polar materials, including metals (e.g. stainless steel) or ceramics (e.g. zirconia, ZrO₂). Copyright © 2007 John Wiley & Sons, Ltd.     

The Influence of Molecular Architecture on the Macroscopic Lubrication Properties of the Brush-Like Co-polyelectrolyte Poly(L-lysine)-g-poly(ethylene glycol) (PLL-g-PEG) Adsorbed on Oxide Surfaces

The co-polymer poly(L-lysine)-g-poly(ethylene glycol) (PLL-g-PEG) has been investigated as a potential biomimetic boundary-lubrication additive for aqueous lubrication systems. In this work, the influence of the co-polymer's architecture on its tribological performance has been investigated. The architectural parameters investigated comprise side-chain (PEG) length, Lys/PEG grafting ratio and backbone chain (PLL) length. The tribological approaches applied in this work include ultra-thin-film interferometry, the mini-traction machine (MTM), and pin-on-disk tribometry. Both an increase in the molecular weight of the PEG side chains and a reduction in the grafting ratio result in an improvement in the lubricating properties of aqueous PLL-g-PEG solution at low speeds. MTM measurements show that an increase in the molecular weight of the PLL backbone results in an increase of the coefficient of friction.     

Boundary Lubrication of Oxide Surfaces by Poly(L-lysine)-g-poly(ethylene glycol) (PLL-g-PEG) in Aqueous Media

In this work, we have explored the application of poly(L-lysine)-g-poly(ethylene glycol) (PLL-g-PEG) as an additive to improve the lubricating properties of water for metal-oxide-based tribo-systems. The adsorption behavior of the polymer onto both silicon oxide and iron oxide has been characterized by optical waveguide lightmode spectroscopy (OWLS). Several tribological approaches, including ultra-thin-film interferometry, the mini traction machine (MTM), and pin-on-disk tribometry, have been employed to characterize the frictional properties of the oxide tribo-systems in various contact regimes. The polymer appears to form a protective layer on the tribological interface in aqueous buffer solution and improves both the load-carrying and boundary-layer-lubrication properties of water.     

Self-healing behavior of a polyelectrolyte-based lubricant additive for aqueous lubrication of oxide materials

We report on the self-healing behavior of a polyelectrolyte-based aqueous lubricant additive, poly(l-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG), during aqueous lubrication of an oxide-based tribosystem. Combined pin-on-disk tribometry and fluorescence microscopy experiments have shown that stable lubricating performance was enabled by means of rapid healing of the worn tribopair surface by polymers dissolved in the adjoining bulk lubricant. This rapid ‘self-healing’ of PLL-g-PEG is attributed to electrostatic interactions between the polycationic poly(l-lysine) (PLL) backbone of the polymer and negatively charged oxide surface. In contrast, a similar healing effect was not readily achievable in the case of methoxy-poly(ethylene glycol)-trimethylsilylether (Sil-PEG), a lubricant additive that is covalently bonded to the surface prior to tribological stress.     

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.     

The hardnesses of poly(methylmethacrylate)

The paper describes an experimental study of the normal and scratch hardnesses of a poly(methylmethacrylate). The deformations have been introduced using hard steel cones of a range of included cone angles. The influence of the state of interfacial lubrication is examined and rationalized. The observed time dependence of the two types of computed hardness data is compared and the nature of the correlations between these data is evaluated. It is observed that when the imposed strains are modest, say less than 0.2, the scratch hardness and normal hardness deformations produce self consistent data using first order and rather indiscriminate analyses for both types of deformations. At higher levels of imposed strain, a more critical appraisal of the nature of the deformation produced in the two cases is necessary in order to provide mutually consistent hardness values and hence unequivocal rheological characteristics for this polymer.     

Pressure-dependence of dielectric relaxation time in poly(propylene glycol) and its application to high-pressure viscosity estimation

Dielectric permittivity and loss of poly(propylene glycol) with different molecular weights (400–3000) and terminal groups (OH and CH₃) have been measured in the frequency range of 100 Hz to 1.5 MHz. Measurements were conducted over the temperature range 202–293 K under atmospheric pressure and 283–320 K under pressure up to 600 MPa. Two relaxation processes, one with strong absorption in the high-frequency region (α-relaxation) and the other a weak process in the low-frequency region (α′-relaxation), were observed for the OH-terminated samples having molecular weights above 2000 and for all the CH₃-terminated samples. Most of the experimental data under high pressure showed a nonlinear decrease in the logarithm of the frequency of maximum dielectric loss with increasing pressure. The pressure-dependence of the dielectric relaxation time of the α-process was analyzed by several models based on the free-volume concept. The regression results of dielectric relaxation time as a function of pressure were applied to the estimation of high-pressure viscosity. The predicted viscosity showed relatively good agreement with viscosity data obtained from a falling-sphere viscometer.     

Tribological performance of poly(sodium 4‐styrenesulphonate) as additive in water–glycol hydraulic fluid

The tribological behaviour of poly(sodium 4‐styrenesulphonate) (PSS) as additive in the base fluid of water–glycol hydraulic fluid was evaluated with four‐ball machine and Optimol SRV‐IV (Optimol Instruments, Munich, Germany) oscillating friction and wear tester, and its viscosity‐enhancing performance was also investigated. The results show that PSS exhibits excellent friction‐reducing and anti‐wear properties in the base fluid and can significantly improve the latter's welding load and viscosity. The worn surfaces were characterised by scanning electron microscope and X‐ray photoelectron spectroscopy. The analytical results of typical elements on the worn surfaces demonstrate that PSS molecules adsorb on the rubbing surface and form a stable chemically absorbed film through the interactions between the sulphonate anions and surface metallic atoms during the sliding process, which contributed to improve the tribological properties of the base fluid. Copyright © 2012 John Wiley & Sons, Ltd.     

Scratch properties of poly(methyl methacrylate) surfaces: The time‐temperature dependence of friction and hardness

Viscoelastic‐viscoplastic behaviour is usually not taken into account in models describing the scratch properties of polymeric surfaces. In the case of a standard indentation test with stationary tip, the elastic‐plastic boundary and the boundary of the region being subjected to hydrostatic pressure beneath the tip are understood. Such well‐known models have been used in this study to understand the geometry of the groove left on the surface of a viscoelastic‐viscoplastic body by a moving diamond tip. A new apparatus was built that can control the velocity of the tip over the range 1 μm/s to 15 mm/s, at several different temperatures from −10 to +100°C. The material used was a commercial grade of cast poly(methyl methacrylate) (PMMA). The normal and tangential loads and groove size were used to evaluate the dynamic hardness, which behaved like a stress‐ and temperature‐activated process. The values for the activation energy and volumes of the dynamic hardness and of the interfacial shear stress were in good agreement with the mechanical properties usually attributed to PMMA.     

Morphological study on thermal treatment and degradation behaviors of solution-grown poly(l-lactide) single crystals

Morphological changes of solution-grown crystals (SGCs) of poly(l-lactide) (PLLA) following thermal treatment and enzymatic degradation were investigated using atomic force microscopy in terms of defects in the crystals. PLLA SGCs were grown from a dilute solution of acetonitrile at 5 °C. The obtained solution-grown monolamellar crystals have a lozenge-shaped morphology containing unique dimensions, with one side measuring 12 μm. To investigate enzymatic degradation behavior, PLLA SGCs were incubated in buffered solution with proteinase-K at 37 °C. The initial stage of enzymatic degradation of PLLA SGCs with proteinase-K occurs in loosely folding chains at the surface of the crystal. Thermally treated PLLA SGCs below the melting temperature showed an increase of the lamellar thickness of the SGCs at the treated temperature and partial surface erosion following enzyme exposure. These results indicate that less ordered chains exist throughout the lamellae and their thermal-induced chain extension makes them more susceptible to enzyme attack.     

Electrically conducting polymers: preparation and investigation of oxidized poly(acetylene) by EFTEM

Energy-filtering transmission electron microscopy (EFTEM) was used to demonstrate that the oxidation of poly(acetylene), necessary to produce a highly conducting phase, proceeds homogeneously on a scale of 100 nm to several micrometres. The distribution of the anions BF₄⁻ and PF₆⁻ serves as indicator for the penetration of poly(acetylene) by the oxidizing agent. The sample preparation necessitates prevention of sample degradation by air and moisture. It was possible to synthesize, orientate, oxidize, embed and section poly(acetylene) samples under inert conditions. Only mounting of the grids into the sample holder of the electron microscope was performed under ambient conditions. EFTEM was possible for phosphorus and boron, but not for fluorine owing to irradiation damage leading to loss of fluorine from the sample. Polyvinylbutyral was chosen as the embedding medium because it allows embedding of the sample prior to oxidation. Embedding of a previously oxidized poly(acetylene) sample leads to migration of the anions from the interior of the sample into the embedding medium.     

Synthesis and characterization of iron(III) oxide/polyvinyl chloride/poly(methyl methacrylate) nanocomposites

Polyvinyl chloride/poly(methyl methacrylate) blended and iron(III) nanoparticle polyvinyl chloride/poly(methyl methacrylate) nanocomposites were prepared by solution casting. The iron(III) oxide nanoparticles were prepared using a sol-gel procedure and their particle size was less than 200 nm. Scanning electron microscopy showed that no phase separation occurred and polyvinyl chloride and poly(methyl methacrylate) were miscible. Scanning electron microscopy also showed that the iron(III) oxide nanoparticles were dispersed well within the polymer blend. Thermogravimetric analysis showed three stages for the thermal degradation for polyvinyl chloride/poly(methyl methacrylate) blend and the iron(III) oxide/polyvinyl chloride/poly(methyl methacrylate). The second degradation was possibly due to dehydrochlorination during the thermal degradation of polyvinyl chloride in the blend system. Young’s modulus of the iron(III) oxide nanoparticle filled nanocomposites was from 1987.7–2471.6 MPa, which was higher than polyvinyl chloride/poly(methyl methacrylate) blend (1955.5 MPa). The stress yield (47.9–51.8 MPa) of the iron(III) oxide nanoparticle composites was higher than pure polyvinyl chloride/poly(methyl methacrylate) (47.0 MPa). The cyclic voltammograms of the pure blend and the nanocomposites were compared.     

Mechanical and tribological properties of poly(hydroxyethyl methacrylate) hydrogels as articular cartilage substitutes

Poly(hydroxyethyl methacrylate) (p(HEMA)) hydrogels have been proposed as promising biomaterials to replace damaged articular cartilage. A major obstacle to their use as replacement bearing tissue is their poor mechanical properties in comparison with healthy articular cartilage. The purpose of this study was to obtain p(HEMA) hydrogels with physicochemical and mechanical properties close to healthy articular cartilage, by introducing a hydrophilic monomer, namely acrylic acid (AA). Formulations of hydrogels with different amounts of hydrophilic monomer (acrylic acid, AA) were synthesized and tested: p(HEMA), p(HEMA-co-5%AA), p(HEMA-co-25%AA). The macro-mechanical tests were reproduced at nanoscale in order to verify if the superficial properties of the hydrogels are similar to the bulk ones.     

Antennal sensilla of Eucryptorrhynchus chinensis (Olivier) and Eucryptorrhynchus brandti (Harold) (Coleoptera: Curculionidae)

Eucryptorrhynchus chinensis (Olivier) (Coleoptera: Curculionidae) and E. brandti (Harold) (Coleoptera: Curculionidae) are the two most important pests of tree‐of‐heaven, Ailanthus altissima (Mill.) Swingle and its variety Ailanthus altissima var. Qiantouchun in China. They are also considered potential biological control agents for tree‐of‐heaven in North America. In this study, the external morphologies and antennal sensilla of both species were examined using scanning electron microscopy to better understand their host‐finding mechanisms. Eleven morphological sensilla types were recorded, that is, Böhm bristles, six types of sensilla chaetica (Sch. 1–6), two types of sensilla basiconica (Sb. 1–2), and two types of sensilla trichodea (St. 1–2). Sch. 5 were absent from the antennae of E. chinensis, while Sch. 2 were absent from the antennae of E. brandti. Abundant cuticular pores were present on the antennae of both species. Three types of sensilla on the antennae of E. chinensis that were not found in a previous study, and ten different types of sensilla on the antennae of E. brandti were identified for the first time. The possible functions of the sensilla types are discussed based on a comparison with previous studies. Four types of sensilla (Sb. 1, Sb. 2, St. 2, and Sch. 6) on the antennae of both species indicate chemoreception may play a significant role in host location. Microsc. Res. Tech. 76:968–978, 2013. © 2013 Wiley Periodicals, Inc.     

Adsorption properties of aqueous methylene blue on mesocellular foam silica: Equilibrium,kinetic, isotherm,and thermodynamic characterization

Abstract

Mesocellular foam silica was prepared by a hydrothermal synthesis protocol. The surface and pore structure of mesocellular foam silica were characterized by low temperature nitrogen adsorption isotherms, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and Fourier transform infrared (FT-IR) spectroscopy. The methylene blue was adsorbed by the synthetic mesocellular foam silica; the optimized adsorption conditions were evaluated and the maximum adsorption capacity of methylene blue by mesocellular foam silica was determined to be 215.5?mg g^?1. The kinetics of the adsorption of methylene blue by mesocellular foam silica were in accordance with a quasi-second-order kinetic equation. The results were analyzed by Langmuir and Freundlich adsorption isotherm models. The adsorption of methylene blue on mesocellular foam silica was shown to follow the Freundlich adsorption isotherm model. The Gibbs free energy change during adsorption showed that this process was spontaneous. The enthalpy change in the process was –28.868?J·mol^?1 K^?1, indicating that the adsorption is exothermic. The negative value of entropy –49.296?J·mol^?1 K^-1 shows that the system disorder decreases due to adsorption.     

智能支持的LC-QDPDS集成模型关键技术应用研究

质量驱动产品设计(QDPD)是一种产品设计新思想，在分析QDPD国内外研究现状的基础上，建立了智能支持的基于全生命周期质量驱动产品设计系统(LC-QDPDS)的集成模型，详细论述了LC-QDPDS集成模型的五大重要组成模块及其实现的关键技术，并将其应用于仪表新产品开发决策支持系统中。     

End-grafted Sugar Chains as Aqueous Lubricant Additives: Synthesis and Macrotribological Tests of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-lysine)-<Emphasis Type="Italic">graft</Emphasis>-Dextran (PLL-<Emphasis Type="Italic">g</Emphasis>-dex) Copolymers

Comb-like graft copolymers with carbohydrate side chains have been developed as aqueous lubricant additives for oxide-based tribosystems, in an attempt to mimic biological lubrication systems, whose surfaces are known to be covered with sugar-rich layers. As adopted in the previous studies of the graft copolymer poly(l-lysine)-graft-poly(ethylene glycol) (PLL-g-PEG), which showed both excellent lubricating and antifouling properties, a similar approach was chosen to graft dextran chains onto the same backbone, thus generating PLL-g-dex. PLL-g-dex copolymers readily adsorb from aqueous solution onto negatively charged oxide surfaces. Tribological characterization at the macroscopic scale, either under pure sliding conditions or a mixed sliding/rolling contact regime, shows that PLL-g-dex is very effective for the lubrication of oxide-based tribosystems. The relative lubricating capabilities of PLL-g-dex copolymers compared with PLL-g-PEG copolymers were observed to be highly dependent on the molecular structure of the copolymers (in particular, side-chain density along the backbone) and the measurement conditions (in particular, time between tribocontacts); the PLL-g-dex copolymers with a low degree of grafted side chains (≤20% grafting of available protonated primary amine groups along the backbone) showed better lubricating performance than their PLL-g-PEG counterparts at high tribocontact frequency (≥ca. 0.32 Hz).