Rheological properties of glass bead-filled low-density polyethylene composite melts in capillary extrusion

The melt flow of glass bead-filled low-density polyethylene composites in extrusion have been observed by using a capillary rheometer to investigate the effects of temperature, shear rate, and filler content on the rheological properties of the melts. The results show that the melt shear flow obeys a power law, and the dependence of the apparent shear viscosity, η_app, on temperature is in accord with an Arrhenius equation. At the same temperature and shear rate, η_app increases slightly with increasing the volume fraction of glass beads, but the flow behavior index decreases with increasing filler content. In addition, the first normal stress difference of the melts linearly increases with increasing wall shear stress. Good agreement is shown with the N₁ calculated with the equation presented in this article and the pressured data from the sample melts. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1451–1456, 1999     

Viscosity,modulus, and die swell of glass bead filled polystyrene-acrylonitrile copolymer

Flow curves were obtained at 190°C over the shear rate range 0.1 to 100 sec^?1 for polystyrene-acrylonitrile copolymer containing up to 36 percent by volume glass beads, using a capillary extrusion rheometer. The addition of glass beads always increased shear stress and viscosity at a given shear rate, with the increase being more pronounced at low shear rates. The addition of glass beads decreased die swell, which also depended on shear-stress and capillary length-to-radius ratio. At low shear rates a lower limiting value of die swell ratio of about 1.1 was achieved. Values of recoverable shear derived from end correction data by the technique of Philippoff and Gaskins and from die-swell data by the method of Bagley and Duffey are compared. A fairly good agreement was found for low concentration blends at low shear, However, the values differed by a factor of up to 3 at higher shear stresses. In all cases, recoverable shear was found to increase with shear stress at a fixed filler loading and to decrease with increased filler loading at a fixed shear stress. Values of shear modulus calculated from the recoverable shear measurements decreased rapidly with increasing shear stress.     

Slip velocity and slip layer thickness in flow of concentrated suspensions

The rheological characterization of highly filled suspensions consisting of a Newtonian matrix (hydroxyl-terminated polybutadiene), mixed with two different sizes of aluminum powder (30% and above by volume) and two different sizes of glass beads (50% and above by volume), was performed using a parallel disk rheometer with emphasis on the wall slip phenomenon. The effects of the solid content, particle size, type of solid particle material, and temperature on slip velocity and slip layer thickness were investigated. Suspensions of small particles of aluminum (mean diameter of 5.03 μm) did not show slip at any concentration up to the maximum packing fraction. However, suspensions of the other particles exhibited slip at the wall, at concentrations close to their maximum packing fraction. In these suspensions, the slip velocity increased linearly with the shear stress, and at constant shear stress, the slip velocity increased with increasing temperature. The slip layer thickness increased proportionally with increasing size of the particles for the glass beads. Up to a certain value of (filler content/maximum packing fraction), ϕ/ϕ_m, the slip layer thickness divided by the particle diameter, δ/D_P, was 0, but it suddenly increased and reached a value that was independent of ϕ/ϕ_m and the temperature. On average, the ratio of δ/D_P was 0.071 for aluminum and 0.037 for glass beads. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 515–522, 1998     

Die–swell behavior of glass bead‐filled low‐density polyethylene composite melts at high extrusion rates

The extrudate swell behavior of glass bead‐filled low‐density polyethylene (LDPE) composite melts was investigated using a constant rate type of capillary rheometer at high extrusion rates and test temperatures varied from 140 to 170°C. The results show that the die swell ratio (B) of the melts increases nonlinearly with increasing apparent shear rates for the system filled with the surface of glass beads pretreated with a silane coupling agent, while the B for the system filled with uncoated particles remains almost constant when the true wall shear rate is greater than 2000 s⁻¹ at a constant temperature. The values of B for both the pure LDPE and the filled systems decreases linearly with an increase of the temperature and an increase of the die diameter at fixed shear rates, and the sensitivity of B on the die diameter and temperature for the former is higher than that of the latter. Furthermore, the effect of the filler content on B is insignificant, while the values of B decreases, obviously, with an increasing glass bead diameter (d) when d is smaller than 50 μm; then B varies slightly with d. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 419–424, 2000     

A Survey of Rheological Properties of One-Component Epoxy Adhesives

Flow characteristics of seven commercially available one-component epoxy adhesive pastes were measured using a controlled shear stress rheometer and a controlled shear rate rheometer over a temperature range from 5°C to 60°C. Combining data obtained from both controlled rate and controlled stress experiments over a wide range of shear rates, we observed Newtonian flow (shear stress proportional to shear rate) at very low shear rates, a plateau “shear thinning” region at intermediate shear rates, and a second region of linear dependence of shear stress on shear rate at high shear rates. The adhesive pastes exhibited a very broad range of rheological behavior. Two flow parameters important to adhesive application technology, the plastic viscosity and the apparent yield stress, were measured for each adhesive. The plastic viscosity ranged from 11.6 to 329.5 Pa. s; the apparent yield stress ranged from 56.2 to 413 Pa. The temperature dependence of the rheological parameters of the epoxy adhesive pastes was also determined. The results are reported as the activation energies, E_η and E_σ , of plastic viscosity and apparent yield stress, respectively. The apparent yield stress of each adhesive paste was much less sensitive to changes in temperature than was the plastic viscosity. This suggests that the processing characteristics are likely to show qualitative as well as quantitative changes with temperature.     

Melt rheological behavior of intimately mixed short sisal–glass hybrid fiber‐reinforced low‐density polyethylene composites. I. Untreated fibers

The melt rheological behavior of intimately mixed short sisal–glass hybrid fiber‐reinforced low‐density polyethylene composites was studied with an Instron capillary rheometer. The variation of melt viscosity with shear rate and shear stress at different temperatures was studied. The effect of relative composition of component fibers on the overall rheological behavior also was examined. A temperature range of 130 to 150°C and shear rate of 16.4 to 5470 s^?1 were chosen for the analysis. The melt viscosity of the hybrid composite increased with increase in the volume fraction of glass fibers and reached a maximum for the composite containing glass fiber alone. Also, experimental viscosity values of hybrid composites were in good agreement with the theoretical values calculated using the additive rule of hybrid mixtures, except at low volume fractions of glass fibers. Master curves were plotted by superpositioning shear stress and temperature results. The breakage of fibers during the extrusion process, estimated by optical microscopy, was higher for glass fiber than sisal fiber. The surface morphology of the extrudates was analyzed by optical and scanning electron microscopy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 432–442, 2003     

导向充气喷动床的临界充气速度

１前言在普通喷动床的环形区底部额外引入一股辅助气体,由于喷动气体和辅助气体各自独立地改变,气固系统将出现下列几种体系或操作状态：①固定床;②充气喷动床;③喷流床;④带射流的流化床。长期以来对充气喷动床与喷流床的区别不是很清楚的［１～５］。张怀清等［６...     

ON THE RHEOLOGICAL BEHAVIOUR OF FILLED POLYMER MELTS†

The viscosity of polymer melts increases when adding fillers. Experiments were conducted with styrene—acrylonitrile copolymers filled with various amounts of glass beads and short glass fibres on a rotational and a capillary rheometer. Further from literature some representative equations have been compiled describing the influence of fillers on the viscosity. Applied to the experimental results it was found that the relative viscosity (R, i.e. the ratio of the viscosities of the filled and unfilled melts, shows a pronounced dependence on the shear rate ? but not on the shear stress t.     

The Melt Flow Properties of Poly(propylene)/Glass Bead Composites

The effects of filler content and its surface treatment on the melt flow properties of A‐glass bead‐filled poly(propylene) (PP) composites have been investigated using a capillary rheometer at a wide apparent shear rate scope of 150 to 7 200 s^–1 and a temperature range of 160 to 200°C. It was found that the melt shear flow obeyed roughly the power law. The melt shear viscosity (η_w) of the treated glass bead‐filled system with a silane coupling agent was somewhat higher than that of the raw glass bead‐filled system when both the systems were subjected to the same test conditions. The increase of the resistance to flow and flow satiability for the former system can be attributed to the improvement of the compatibility and interfacial adhesion between the filler and matrix as well as the dispersion of the filler in the matrix due to the surface treatment of the glass beads. The dependence of η_w on temperatures can be expressed with an Arrhenius relationship. The temperature sensitivity of η_w for the composite melts is greater than that of the unfilled PP. Furthermore, η_w increases obviously with the volume fraction (ϕ_f) of the fillers at lower shear rates, while the dependence of η_w on ϕ_f decreases with the increase of shear rates. This is attributable to the increase of the ability of relative movement between the filler and matrix melt at high extrusion rates.     

Viscoelastic properties of suspensions with weakly interacting particles

Rheological characterization of a model suspension containing hydroxyl-terminated polybutadiene and glass beads with filler concentration up to 30% by volume was performed by using a Haake parallel disk rheometer. The rheological tests conducted were the measurement of the storage modulus, G′, loss modulus, G′, and complex viscosity, η*, as functions of the frequency and the steady shear viscosity as a function of the shear rate. The linear viscoelastic region was determined to extend up to 50% strain by measuring G′, G′, and η* as functions of strain amplitude. By using multiple gap separations between the disks, it was found that the suspension did not exhibit slip at the walls of the rheometer. G′ and G′ were used to determine the relaxation times distribution, G_i(λ_i, ⊘) as functions of the relaxation time, λ_i, and the filler content, ⊘. The relaxation moduli, G_i(λ_i, ⊘), decreased with the relaxation time, but increased with the filler content. The Cox–Merz rule was also observed to be valid for these suspensions. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 507–514, 1998     

Adjustable Twin‐Slit Rheometer for Shear Viscosity Measurement of Extruded Complex Starchy Melts

An online rheometer with an innovative system of height‐adjustable and independently temperature‐controlled slits was designed to measure the shear viscosity of extruded wheat bran fiber‐containing starchy materials. The range of melt pressures and temperatures, obtained with a die, could be covered by the rheometer. A close ingredient thermomechanical history in the extruder was achieved both with the die and the rheometer, while covering an apparent shear rate from 5 to 30 s^–1. Although minor technical problems remained, first rheological data were obtained and showed a pseudoplastic flow behavior for all recipes. The flow curves were fitted by a power law model. Wheat bran fiber addition influenced both the K‐ and n‐values, leading to more shear‐thinning melt behavior and an increase in true shear viscosity. Only a limited effect on these values was found in these preliminary experiments when further increasing the fiber content.     

A modified rheological model of viscosities for BR–SBS blends

Blends of polybutadiene (BR) and styrene–butadiene–styrene triblock copolymer (SBS) have been prepared by a two‐roll mill. The morphologies of extruded samples from a capillary rheometer were observed by scanning electron microscopy (SEM). It is found that PS phase is dispersed in the BR phase. The glass transition temperature (T_g) of the blend has been examined by using differential scanning calorimetry (DSC). From the T_g behavior and the electron microscopy study, it is found that certain degree of miscibility between the polystyrene phase and the BR phase is observed. The rheological behavior of the blend has been investigated by a capillary rheometer. It is found that the viscosity of the blend increases with increased content of PS phase. The behavior is in accord with the expected behavior of filler effect. To predict the filler effect of PS phase on the BR–SBS blend, a modified model of Chen and Cheng is proposed to elucidate the rheological properties of the BR–SBS blends with different compositions. Chen and Cheng's micromechanical model derived in Part I of this series, which relates the macroscopic shear stress to the macroscopic shear rate of a rigid non‐Newtonian suspension when the direct contribution of Brownian force is completely neglected. The agreement between the theoretical predictions and the experimental results is satisfactory. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 39–46, 1999     

Fatigue crack propagation in composites with spherical fillers-II effect of the size of the filler

A study of the effect of spherical glass beads of mean diameters of 46 microns, 89 microns, and 133 microns, on fatigue crack propagation rates, was carried out at ten and thirty weight-percent beads. The resin was a low-molecular-weight [M_n = 8200, (M_wM_n) = 2.04] Bisphenol A-terephthalate/isophthalate thermoplastic copolyester. Fatigue crack-grwoth rates were measured using compliance method. The relationship between logarithm of stress intensity factor change and logarithm of crack-growth rate is linear for 46 micron beads. For the 89 micron beads, the relationship is still approximately linear. The incorporation of 133 micron beads, however, results in large fluctuations in crack-growth rates with changes in stress intensity factor range. A mechanism is proposed to explain this behavior. A relationship between interparticle distance and fatigue crack-growth resistance is also observed.     

Modifications of the weissenberg rheogoniometer for measurement of transient rheological properties of molten polyethylene under shear. Comparison with tensile data

Improvements to the Weissenberg rheogoniometer are necessary in order to measure the transient rheological properties of polymer melts correctly. The improvements reported concern the mechanical design, a new heating system, a new normal force measuring system, and additional equipment for the relaxation test. Reliable short-time results require sufficiently stiff torque and normal force springs, and a small radius and relatively large angles of the cone-and-plate gap. The behavior of the LDPE melt under test is “linear viscoelastic,” if shear rate or total shear are small: The relaxation modulus, the stress growth at the onset of constant shear rate, the stress relaxation after cessation of steady shear flow, and, in addition, dynamic shear data (from an oscillation viscometer) all show consistent results when correlated by means of formulae from the theory of linear viscoelasticity. Shearing in the nonlinear range with constant shear rate leads to pronounced maxima of the shear stress p₁₂ and of the first normal stress difference p₁₁ ? p₂₂ which occur at constant total shear, almost independent of shear rate. Comparison of shear and tensile data (from extensional rheometer) confirms the Trouton relation in the linear-viscoelastic case. In the nonlinear case, there is a “work softening” in shear and a “work hardening” in extension.     

Rheology of unsaturated polyester resins. I. Effects of filler and low-profile additive on the rheological behavior of unsaturated polyester resin

Measurements were taken of the bulk rheological properties of concentrated suspensions of particulates in unsaturated polyester resins, using a cone-and-plate rheometer. The particulates used were clay, calcium carbonate, and milled glass fiber. With clay and milled glass fibers, shear-thinning behavior of suspensions was observed at low shear rates or low shear stresses as the concentration of particulates was increased, whereas concentrated suspensions of calcium carbonate exhibited Newtonian behavior over the range of shear stresses or shear rates investigated. The cone-and-plate rheometer was also used for measurements of the bulk rheological properties of various mixtures of polyester resin and low-profile additives. For low-profile additives, solutions, in styrene, of poly(vinyl acetate) (PVAc) and poly(methyl methacrylate) (PMMA) were used. It was found that the bulk viscosities of all mixtures of polyester resin and PVAc solution lie between those of the individual components, whereas the bulk viscosities of some mixtures of polyester resin and PMMA solution go through a minimum and a maximum, depending on the composition of the mixture. While all mixtures of polyester resin and PVAc solution exhibited negligible normal stress, some mixtures of polyester resin and PMMA solution exhibited noticeable normal stresses. It should be mentioned that polyester resin follows Newtonian behavior. It turned out that all mixtures of polyester resin and PVAc solution exhibited clear, homogeneous solutions, whereas mixtures of polyester resin and PMMA solution exhibited optical heterogeneity, i.e., turbidity. When polyethylene powders were used as low-profile additives, suspensions of polyester resin and polyethylene powders exhibited negative values of normal stress as the concentrations of suspension reached a critical value. When both filler and low-profile additive were put together in polyester resin, the rheological behavior became quite complex, indicating that some interactions exist between the filler and the low-profile additive.     

Effects of extrusion conditions on rheological behavior of acrylonitrile–butadiene–styrene terpolymer melt

The influence of temperatures and flow rates on the rheological behavior during extrusion of acrylonitrile–butadiene–styrene (ABS) terpolymer melt was investigated by using a Rosand capillary rheometer. It was found that the wall shear stress (τ_w) increased nonlinearly with increasing apparent shear rates and the slope of the curves changed suddenly at a shear rate of about 10³ s^?1, whereas the melt‐shear viscosity decreased quickly at a τ_w of about 200 kPa. When the temperature was fixed, the entry‐pressure drop and extensional stress increased nonlinearly with increasing τ_w, whereas it decreased with a rise of temperature at a constant level of τ_w. The relationship between the melt‐shear viscosity and temperature was consistent with an Arrhenius expression. The results showed that the effects of extrusion operation conditions on the rheological behavior of the ABS resin melt were significant and were attributable to the change of morphology of the rubber phase over a wide range of shear rates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 606–611, 2002     

Shear viscosity of carbon black filled polypropylene at very low shear stresses

The shear viscosity of carbon black filled polypropylene with a range of different carbon blacks was investigated. This was accomplished using (a) a constant shear stress creep instrument, (b) a cone-plate rotational rheometer, (c) a capillary extrusion rheometer. It was found that stresses exist for these compounds below which there are only finite deformations and no steady flow, Much attention was given to measurements of creep at low stresses, especially in the neighborhood of yield values. The magnitudes of yield stresses obtained from such creep measurements are significantly lower than those obtained using standard extrapolation to zero shear rate of higher stress data from rotational instruments. The shear viscosity behavior near the yield value differs significantly depending upon the carbon black used. A high viscosity was observed (～10⁹ to 10¹⁰ Pa.s) plateau in some compounds.     

Oscillating flow behavior of high-density polyethylene melts

The oscillating flow behavior of a variety of high-density polyethylene and copolymer samples was studied in a constant displacement rate rheometer. At any plunger velocity, the period of the oscillations decreases linearly with melt depth, suggesting a resonance phenomenon. As plunger velocity is increased, the load waveform changes in a regular manner that indicates a progressive increases in the proportion of each cycle spent on the right-hand branch of the flow curve. Little difference was found in the shear stress at which oscillating flow began for samples differing in molecular weight, molecular weight distribution, and manufacturing process. However, the shear rate at which oscillating flow begins depends, strongly on both molecular weight and distribution. Oscillating flow is shifted to higher shear rates by broadening distribution, reducing molecular weight, increasing temperature, or decreasing the L/D ratio of the capillary.     

Viscoelastic behavior of AN‐g‐casein copolymer concentrated solution of sodium thiocyanate

The viscoelastic behavior of sodium thiocyanate concentrated solution of graft copolymer of acrylonitrile onto casein (AN‐g‐casein) was investigated in detail by nitrogen pressure capillary rheometer. The experimental results show that the concentrated solution of AN‐g‐casein is a non‐Newtonian fluid of shear thinning. The end correction increases with the increase of shear rate. In the course of practical spinning, the real shear stress only attributes about 35% to the apparent shear stress, which confirms the essentiality of end correction for the capillary extrusion of the concentrated solution of the graft copolymer. By using the Dewitt model, the Couette correction ξ and recoverable shear strain S_R were analyzed and separated. Quantitative function relation of ξ and S_R versus shear rate and temperature were deduced. It is a common equation within the range of experiment. In practical spinning process, the real viscoelastic parameters can be easily predicted by only a piece of flowing curve based on the common equation. Real elastic model G under any shear rate in the range of experiment was calculated. It was found that G increases with an increase of shear rate, which is opposite to the conclusion reported by Hayahara. The main reason for the error may be that Hayahara used the same Couette correction at a higher shear rate. Further, the die swell in the spinning process can be estimated efficiently. The theoretical base for the stability of AN‐g‐casein spinning technology was provided. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1721–1728, 2002; DOI 10.1002/app.10554     

Anomalous first normal stress difference behavior of polymer nanocomposites and liquid crystalline polymer composites

The first normal stress difference (N₁) behavior of polymer nanocomposites and liquid crystalline polymer (LCP) composites is a measure of elasticity and is affected by shear stress as a result of morphological alterations at the molecular and nanostructure levels. In this study, the steady shear rheological behaviors of polylactide (PLA) and nanographite platelet (NGP) bionanocomposites containing 1, 2, 3, and 5 wt% nanofiller were investigated. The shear rheological properties of glass fiber‐filled LCPs (filler aspect ratio > 100) were also examined. One of the objectives of this study was to obtain a correlation between N₁, filler contents, and shear stress/rate of the measurements. The results suggest that N₁ in PLA/NGP bionanocomposites is dependent on the level of filler loading as well as the shear rate beyond a critical value. For the LCP systems, N₁ is positive for the unfilled and negative for the glass fiber‐filled LCPs, respectively. A novel rectangular hyperbola model was successfully developed and utilized to fit the N₁ data of the neat PLA and PLA/NGP composites as well as the unfilled LCPs. The anomalous N₁ behavior of PLA/NGP and LCP composites was also thoroughly discussed in this study. POLYM. ENG. SCI., 54:1300–1312, 2014. © 2013 Society of Plastics Engineers