Rheological behavior of low molecular weight polystyrene composites containing monodisperse crosslinked polystyrene beads

Steady shear viscosities and dynamic moduli of polymer composites, consisting of crosslinked polystyrene beads and low molecular weight polystyrene matrix, were measured in a cone-and-plate rheometer at different temperatures. Viscosities and dynamic moduli were found to be very sensitive to filler loading and measurement temperature. Steady shear viscosities of 30% and 40% loaded low molecular polystyrene composites showed a power-law behavior over the entire range of shear rates. Storage and loss moduli were initially linear with frequency on double logarithmic plots, with limiting slopes of 0.3 and 0.1. At high concentration of filler particles, they showed a flat plateau at low frequencies, indicating that these systems exhibit a yield behavior. A 20% PS composite loaded with beads of high crosslink densities resulted in poor dispersion of beads as a result of poor dispersion of particles. PS beads 1.16 μm in diameter showed a higher viscosity. It is due to the apparent increase in loading resulting from broken particles. At low measurement temperature, filler effects were suppressed by high viscosity matrix and showed a similar rheological behavior to high molecular weight by PS matrix. We suggest that rheological behavior reflects the state of dispersion of beads in the matrix.     

Model filled polymers. XIV: Effect of modifications of filler composition on rheology

Steady shear vxiscosity, dynamic moduli and the appearance of fracture surfaces of model composites, consisting of monodisperse crosslinked polymeric spheres of varied composition in a polymethyl-methacrylate matrix, depend on the compatibility of filler particle and matrix. After intensive mixing, “compatible” systems form uniform and stable dispersions. Filler particles cluster in incompatible composites producing a highly non-Newtonian response. At 40 w% filler, yield behavior results, with a yield stress of 3100 Pa for polystyrene particles and 1900 Pa for copolystyrene-acetoxystyrene particles. The flow properties of compositionally complex particles from seeding are determined by particle surface composition.     

Model filled polymers: The effect of particle size on the rheology of filled poly(methyl methacrylate) composites

The effect of size of crosslinked monodisperse spherical polymer particles on the steady shear and dynamic rheology of filled poly(methyl methacrylate) (PMMA) composites was studied for PMMA and polystyrene (PS) particles in the range from 0.1 to 1.3 micron particle size. For PMMA matrices filled with crosslinked PS particles, reduction in filler size increases non‐Newtonian behavior. Particle size effects on the rheology of filled PMMA were much less pronounced for PMMA filler. The rate of growth of steady shear viscosity with aging time was much larger for PMMA filled with PS particles than with PMMA particles. The apparent yield stress of filled PMMA composites was estimated from Casson plots. The yield stress was negligible for PMMA filler but increased with decreasing particle size for PS filler. We suggest that PS particles are rejected by the PMMA matrix and form clusters, causing large enhancements in viscosity and moduli. Polym. Eng. Sci. 44:452–462, 2004. © 2004 Society of Plastics Engineers.     

Model filled polymers. XIII: Mixing and time-dependent rheological behavior of polymer melts containing crosslinked polymeric particles

The rheological properties of polystyrene (PS) and poly(methyl methacrylate) (PMMA) composites filled with monodisperse sized crosslinked polymeric particles are sensitive to processing history and chemical composition. Particles compatible with the matrix, such as PMMA or copolystyrene-vinylphenol in a PMMA matrix, are randomly dispersed on mixing, yielding (almost) Newtonian fluids. Particles incompatible with the matrix, such as PS or copolystyrene-acetoxystyrene in PMMA, produce composites whose steady shear viscosities depend on shear rate and whose dynamic moduli are elevated at low frequency. Particles in incompatible composites tend to cluster, producing a structure that is destroyed at high shear rates and that reforms on aging at elevated temperatures.     

Model-Filled polymers. III: Rheological behavior of polystyrene containing cross-linked polystyrene beads

The steady shear viscosity and dynamic moduli, at 180 and 200°C, of polystyrene composites, containing cross-linked monodisperse polystyrene beads varying in diameter from 0.2 to 0.8 μm, are independent of bead size and cross-link density, but increase with the volume fraction of beads. Steady shear viscosities exhibit power-law regions up to 40% concentration of beads, but no yield stress. Storage and loss moduli are initially linear with frequency, on double logarithmic plots, with limiting slopes of 1.3 and 0.9, respectively. Uncross-linked beads and beads cross-linked with 0.1% divinylbenzene are destroyed by thermomechanical dispersion in the melt.     

Model filled polymers. XV: The effects of chemical interactions and matrix molecular weight on rheology

In order to explore the effects of chemical composition on the rheological behavior o filled polymeric systems, we prepared polystyrene (9PS) and poly(methyl methacrylate) (PMMA) particles crosslinked with either ethylene glycol dimethacrylate (EGDMA) or divinyl benzene (DVB), and mixed these particles in a PMMA matrix. PS particles crosslinked with 10% EGDMA are better dispersed in a PMMA matrix, compared to PS particles, crosslinked with 10% DVB, due to the compatibilizing effect of EGDMA. For PMMA particles crosslinked with DVB, particle-matrix interactions in a PMMA matrix are smaller than in EGDMA-PMMA filled PMMA. Therefore, particles tend to agglomerate in PMMA composites filled with DVB-PMMA particles, especially in a low molecular weight matrix. We compared PMMA matrices of molecular weights 35,000 and 75,000. Higher particle-matrix interaction in the higher molecular weight matrix resulted in lower relative viscosities for DVB-PS filled systems, due to better dispersion of the particles. Composites filled with EGDMA-PS particles behave similarly to those filled with DVB-PS particles. PMMA composites filled with DVB-PMMA particles have a lower relative viscosity in the higher molecular weight PMMA matrix at low shear rates, due to better dispersion in the higher molecular weight matrix. However at high shear rates, particles are well dispersed in both PMMA matrices and, then, the relative viscosity is higher due to better bonding in the higher molecular weight matrix.     

PS/PMMA共混体系的挤出流变行为

利用单螺杆挤出机,配备特殊设计的狭缝模头,在不改变螺杆转速的情况下获得流经口模的不同流量,研究了聚苯乙烯(PS)/聚甲基丙烯酸甲酯(PMMA)共混体系的挤出流变行为。结果表明,PS/PMMA共混物熔体的流变行为和其组分熔体的流变行为类似,都表现出假塑性流体的流动行为;在所研究的组成范围内,共混物熔体的非牛顿指数低于任一组分熔体。随着共混物黏度比的减小,其熔体的非牛顿指数呈下降的趋势;共混物熔体的黏度对加和性法则皆表现为负偏差,表明在界面处具有弱的相互作用。     

Rheological properties of hydrolyzed polyacrylonitrile-grafted cellulose

The rheological properties of aqueous dispersions of hydrolyzed polyacrylonitrile-grafted cellulose (H-CPAN) have been investigated. The experimental results are consistent with the idea that the elementary particle is a rigid cellulose protofibril stabilized in suspension by associated polyelectrolyte side chains (polyacrylamide–polyacrylic acid copolymer grafts). The behavior of intrinsic viscosity with electrolyte concentration, the concentration depependence and shear dependence of the viscosity and of the steady-state and dynamic shear moduli are qualitatively explained on this basis.     

The glass transition temperature of filled polymers and its effect on their physical properties

The glass transition temperature, dynamic shear moduli, and bulk viscosities of Phenoxy PKHH (a thermoplastic polymer made from bisphenol-A and epichlorohydrin) filled with glass beads and Attapulgite clay were investigated. The glass temperature of the polymer increased with increasing filler concentration and with increasing specific surface area of the filler. The data were interpreted by assuming that interactions between filler particles and the polymer matrix reduce molecular mobility and flexibility of the polymer chains in the vicinity of the interfaces. From the measured moduli and the viscosities of the filled and unfilled materials, the modulus reinforcement ratio in the glassy state and the relative viscosity in the viscous state were obtained as functions of the filler type and concentration. The relative modulus for the glass bead composite system follows the Kerner equation, while the clay-filled systems exhibit slightly greater reinforcement. The relative viscosities are strongly temperature dependent and do not follow conventional viscosity predictions for suspensions. It is suggested that the filler has a twofold effect on the viscosity of the composite materials; one is due to its mechanical presence and the other is due to modifications of part of the polymer matrix caused by interaction. Using the WLF equation to express all modifications of the matrix, one can isolate a purely mechanical contribution to the viscosity reinforcement. This mechanical part is approximately bounded by the theoretical predictions of Kerner,³² Mooney, ³⁶ and Brodnyan,⁴¹ for suspension viscosities.     

Chemorheology of model filled rubber compounds during curing

The rheological behavior and crosslinking kinetics of model filled rubber compounds during curing were investigated. The effect of chemical composition of monodisperse size particles, prepared by emulsifier‐free emulsion polymerization, on dynamic moduli and gelation time of the filled compounds was studied. All filled systems showed much shorter gelation times than the pure matrix in the order PSVP < PS < PMMA ? Pure Matrix. The dynamic moduli during curing increased with increasing interactions between particles and matrix. Physical crosslinking, due to either particle clustering or a network of filler particles with an adsorbed polymer layer, made a significant contribution to the overall crosslink density and the gelation of rubber compounds. As a result, the dynamic mechanical properties and curing kinetics of the rubber compounds varied with the chemical nature of the filler particles.     

Mechanical and rheological behavior of highly filled polystyrene with lignin

The mechanical, rheological, and morphological properties of polystyrene (PS)/lignin blends over a wide range of lignin content (0–80 wt%) have been studied in this work. PS/lignin blends were compounded in an internal batch mixer with and without the addition of a linear triblock copolymer based on styrene, ethylene, and butylene (SEBS). A morphological analysis was carried out by scanning electron microscopy to determine the state of dispersion and the interfacial adhesion between the lignin particles and the PS matrix. It was found that the flexural and torsion moduli both increased, while the tensile properties decreased with increasing lignin content. Nevertheless, compatibilizer addition was found to improve the tensile properties of the lignin/PS blend. The shear rheological behavior of the lignin/PS blends was also studied in this work where viscosity, dynamic moduli, and activation energy were found to be very sensitive to both lignin and compatibilizer contents. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Effect of high molecular weight acrylic copolymers on the viscoelastic properties of engineering resins

In this work, the viscoelastic properties of acrylic‐based copolymer blends with poly(methyl methacrylate) (PMMA) and polycarbonate were investigated in the molten and solid states. High molecular weight copolymers of methyl methacrylate with butyl acrylate (MMA‐co‐BA) having varying molecular weight and composition were used to enhance the rheological properties in shear and extension. Blends containing up to 15 wt% of copolymer were prepared at 200°C and 150 rpm by using a DSM micro‐compounder. The samples were characterized by size exclusion chromatography (SEC), dynamic mechanical analysis (DMA), and rheology. The rheological properties were determined by using small amplitude oscillatory measurements (SAOM) in shear and a Rheotens? device for melt strength determination. For PMMA, the effects of high molecular weight PMMA copolymer on the matrix were related to the molecular weight, the tacticity of the copolymer, and the individual components. The rheological properties in shear showed enhanced storage and loss moduli at low frequency, while no change was observed at high frequency. In addition, extensional viscosity measurements made by using the filament stretching technique showed a significant increase in melt strength compared to that of the base PMMA with the blend containing the highest molecular weight copolymer showing the maximum force and a reduced drawdown ratio. For polycarbonate, its blends with acrylic copolymer were found to be immiscible. Similar enhancement in the moduli at low frequencies was observed, but a significant increase in the viscosity was obtained as well, resulting from the response of the two‐phase system. This change in the rheological properties was further increased at 15 wt% loading. Owing to the formation of a phase‐separated morphology, the melt strength was found to increase only slightly. J. VINYL. ADDIT. TECHNOL., 12:143–150, 2006. © 2006 Society of Plastics Engineers     

Use of Carbopol 980 and carboxymethyl cellulose polymers as rheology modifiers of sodium-bentonite water dispersions

The effects of polymer addition on the rheological parameters of sodium bentonite water dispersions at ambient conditions were studied using high molecular mass carboxymethylcellulose (CMC) and Carbopol 980. Adsorption isotherms using the batch equilibrium technique of the polymers onto the bentonite particles were Langmuir isotherms of the L1 type, indicating monolayer adsorption of the polymers onto the surface of the bentonite particles. The aqueous dispersions of 3% and 4% sodium bentonite exhibited Herschel–Bulkley rheological behavior. Addition of CMC up to 1.5% by mass to the 3% sodium bentonite dispersions decreased the yield stress and the flow consistency index because of the steric effects caused by the adsorption of the polymer. This state was then followed by a plateau of the yield stress and a considerable increase of the flow consistency index, indicating that after a particular polymer concentration, further addition merely increased the liquid viscosity of the mixture. The flow behavior index was not affected by CMC addition. Addition of Carbopol 980 to the 3% and 4% sodium bentonite dispersions up to 0.15% by mass again firstly decreased the yield stress and the flow consistency index, then increased the yield stress and the flow consistency index with increasing polymer concentration. The high shear viscosity of bentonite–Carbopol dispersions showed also a minimum followed by a drastic increase. The flow behavior index was not affected significantly by the polymer addition.     

Rheological behavior of semidilute solutions of ultrahigh-molecular-weight polyethylene

The rheological behavior of spinning solutions of ultrahigh-molecular-weight polyethylene was investigated in stationary and dynamic conditions of shear flow. It was shown that at the shear rates characteristic of real spinning conditions, the elastic reaction of the solution is much higher than the viscous reaction. In conditions of constant shear stress that ensure non-Newtonian flow of the solution, the uniform decrease in the viscosity is replaced by an increase in time due to gradual formation of a cross-linked layer adjacent to the rotating disk of the working unit of the rheometer.     

The Smectic Rheology of a Polysiloxane Side Chain Liquid Crystalline Polymer

The rheology of a side chain liquid crystalline polymer (SLCP) with a polysiloxane backbone was investigated. The dynamic shear moduli of the SLCP in a smectic phase did not show the normal terminal behavior as the homogenous polymeric melts did, and instead, they tended to level off in the low frequency terminal zone. Time–temperature superposition failed for both dynamic moduli in the low frequency terminal zone and the departure from the superposition became more evident in the vicinity of smectic/isotropic transition. The plateau-like moduli in the terminal zone indicated the layer structure of the smectic phase. The steady shear viscosities of the smectic phase exhibited a shear thinning behavior over the shear rates investigated. The shear thinning was lost at low shear rates when the temperature passed the smectic/biphasic border. The shear viscosity and the dynamic moduli showed a divergence in the neighborhood of the smectic/isotropic temperature. The activation energies of the shear viscosity and the moduli were smaller than that of the SLCP with polymethacrylate backbone. The rheological behavior of the SLCP at low frequencies and low shear rates was dominated by the smectogen.     

Characterization by dilute solution and rheological methods of polystyrene and poly(methyl methacrylate) produced with a tetrafunctional peroxide initiator

Polystyrene (PS) and poly(methyl methacrylate) (PMMA) samples produced by the bulk homopolymerization of styrene and methyl methacrylate with a tetrafunctional peroxide initiator (JWEB50) are characterized in detail by various solution and rheological methods. For comparison purposes, “linear” PS and PMMA samples were produced under similar conditions with a monofunctional initiator (TBEC). The four sample types were characterized by size exclusion chromatography (SEC) setups to determine molecular weight, radius of gyration, and intrinsic viscosity distributions. Contraction factors were calculated and indicated evidence of branching for polystyrene produced with JWEB50 while no such effects were observed with PMMA. The rheological behavior of the samples was subsequently investigated by performing oscillatory shear and creep experiments. Compared to the “linear” material, samples produced with JWEB50 exhibited a reduction in zero‐shear viscosity that was attributed to long‐chain branching. Retardation spectra were calculated based on creep data and converted to dynamic compliances that were then combined with the oscillatory data. This provided master curves spanning a much wider frequency range than could be obtained experimentally. Examination of various viscoelastic functions showed evidence of long‐chain branching for both polystyrene and poly(methyl methacrylate) samples produced with JWEB50. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1340–1355, 2007     

Rheological properties of fumed silica filled Bis-GMA dispersions

The rheological properties of Bis-GMA dispersions filled with fumed silica were investigated to optimize the manufacturing process and mechanical properties by using a Rheometrics Mechanical Spectrometer (RMS). Steady and dynamic measurements on the RMS were carried out to obtain shear viscosity and dynamic mechanical properties. The effect of several factors on the rheological properties of fumed silica dispersions was also examined. The factors were a concentration of a silane coupling agent (γ-MPS), the methods of surface treatment of fillers, silica content, diluent concentration, shear rate, and operating temperatur. From these studies, it was observed that shear viscosity showed an asymptotic phenomenon at a higher concentration than a uniform multi-layer coverage concentration of γ-MPS. The silane coupling agent had a significant role in the reduction of tan δ, resulting from a decrease of loss modulus, while fillers decreased tan δ by increasing the storage modulus. In cases where the silica content and diluent concentration increased simultaneously, the Barcol hardness of Bis-GMA/silica composites was increased, but there was no change in the viscosity of dispersions and diametral tensile strength of those composites.     

Rheology of Nano‐Scale Aluminum Suspensions

Nano‐scale aluminum particles are innovative materials which are used increasingly in energetic formulations. In this contribution, the rheological behavior of suspensions with either paraffin oil or HTPB as the matrix fluid and nano‐scale aluminum (ALEX) as the dispersed phase is described and discussed. The paraffin oil/aluminum suspensions exhibit non‐Newtonian flow behavior over a wide range of concentrations, whereas the HTPB/aluminum suspensions exhibit Newtonian behavior (i.e. the viscosity is independent of shear stress) up to a concentration of 50 vol.% aluminum. Both systems have unusual viscoelastic properties in that their elastic moduli are independent of the solids concentration.     

Viscosity decrease by interfacial slippage between immiscible polymers

The rheological behavior under pressure-driven shear flow was studied using binary blends with a sea-island structure. The addition of a low-viscosity dispersion having a high interfacial tension with the continuous phase greatly reduces the shear viscosity, for example, the addition of atactic polystyrene (PS) with a low viscosity to isotactic polypropylene (PP) and the addition of PP with a low viscosity to PS. The interfacial slippage occurs because of the poor adhesive strength with the enlarged interfacial area and is responsible for the viscosity decrease. When the dispersion has a similar viscosity to the continuous phase, the viscosity decrease is barely detected. This is because the deformation of dispersed droplets is restricted, which creates a small interfacial area. The interfacial tension between the continuous and dispersed phases plays a crucial role on the shear viscosity. In the case of PP, the addition of linear low-density polyethylene with a relatively low interfacial tension to PP has almost no impact on the shear viscosity. This is despite the polyethylene having a low viscosity.     

基于流变特性探讨聚芳砜酰胺纺丝液的稳定性

利用旋转流变仪研究了聚芳砜酰胺(PSA)纺丝液的稳态和动态流变行为,结果表明:以二甲基乙酰胺(DMAc)为溶剂的聚芳砜酰胺溶液表现出典型的聚合物浓溶液流变特性,在低剪切速率区表现为牛顿流体特性,而随着剪切速率的增大,呈现出切力变稀行为,纺丝液的零切黏度、松弛时间随PSA特性黏度的增大而增大,非牛顿特性增强;证明了PSA纺丝溶液在测试温度范围内处于均质溶液状态,在进一步的动态温度扫描分析中,没有发现溶液的凝胶化转变现象,说明在试验温度范围内,PSA纺丝液处于均质稳定状态。