The growth of shear bands in polystyrene

Shear-band growth velocities have been determined as a function of stress and temperature in polystyrene. The results demonstrate that shear bands can propagate under isothermal conditions; an adiabatic temperature rise at the shear band tip is not necessary for continued localization and growth of the band. The velocity is stress activated with a shear activation volume of 4600 ų and thermally activated with an activation enthalpy of 2.8 eV. Comparison of these values of the activation parameters with those for bulk shear flow in polystyrene indicates that the shear band propagation is controlled by the plastic strain rate of the glassy polymer immediately ahead of the tip of the band. Argon's molecular kink model of the elemental deformation process is consistent with measured values of the activation parameters whereas Bowden and Raha's dislocation model is not. The shear bands grow at an angle of ca. 38° to the axis of compression, and if the direction of compression is altered, the shear bands will change direction so as to maintain the 38° angle. Current explanations can not quantitatively account for the large deviation of the shear bands from the 45° plane of maximum shear stress.     

Craze and crack growths in polycarbonate

Craze and crack growth have been studied in polycarbonate. The results are correlated by a stress intensity factor derived from fracture mechanics. A new model taking creep into account is proposed to explain the experimental results. Theoretical predictions derived from the model are compared with experimental results. Fair agreement is obtained.     

聚合物的银纹研究进展

综述了国内外有关聚合物银纹研究的进展,内容包括银纹的定义、分类、引发、生长、断裂及结晶聚合物中银纹的情况。     

Electron microscopic investigations of initiation and growth of crazes in polystyrene

The crazes in polystyrene (PS) were investigated by using a high voltage electron microscope (HVEM, accelerating voltage of 1000 kV). The early stages of the formation and the growth of the crazes were studied in detail.The smallest deformation structures visible are weak domains or microvoids with diameters of 10–15 nm and distances of a few 10 nm between them. They act as craze nuclei and are located in narrow, long pre-craze zones. Conclusions are drawn on the processes of initiation and propagation of the crazes; both are based on molecular heterogeneities and on an increasing heterogeneity of deformation. In particular, the transformation of the closed cell structure of the voids into the open cell structure of the craze fibrils is described.Growth of crazes in thickness definitely occurs by drawing new polymeric material from the craze boundaries into the craze.     

Affinity chromatography of fibroblast growth factors on substituted polystyrene

The heparin-binding growth factors aFGF and bFGF (acidic and basic fibroblast growth factor) from crude bovine brain extract were co-eluted with purified [125I]aFGF and/or [125I]bFGF as tracers from heparin-Sepharose and from several insoluble substituted polystyrenes used as stationary phases in low-pressure affinity chromatography. The ability of the resins to isolate FGFs was determined by measuring the eluted radioactivity. It was demonstrated that the various substituted polystyrene resins retain [125I]aFGF and [125I]bFGF with different specificities according to the chemical nature of the substituted groups bound to the polystyrene support. Bifunctional resins substituted with sulphonate and phenylalanine sulphamide groups adsorbed both [125I]aFGF and [125I]bFGF whereas bifunctional resins substituted with sulphonate and sulphamide serine adsorbed only [125I]bFGF. These stationary phases could be adapted to high-performance affinity chromatography and used to isolate growth factors of the FGF family.     

Initial growth process of polystyrene particle investigated by AFM

We carried out molecular-scale and in situ investigations of the initial growth process of polystyrene particles in soap-free polymerization, where a cationic initiator, V-50, was used to make the formed particles transfer onto the mica plate in sampling, using an atomic force microscope. It was found that the particles coagulated soon after the nucleation process. Such coagulation was estimated from a macroscopic research, however; microscopic evidence was not enough. This study verifies it from a microscopic view.     

Ar atom emission as a probe of craze formation and craze growth in polystyrene

A report of measurements of Ar emission during the loading of polystyrene and high impact polystyrene in vacuum is presented. Argon was introduced into the material prior to the experiment by storing the samples in an Ar atmosphere. The development of crazes during loading was monitored by videotaped visual observations and scattered light measurements. Increased Ar emission is observed at the onset of crazing, provided that the crazes intersect the surface. The strength of the Ar signal depends upon the extent of crazing; especially intense signals are observed from samples which display significant crazing prior to fracture. High-impact polystyrene shows intense emissions at yield which soon decay due to the depletion of Ar from the near surface material. The emission intensity rises again prior to fracture, when surface crazes become connected to crazes in the bulk. Thus the emission of volatile species during deformation reflects the growth of crazes intersecting the surface, as well as changes in the “connectivity” of the craze network. © 1993 John Wiley & Sons, Inc.     

Craze fibril extension ratio measurements in glassy block copolymers

The extension ratios of crazes in triblock copolymer films of poly(2-vinylpyridine)-polystyrene-poly(2-vinylpyridine) [PVP-PS-PVP] which had lamellar microphase domain structure were measured by transmission electron microscopy. The extension ratio when the lamellae were oriented parallel to the craze fibril direction was always greater than that when the lamellae were oriented perpendicular to this direction, reflecting the stretching of the chains of the block copolymer in a direction normal to the interfaces of the lamellar domains.     

Craze fibril structure and coalescence by low-angle electron diffraction

Brown has shown that low-angle electron diffraction (LAED) may be used to determine fibril diameters D and spacings D₀ of crazes in thin polymer films. He found, however, that the D and D₀ determined for air crazes in polystyrene (PS) thin films were larger by about a factor of 3 than those in PS bulk crazes determined by using small-angle x-ray scattering (SAXS). We have repeated Brown's LAED experiments and find that the discrepancy may be caused by an aging effect. Our fresh crazes have D and D₀ values from LAED that are comparable to those of bulk PS crazes determined by SAXS. As the craze ages, however, fibrils retract and coalesce in wide regions of the craze, leading eventually to an observable “skin.” Aged crazes thus have much larger D and D₀ values than do fresh crazes. The large molecular mobility of the PS molecules in the fibrils necessary for this aging to occur at room temperature has important implications for fibril failure.     

Crystallization kinetics of isotactic polystyrene. I. Spherulitic growth rate

The spherulitic growth rate of isotactic polystyrene has been measured in a wide range of temperature by means of a polarizing microscope provided with a hot stage. It was possible to fit the experimental data to theory by choosing a value of 75 for the constant C₂ of the WLF equation. The growth rate parameters were compared with those of polyethylene and polychlorotrifluoroethylene. The slowness of crystallization of isotactic polystyrene is mainly a consequence of the lower mobility of the molecules caused by the bulky phenyl groups.     

The crystalline core of the row structures in isotactic polystyrene. I. Nucleation and growth

The nucleation and growth of the crystalline core in the row structures of isotactic polystyrene were investigated by transmission electron microscopy. The number of core crystals, nucleated at a specific temperature, depends on the external strain. Their length was found to increase with time if the sample is kept at the straining temperature. If a strained sample is cooled to room temperature and subsequently reheated, no further growth of the core crystals is observed. Obstacles in the path of growth were circumvented by local changes of the growing direction. Melt-soluble noncrystallizable molecules are rejected by the growing core into the surrounding melt. The observations suggest a growth mechanism of the cores based on the successive self-induced alignment of molecules at the tip of the growing cores.     

Synthesis of Ag-coated polystyrene colloids by an improved surface seeding and shell growth technique

In this paper, an improved surface seeding and shell growth technique was developed to prepare Ag-polystyrene core shell composite. Polyethyleneimine (PEI) could act as the linker between Ag ions (Ag nanoparticles) and polystyrene (PS) colloids and the reducing agent in the formation of Ag nanoparticles. Due to the multi-functional characteristic of PEI, Ag seeds formed in-situ and were immobilized on the surface of PEI-modified PS colloids and no free Ag clusters coexist with the Ag “seeding” PS colloids in the system. Then, the additional agents could be added into the resulting dispersions straightly to produce a thick Ag nanoshell. The Ag nanoshell with controllable thickness was formed on the surface of PS by the “one-pot” surface seeding and shell growth method. The Ag-coverage increased gradually with the increasing of mass ratio of AgNO₃/PS. The optical properties of the Ag-PS colloids could be tailored by changing the coverage of Ag.     

Craze initiation in poly(methyl methacrylate) under biaxial stress

Criteria for craze initiation in poly(methyl methacrylate) have been investigated under various combined loadings including biaxial tension and torsion-compression at 65°C in air and at room temperature in a crazing agent, kerosene. Environmental crazes are observed even under torsion-compression loading when air crazing does not occur, and the stress locus for environmental crazing is very different from that for air crazing. A theoretical model analogous to the Cottrell model in crystal plasticity is proposed. Theoretical crazing loci derived from the model are compared with the experimental results.     

Surface and interfacial segregation in blends of polystyrene with functional end groups and deuterated polystyrene

The effect of chain-end chemistry on surface and interfacial segregation in symmetric blends of polystyrene (hPS)/deuterated polystyrene (dPS) has been investigated by X-ray photoelectron and secondary ion mass spectroscopy in conjunction with neutron reflectivity measurements. Alpha,omega-fluoroalkyl- and alpha,omega-carboxy-terminated polystyrenes (alpha,omega-hPS(Rf)2 and alpha,omega-hPS(COOH)2) were used as end-functionalized polymers; the former possesses chain ends with lower surface energies, and the latter possesses higher surface energies compared with that of the main chain. In the case of an alpha,omega-hPS(Rf)2/dPS blend film, alpha,omega-hPS(Rf)2 was enriched at the surface owing to the surface localization of the Rf groups, although the surface energy of the hPS segments was slightly higher than that of the dPS ones. On the contrary, in the case of an alpha,omega-hPS(COOH)2/dPS blend film, dPS was preferentially segregated at the surface. This may be due to a surface depletion of COOH ends and an apparent molecular weight increase of alpha,omega-hPS(COOH)2 produced by a hydrogen-bonded intermolecular association of COOH ends in addition to the surface energy difference between hPS and dPS segments. Interestingly, both Rf and COOH chain ends were partitioned to the substrate interface for the alpha,omega-hPS(Rf)2/dPS and alpha,omega-hPS(COOH)2/dPS blend films, resulting in the segregation of the hPS component at the substrate interface for both blends. The results presented imply that surface and interfacial segregation in polymer blends could be regulated by incorporating functional groups into the end portions of one component.     

Craze-initiation kinetics in polystyrene

In this study it is shown, for a commercial polystyrene grade, that the strain-rate dependence of craze initiation is equivalent to that of yielding. This implies that the kinetics of craze initiation are determined by the nonlinear flow behavior, and that the actual cavitation process is governed by an additional, apparently rate-independent, criterion. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2066–2073, 2004     

First normal stress difference-temperature dependence for polystyrene and high-impact polystyrene melts

The method of reduced variables or superposition is applied to investigate the first normal stress difference (N₁)-temperature dependence over the shear rate (γ) range 10–1000 s^?1 for polystyrene (PS) and high-impact polystyrene (HIPS) melts, at temperatures of 180 C and above. These conditions are similar to those for industrial polymer processing. For PS, the first normal stress differences are obtained using Tanner's equation, leading to good agreement with values obtained by other authors and methods. For HIPS we have not found data in the literature for N₁ at shear rates above 10s^?1. In our case N₁ was obtained by measurements of entrance pressure losses. Correlations, based on master curves, are found for first normal stress difference in terms of shear rate and temperature. All samples follow the power law equation $\text{N}{}_1\text{= k}\text{γ}\text{?}{}^{\mathrm{m}}$, with values of m ranging from 0.50 to 0.64.     

Monodisperse micron-sized cross-linked polystyrene particles. VI. Understanding of nucleated particle formation and particle growth

 The procedure of nucleated particle formation and particle growth in dispersion polymerization was studied with the intention of understanding the production of monodisperse polystyrene particles cross-linked with urethane acrylate (UA). The time required for the formation of primary particles was determined exactly from the turbidity measurement of the reaction mixture with the polymerization time. It could be found that differing from conventional divinyl cross-linkers, such as divinylbenzene, UA had a boundary concentration where the association and coagulation of preformed nuclei with other oligomers and/or nuclei effectively took place until the primary particle formed. Similarly to linear polystyrene particles, the particle number density of the primary particles cross-linked with UA remained constant to the final particles. This observation verifies the suggestion that the primary particles cross-linked with UA readily absorbed the monomers from the medium during the stage of particle growth. Received: 31 August 1999 Accepted: 7 January 2000