Quantitative modeling of scratch-induced deformation in amorphous polymers

In order to predict scratch performance of polymers, the present study focuses on quantitative assessment of various scratch-induced deformation mechanisms based on a set of model amorphous polymers via numerical modeling. A modification of Ree-Eyring theory is used to account for the rate dependent behavior of the model polymers at high strain rates using the experimental data obtained at low strain rates. By incorporating the rate and pressure dependent constitutive and frictional behaviors in the finite element methods (FEM) model, good agreement has been found between FEM simulation and experimental observations. The results suggest that, by including appropriate constitutive relationship and frictional model in the numerical analysis, the scratch behavior of polymers can be quantitatively predicted with reasonable success. Usefulness of the present numerical modeling for designing scratch resistant polymers is discussed.     

Plasticity/damage coupling in semi-crystalline polymers prior to yielding: Micromechanisms and damage law identification

This work addresses the question of the intimate coupling of plastic and damaging processes during the deformation of semi-crystalline polymers at small strains. The evolution of the spherulitic structure in the pre-yield strain range under tensile testing is investigated by atomic force microscopy for three semi-crystalline polymers, namely polycaprolactone, poly(1-butene) and polyamide 6. These materials have different spherulite size, crystallinity index and lamella thickness, and different glass transition temperature of the amorphous phase. Strain-induced damage is clearly evidenced through the gradual loss of elastic properties upon cyclic tensile tests, since the early stage of stretching. In parallel, volume strain appears to be about nil up to the yield point for the three polymers. AFM reveals that fragmentation of the crystalline lamellae occurs well before the yield strain at room temperature, starting about the core region of the spherulites and extending towards the periphery, for all polymers. This is claimed as evidence that lamella fragmentation is a basic mechanism of damage without significant cavitation at low strain. An approach of damage modeling is carried out via preliminary assessment of the viscoelastic contribution from low strain dynamic mechanical analysis using a generalized Maxwell model. It is shown that computing the viscoelastic contribution in the strain range up to yielding, in the assumption of linearity, fairly account for the loading-unloading hysteresis of the tensile cycles. A phenomenological plasticity/damage coupling law is established from the elastic modulus drop with increasing plastic strain, both assessed from the “relaxed” tensile cycles. The same kind of law is shown to apply for the three polymers. A physical meaning to the phenomenological law is proposed via a simple model of fiber rupture in single-fiber-reinforced composite.     

Effects of carbon black on tribology of blends of poly(vinylidene fluoride) with irradiated and non-irradiated ultrahigh molecular weight polyethylene

Friction and wear resistance are two vital tribological properties of polymer-based materials but optimization of both is rarely attempted. We have investigated blends of 70 wt% poly(vinylidene fluoride) (PVDF)+30% ultra high molecular weight polyethylene, the latter either un-irradiated or else γ-irradiated. Each sample contained varying amounts of carbon black (CB) and also had a varied degree of crosslinking and irradiation dose. We have determined static and dynamic friction, scratch resistance, and sliding wear in multiple scratching tests. Effects of the irradiation dose and CB concentration have been quantified. The electric conductivity threshold is reflected in a drop of static friction; formation of a continuous phase of the lubricant affects tribology as well as electrical properties—both for irradiated and for un-irradiated samples. The scratch resistance as represented by the residual (healing) depth is affected by crosslinking, by the stage at which irradiation is applied (before or after blending) and by CB addition. Crosslinking by moderate amounts of irradiation provides shallower residual depths while higher doses cause adverse results. Similarly, the CB lubricant can either improve or worsen the scratch resistance. A combination of both approaches produces either better or else worse results than crosslinking alone. Lower friction seems accompanied by higher scratch resistance. A combination of a specific irradiation dose and an optimized CB concentration lowers the sliding wear significantly. Strain hardening in sliding wear determination takes place for all materials studied, irrespective of the extent or radiation-induced crosslinking and of the presence and concentration of carbon black.     

Contact/scratch-induced surface deformation and damage of copper-graphite particulate composites

The elastoplastic surface deformation and damage under frictional sliding contact of copper-graphite particulate composites with Cu-content ranging from 0 to 40 vol% are examined in indentation and scratch tests using a load controlled test system. The contact areas in indentation and scratch tests are estimated with the Field-Swain approximation. The characteristic material parameters of the elastic modulus E′, yield stress Y, interfacial shear strength s, and the scratch resistance are discussed in relation to the Cu-content of the composites. The microscopic mechanisms and processes for the surface deformation and damage induced by frictional sliding contact are also examined. With the increase in the normal contact load, the scratch-induced surface deformation and damage are transiently followed with the sequential four stages: (I) the elastoplastic grooving, (II) plastic plowing, (III) microcracking, and (IV) the inter- and intra-fractures and chipping of graphite particles. The Cu-content in the composite plays the key role in controlling the characteristic contact pressures for these transitional deformation/damage processes.     

‘Stuffed’ conducting polymers

Conducting polymers (CP) obtained by oxidative polymerization using iron(III) salts shrink when Fe(II) and the excess counter ions are washed out after polymerization. This phenomenon can be used to incorporate active molecules into the CP matrix via their addition to the wash liquid. In the present work we demonstrate this principle on three different CP's: polypyrrole (PPy), poly-terthiophene (PTTh) and poly(3,4-ethylenedioxy thiophene) (PEDT), using ferrocene as a model molecule to be trapped in the polymer films.     

Compressive strength and damage mechanisms of 2D-C/SiC composites at high temperatures

Compressive strength of 2D-C/SiC composite was investigated from room temperature(RT) to 1600?°C at present work. Damage evolution was investigated by conducting loading/unloading tests at RT and the damage mechanisms were elucidated by observing the fracture morphology. It is found that compressive strength of 2D-C/SiC was retained until 1200?°C and then decreased with increasing temperature. The variation of compressive strength is closely related to the degradation in matrix modulus. The compressive damage of 2D-C/SiC starts at the buckling of 0° fiber and is followed by opening and closing of original pores, initiation and growth of longitudinal interbundle cracks, separation of 90° fiber bundles by longitudinal cracks, matrix cracking from intrabundle pores, propagation of matrix cracks into 0° fiber bundles, connection of cracks in 0° fiber bundles and longitudinal cracks in 90° fiber bundles.     

Recent advances in electrochromic polymers

Electrochromic polymers are attractive materials with enormous potential in the rapidly developing area of plastic electronics due to their flexibility, low-power consumption, ease of processing and low processing cost. Electrochromic devices created with electrochromic polymers are likely to be alternatives or supplements to the conventional inorganic electrochromic devices, which face challenges of durability and electrochromic properties. Several novel electrochromic polyimides, polyamides, and polynorbornenes prepared via polycondensation, ring-opening metathesis polymerisation (ROMP), etc., are introduced in this article. These various polymer species exhibit high thermal stability and mechanical strength.     

Automatic coarse graining of polymers

Several recently proposed semi-automatic and fully-automatic coarse-graining schemes for polymer simulations are discussed. All these techniques derive effective potentials for multi-atom units or super-atoms from atomistic simulations. These include techniques relying on single chain simulations in vacuum and self-consistent optimizations from the melt like the simplex method and the inverted Boltzmann method. The focus is on matching the polymer structure on different scales. Several ways to obtain a time-scale for dynamic mapping are discussed additionally. Finally, similarities to other simulation areas where automatic optimization are applied as well are pointed out.     

Structure of polymers in the vicinity of convex impenetrable surfaces: the athermal case

The influence of the presence of a curved (convex) solid wall on the conformations of long, flexible polymer chains is studied in a dense polymer system and in the athermal limit by means of lattice Monte Carlo simulations. It is found that the chain conformation entropy drives a reduction of the density at the wall, similar to the flat wall case. The chain end density is higher next to the interface compared to the bulk polymer (segregation), with the difference increasing with chain length. The wall curvature does not significantly affect the segregation. The bonds are preferentially oriented in the direction tangential to the wall. The distance from the interface over which this effect is observed is about two bond lengths. Similar results are obtained when probing the preferential orientation of chain segments. In this case, the perturbed region has a thickness on the order of the considered probing chain segment length. This suggests that experimental results on the thickness of the ‘bonded layer’ next to a wall depend on the wavelength of the radiation employed for probing. The chains are ellipsoidal in the bulk and rotate close to the surface with the large semi-axis of the ellipsoid normal to the line connecting their center of mass with the filler center. Since there is no energetic interaction with the filler, no adsorption transition is observed, but the chains tend to wrap around the filler once the gyration radius becomes comparable to the filler radius.     

Macroporous polymers from particle-stabilized emulsions

Macroporous polymers are attractive materials due to their low density, low cost, recyclability and tunable mechanical and functional properties. Here, we report a new approach to prepare macroporous polymers from emulsions stabilized with colloidal polymeric particles in the absence of chemical reactions. Stable water-in-oil emulsions were prepared using poly(vinylidene difluoride) (PVDF), poly(tetrafluoroethylene) (PTFE), and poly(etheretherketone) (PEEK) as stabilizing polymeric particles in emulsions. The partial wetting of the polymeric particles by the two immiscible liquids drives particles at the water-oil interface during emulsification, leading to extremely stable water-in-oil emulsions. The particle-stabilized emulsions were processed into highly porous solid polymer components upon drying and sintering. The high stability of emulsions also allows for the preparation of hollow polymeric microcapsules. We describe the conditions required for the adsorption of particles at the liquid-liquid interface, we show the rheological behavior of the polymer-loaded wet emulsions and, we discuss the effect of the emulsions' initial compositions on the final sintered porous structures. This new approach for the fabrication of macroporous PVDF, PTFE, and PEEK polymers is particularly suited for the preparation of porous materials from intractable polymers but can also be easily applied to a variety of other polymeric particles.     

Fatigue failure mechanisms in polymers

Fatigue testing of polymers has revealed significant differences between the fatigue response of polymers and metals. Generally, fatigue failure in metals is a process of crack initiation, propagation, and failure. Also, fatigue damage in metals is cumulative and cycle dependent, but remains essentially independent of test frequency. Unlike that of metals, the fatigue behavior of polymers is influenced by viscoelastic effects. At high frequencies, softening and melting occur, and fatigue failure depends largely on the test frequency. At lower frequencies, fatigue failure becomes less sensitive to test frequency and results from crack initiation and propagation. These polymer characteristics arise from the production of hysteresis energy during fatigue. A portion of this energy is released as heat, some of which is dissipated, but most is absorbed in the sample, raising its temperature. This temperature rise leads to degradation of the material and a short fatigue life. Experiments were conducted to measure hysteresis energy and temperature rise for a talc-filled polypropylene. A mathematical model was developed to calculate the energy and temperature distribution during fatigue. Correlation of the temperature rise predicted by the model with that observed experimentally provided values for the various energy terms that quantitatively defined the thermomechanical fatigue response of this polymer.     

耐火材料损伤蚀变研究的进展

简述了高温、化学腐蚀、热震和多种机械载荷对耐火材料损伤依变的影响；综述了陶瓷耐火材料冲击、磨损、热震、疲劳和慢速裂纹扩展方面研究的进展；讨论了综合破坏作用下材料的行为及模拟性试验。     

Diffusion of organic solvents in isobutylene-based polymers

Diffusion behavior of several organic solvents in polyisobutylene (PIB) and in poly(p-methylstyrene-co-iso-butylene) (PMS-BR) with different monomer ratios has been studied. The experiments have been conducted over a temperature range of 50 to 100°C using a conventional gravimetric Sorption technique. The PMS-BR copolymers contained 2, 7, and 15 weight percent p-methylstyrene, respectively. Although employing temperatures were far above the glass transition temperatures of polymers, the diffusion coefficients are correlated well with the Vrentas-Duda free-volume theory. For all the solvents, the PIB shows the highest diffusivity while the copolymer with the 15% p-methylstyrene gives the lowest value. This behavior can be explained by the amount of fractional free-volume present in a system.     

Post-synthetic modification of conjugated microporous polymers

Control over the surface functionality and microporosity in conjugated microporous polymers (CMPs) has been achieved by the post-synthetic modification of amines into amides of with different alkyl chains, one of which was chiral. The surface areas, pore volumes, carbon dioxide uptakes and isosteric heat of adsorption for carbon dioxide can be rationally tuned.     

Viscoelastic effects on the scratch resistance of polymers: relationship between mechanical properties and scratch properties at various temperatures

Scratch durability of polymer surfaces and coatings is becoming critical for the increasing use of these materials in new applications, replacing other materials with harder surfaces.

Scratch resistance of polymers has been the subject of numerous studies, which have led to specific definitions for plastic deformation characterization and fracture resistance during scratch testing. Viscoelastic and viscoplastic behavior during a scratch process have been related to dynamic mechanical properties that can be measured via dynamic nano-indentation testing. Yet, the understanding of the origin of the fracture process of a polymer during scratch remains approximate. Parameters like tip shape and size, scratch velocity and loading rate, applied strain and strain rates, have been considered critical parameters for the fracture process, but no correlation has been clearly established.

The goal of this work is to define and analyze scratch parameters that relate to mechanical properties. The evolution of scratch resistance parameters as a function of temperature and strain rate, compared to the evolution of dynamic mechanical properties obtained from indentation and uniaxial tensile tests over a range of temperature for poly(methyl methacrylate) (PMMA) helped in identifying a correlation between the tensile stress–strain behavior and scratch fracture toughness.

This correlation brings a new understanding of the origin of the fracture mechanisms during a scratch process. In particular, it is demonstrated that the characteristic strain applied by the indenter is a most relevant parameter to describe the fracture resistance during a scratch process, independently of the indenter geometry.     

柳钢炼钢厂混铁炉破损分析

通过对混铁炉（６００ ｔ） 使用中出现异常破损的剖析,查明了事故原因,并为今后炉子的施工设计及检修提供了科学依据,提出了相应的改进措施和建议。     

NLO-active polymers containing triazolo-thiadiazole segments

Polymethacrylate and polycondensated polymers based on chromophores containing the s-triazolo[3,4-b]-thiadiazole heterocycle were synthesized. Chromophore and polymer preparations are described. Second order NLO measurements are reported for polymers and for one functionalized chromophore. The maximum value of second harmonic generation coefficient (d₃₃) measured is 11.5 pm/V at incident laser wavelength of 1368 nm. For the most active polymer, 85% of the initial d₃₃ value is retained after 27 days at 80 °C.     

Brittle-ductile transition of polymer blends

Based on the Ludwik-Davidenkov-Orowan theory, a new criterion of BDT for polymer blends is proposed. In this approach fracture stress (_b) and shear yielding stress (_y) governing the brittle-ductile transition (BDT) of polymer blends is combined into a dimensionless group as D_a = _b ²/_y ². The theory dictates that BDT occurs at a critical condition D_ac = 1, brittle fracture occurs when D_a < 1, and ductile fracture occurs when D_a > 1. It can be shown that D_a = F_g · L_ym/L_D, where L_ym measures the length of shear band of the matrix, L_D is a parameter determined by the morphology and interfacial adhesion of dispersed phase, and F_g is related to specimen geometry and other extrinsic parameters. It is suggested that the onset of BDT depends on the competition between the L_ym and L_D. With due consideration to blend morphology, interfacial adhesion and matrix properties, existing experimental evidence supports the applicability of the proposed criterion.The project supported by FORD and NSFC No. 09415312     

Preferential adsorption coefficient of polymers

The recent formulation of the preferential adsorption coefficient, λ, which takes into account differences in molecular contact surface and in free volume, is tested by comparing theoretical with experimental values of λ from the literature. Seven different systems containing polystyrene and poly(methyl methacrylate) are considered. Agreement between theory and experiment is reached by treating the contact surface of the polymer as a fitting parameters, s. The adjusted values of s are: (a) systematically higher than the ones calculated from chain geometry; (b) largest in systems containing specific interactions (methanol). The connection between this enhanced apparent contact surface of the polymer and the ternary interaction parameter of the classical theory of λ, is analysed.     

Interlaminar damage in carbon fiber polymer-matrix composites, studied by electrical resistance measurement

Interlaminar thermal damage in continuous carbon fiber polymer-matrix composites was monitored in real time during thermal cycling by measurement of the contact electrical resistivity of the interlaminar interface. Damage was accompanied by an abrupt increase of the resistivity for a thermoset-matrix composite, and by an abrupt decrease of the resistivity for a thermoplastic-matrix composite. Both phenomena are due to the effect of matrix damage on the chance of fibers of one lamina touching those of an adjacent lamina. The damage involved matrix molecular movement in the thermoplastic case, but not in the thermoset case.