Experimental developments in different areas of polymer melt rheology and recent results are reviewed: Shear oscillations were performed with mixtures of polyisobutylenes (PIB) of relatively small molecular mass distributions and with blends of polystyrene (PS) and polymethylmethacrylate (PMMA). For the latter, the interfacial tension between the melts of PS and PMMA can be derived from the results. - In constant shear rate flow, the measurement of the first normal stress difference N1 in a commercial cone-and-plate rotational rheometer is simple if the test temperature is kept extremely constant. By a further modification a partial integral of the pressure distribution is measured from which the second normal stress difference N2 can be determined. - The molecular orientation in shear flow results in a rheological anisotropy that can be studied in a parallel-plate shear rheometer in which the polymer melt sample can arbitrarily be sheared in two perpendicular directions. - For melt elongation by rotary clamps constant, arbitrary ratios of the strain rate components can be applied. Planar elongations of the PIB samples indicate an influence of the width of the molecular mass distribution. More general elongations with a change of the strain rate ratio during the test are of especial interest as is documented by the comparison of the resulting stresses with predictions from different network theories. - In a rheometer for simple elongation at 170°C, recovery after melt extension of the PS/PMMA blends reveals a value of the interfacial tension equal to the one obtained from shear oscillations. 相似文献
Secondary flow (also termed as stagnation flow, dead space, recirculation zone, and vortex) is rheological phenomenon occurring during flow of polymer melts through abrupt contraction channels as result of flow separation from solid boundary leading to accelerating flow regime with recirculating material in corners. Polymer melt captured in secondary flow slowly rotates in direction opposite to main flow direction and simultaneously moves in third direction through helical motion. This may first reduce flow stability and second increase residence time initiating highly undesirable thermal degradation of polymer melt. Since the first visual experimental observation performed by Tordella and preliminary theoretical prediction made by Langlois and Rivlin at the end of the 1950s, this phenomenon represents one of the most fundamental rheological problems ever with many practical and theoretical impacts discussed here. This comprehensive review written in historical perspective summarizes key factors (Newtonian viscosity, shear thinning, viscoelasticity, flow geometry, and extensional viscosity) influencing secondary entry flows for polymer melts and provides deep and critical discussion of the most important experimental and theoretical works on this topic (such as branched low-density polyethylene, LDPE, linear low-density polyethylene, LLDPE, high-density polyethylene, HDPE, polystyrene, PS, isotactic polypropylene, PP, polymethyl methacrylate, PMMA, polyamide, Nylon PA 66, or polybutadiene, BR). 相似文献
This article reports the study of the effect of relative grafting densities of two polymer chains on solvent-induced self-assembly of mixed poly(methyl methacrylate) (PMMA)/polystyrene (PS) brushes through a combinatorial approach. Gradient-mixed PMMA/PS brushes were synthesized from a gradient-mixed initiator-terminated monolayer by combining atom transfer radical polymerization (ATRP) and nitroxide mediated radical polymerization (NMRP) in a two-step process. The gradient-mixed initiator-terminated monolayer was fabricated by first formation of a gradient in density of an ATRP initiator through vapor diffusion followed by backfilling of an NMRP-initiator-terminated trichlorosilane. After treatment of a gradient-mixed brush whose PS Mn was slightly lower than that of PMMA with glacial acetic acid, a selective solvent for PMMA, relatively ordered nanodomains were observed in the region where the ratio of PS to PMMA grafting density (number of polymer chains/nm2) was in the range from 0.67 to 2.17 and the overall grafting density was approximately 0.85 polymer chains/nm2. Contact angle hysteresis were high (> or =40 degrees ) in this region and XPS studies confirmed that the PMMA chains were enriched at the outermost layer. The nanodomains are speculated to be of a micellar structure with PS chains forming the core shielded by PMMA chains. 相似文献
In-situ polymer blends of polystyrene (PS)/poly(methyl methacrylate) (PMMA) with controlled and variable different compositions and molecular weights were found to be successfully synthesized by “chain transfer living polymerization (CTLP)” methodology by a combination of size-exclusion chromatographic analysis, differential scanning calorimetry (DSC), UV/Vis and H NMR spectroscopy, and optical microscopic analysis. The PMMAs prepared in tetrahydrofuran (THF) in the presence of polystyrene exhibit highly syndiotactic stereoregularity (over 70 mol-%) and a glass transition temperature over 120°C. A dispersed morphology was found even for blends with over 31 vol.-% of the weight fraction of one component due to the discrepancy in the molecular weights of two components in the PS/PMMA blends. A ternary polymer blend system having PS/PMMA/PS -block- PMMA can be generated by control of the concentration of fluorene as the chain transfer agent in the CTLP. 相似文献
Spherical polystyrene (PS) micronetworks can be prepared in microemulsion with bulk radii of 5–60 nm and different cross-linking densities. The diffusion of these PS spheres has been studied in polymer diluent systems ranging from dilute solutions to plasticized melts by using forced Rayleigh scattering and photon correlation spectroscopy. On increasing the PS concentration, a colloid glass transition is observed at a volume fraction ΦC ≈ 0.64 of the swollen spheres. At higher concentration inside the “colloid glass” state the sphere diffusion is slowed down and becomes very complex but can be observed up to the limit of a melt of collapsed spheres. 相似文献
The hydrodynamics near moving contact lines of two room-temperature polymer melts, polyisobutylene (PIB) and polystyrene (PS), are different from those of a third polymer melt, polydimethylsiloxane (PDMS). While all three fluids exhibit Newtonian behavior in rotational rheological measurements, a model of the hydrodynamics near moving contact lines which assumes Newtonian behavior of the fluid accurately describes the interface shape of a variety of PDMS fluids but fails to describe the interface deformation by viscous forces in PIB and PS. The magnitude of the deviations from the model and the distance along the liquid-vapor interface over which they are seen increase with increasing capillary number. We conclude that the wetting behaviors of PIB and PS are influenced by weak elasticity in these low molecular weight melts and that dynamic wetting is more sensitive to this elasticity than standard rheometric techniques. 相似文献
Using a Monte‐Carlo simulation of a continuous space Rod Bead Model the interface properties of systems of flexible polymer chains with different sizes of monomers are investigated. An immiscible polymer blend in the strong segregation state is modeled by a double sandwich system of chains differing by an factor of two in the size of the beads and the interfacial tension is calculated by a virial theorem method. The simulation data are compared to self‐consistent mean field and experimental data. The results show that the simulation data agree very satisfactory with mean‐field results. The interfacial tension decreases for asymmetric systems in comparison to symmetric systems with comparable volume contents of monomers and interaction strengths due to a decrease of the effective interaction. The parameters of the investigated systems are close to the properties of PS, PMMA and PI melts. A comparison with experimental results yields a very good agreement with data for PS/PMMA and less satisfactory for PS/PI. Additionally to the interfacial tension we have studied the interfacial width, the deformation of polymer chains near the interface, distributions of chain ends, monomer densities and distributions of centers of mass of chains.
Snapshot of a typical configuration for chains with different monomer sizes and equal number of monomers per chain. 相似文献
Cellulose-synthetic polymer nanocomposite films were prepared by immersion of cellulose gel in polymer solutions followed
by dry casting. The cellulose hydrogel was prepared from aqueous alkali-urea solution. As the synthetic polymer, polystyrene
(PS) and poly(methyl methacrylate) (PMMA) were used. The polymer content could be changed between 10 and 80% by changing polymer
concentration of immersing solution. While the mechanical properties of the cellulose-PMMA composite films showed a nearly
linear dependence on PMMA content, those of cellulose-PS composites showed an anomalous behavior; both tensile strength and
Young’s modulus showed prominent maxima at 15–30 wt% PS contents. This anomaly may have resulted from the specific interaction
between the aromatic ring of PS and the hydrophobic plane of the glucopyranoside. Both PMMA and PS composite films showed
significant improvements in dimensional thermal stability; up to 25 wt% synthetic polymer content, the coefficient of thermal
expansion (CTE) was as low as ca. 30 ppm/K, about 1/3 of the pure polymers. This indicates that the regenerated cellulose
network is effective in suppressing thermal expansion of the synthetic polymers. 相似文献
We present results on the glass transition in polymer melts using Monte Carlo simulations of the bond fluctuation lattice model. There are two questions we address in this work. What is the temperature dependence of the entropy density in such a model polymer melt and how well is it described by theories like the Gibbs-DiMarzio theory of the glass transition? And to what degree is one able to map the Hamiltonian of such an abstract lattice model onto a specific polymer material and use it to model the large scale and long time properties of a realistic polymer melt? 相似文献
Elongation viscosity is an important characterization of flow properties for polymer melts. In the present article, a new extensional viscosity equation for polymer melts was established by introducing a relaxation time equation based on the Cross model. The elongation viscosities of a low-density polyethylene (LDPE) melt at 200 °C and a metallocene linear low-density polyethylene (mLLDPE) melt at 130 °C were estimated using this equation; then, the calculations of the melt elongation viscosity were compared with the measured data from the extension experiments of the LDPE melt and the mLLDPE melt reported in the reference. Good agreement was found between the predictions and the measured data from the LDPE and mLLDPE melts. In addition, this equation is easy to use for characterization of elongation viscosity during single shaft elongation flow for polymer melts. 相似文献
We propose a statistical dynamical theory for the violation of the hydrodynamic Stokes-Einstein (SE) diffusion law for a spherical nanoparticle in entangled and unentangled polymer melts based on a combination of mode coupling, Brownian motion, and polymer physics ideas. The non-hydrodynamic friction coefficient is related to microscopic equilibrium structure and the length-scale-dependent polymer melt collective density fluctuation relaxation time. When local packing correlations are neglected, analytic scaling laws (with numerical prefactors) in various regimes are derived for the non-hydrodynamic diffusivity as a function of particle size, polymer radius-of-gyration, tube diameter, degree of entanglement, melt density, and temperature. Entanglement effects are the origin of large SE violations (orders of magnitude mobility enhancement) which smoothly increase as the ratio of particle radius to tube diameter decreases. Various crossover conditions for the recovery of the SE law are derived, which are qualitatively distinct for unentangled and entangled melts. The dynamical influence of packing correlations due to both repulsive and interfacial attractive forces is investigated. A central finding is that melt packing fraction, temperature, and interfacial attraction strength all influence the SE violation in qualitatively different directions depending on whether the polymers are entangled or not. Entangled systems exhibit seemingly anomalous trends as a function of these variables as a consequence of the non-diffusive nature of collective density fluctuation relaxation and the different response of polymer-particle structural correlations to adsorption on the mesoscopic entanglement length scale. The theory is in surprisingly good agreement with recent melt experiments, and new parametric studies are suggested. 相似文献