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     

Rheological and mechanical properties of poly (ethylene acrylic acid) and low density polyethylene blends

Rheological properties of poly (ethylene‐acrylic acid) (PEA) and low density poly ethylene (LDPE) blends having varied amounts of LDPE from 0 to 100% have been evaluated at different temperatures (115, 120, and 130°C) and shear rates (61.33–613.30 s^?1) using a Monsanto processability tester. A reduction in the melt viscosity of the PEA/LDPE blends was noticed with increasing the shear rate. The observed positive deviation in the experimental melt viscosities of the blends is an indication of the synergy present in the blends during melt processing. The activation energy (E_a) of flow calculated using Arrhenius relation for PEA, LDPE, and their respective blends lies in the range 29.98–40.56 kJ mol^?1. The experimental activation energy of flow of the blends was higher than that obtained from the additivity rule. Highest activation energy was noticed for the blends containing 60–80% by weight of LDPE in PEA/LDPE blends, which is an indication for the miscibility of the blends at these ratios. The physicomechanical properties such as density, tensile behavior, tear strength, and hardness (Shore A) of PEA, LDPE, and their blends have been evaluated as a function of varying amounts of LDPE. The obtained physicomechanical properties of the PEA/LDPE blends lie in between that of pure polymers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Shear rate dependence of viscosity and first normal stress difference of LCP/PET blends at solid and molten states of LCP

The liquid crystalline polymer (LCP) and polyethylene terephthalate (PET) were blended in an elastic melt extruder to make samples having 20, 40, 60, 80, and 100 wt % of LCP. Morphology of these samples was studied using scanning electron microscopy. The steady state shear viscosity (η), dynamic complex viscosity (η*) and first normal stress difference (N₁) were evaluated and compared at two temperatures: 265°C, at which LCP was in solid state, and 285°C, at which LCP was in molten state. The PET was in molten state at both the temperatures. The shear viscosity of the studied blends displayed its dependence on composition and shear rate. A maxima was observed in viscosity versus composition plot corresponding to 80/20 LCP/PET blend. The N₁ increased with LCP loading in PET and with the increased asymmetry of LCP droplets. The N₁ also varied with the shear stress in two stages; the first stage demonstrated elastic deformation, whereas second stage displayed dominant plastic deformation of LCP droplets. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2212–2218, 2007     

Flow properties of molten ethylene–vinyl acetate copolymer and melt fracture

In an investigation of the behavior and formation mechanism of melt fracture the flow properties of molten ethylene–vinyl acetate (EVA) copolymer in the region of high shear rate were measured with a capillary-type rheometer. EVA copolymer differs slightly in flow curve from low-density polyethylene (LDPE); it seems, however, that the difference is due to the difference in molecular weight distribution (MWD) rather than to the materials themselves. The fluidity of molten EVA copolymer having a narrow MWD is equivalent to that of LDPE having a broad MWD and, generally, EVA copolymer has a higher fluidity than LDPE. It is expected that the fluidity increases with incorporation of vinyl acetate at the same MWD and the same M?_w. The critical shear rate increases with melt index and temperature. It cannot be found that the materials themselves and the MWD directly influence the critical point of melt fracture formation when the melt index is taken as a parameter. The critical viscosity (η_c) at which melt fracture forms decreases in an almost straight line with an increase of melt index. It was found from the studies of end correction and behavior of melt fracture formation that melt fracture occurs at the inlet of the die, and it is supposed that the melt fracture formation is caused by the elastic turbulence in the flow pattern due to a failure of recoverable shear strain at the die inlet.     

Elastic behavior of LDPE/HEPE blend melts in capillary extrusion

The studies of the elastic behavior in the capillary flow of LDPE/HDPE blend melts were carried out at a test temperature range from 180 to 200°C and at an apparent shear rate of about 25–120 s⁻¹. The end‐pressure drop (ΔP_end) increased nonlinearly with increasing wall shear stress (τ_w) and achieved a minimum value at a weight fraction (ϕ_HD) of HDPE of 50%. The die‐swell ratio (B) increased basically linearly with increasing τ_w or ΔP_end and achieved a maximum value at ϕ_HD of 50%. With the addition of the die length–diameter ratio, the values of B were decreased linearly. At a low shear rate, the temperature sensitivity of the melt die‐swell was more significant than at a high shear rate. With increasing ϕ_HD, B increased when ϕ_HD < 50%, then decreased. B reached a maximum value at ϕ_HD of 50% and a fixed apparent shear rate. This phenomenon may be explained by using the theory of viscoelastic competition between components of polymer blend melts. Furthermore, the first normal stress difference (N₁) of the sample melts was estimated by using an equation published in a previous work. The results showed that B increased linearly with increasing N₁. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 759–765, 2000     

Peroxide induced cross‐linking by reactive melt processing of two biopolyesters: Poly(3‐hydroxybutyrate) and poly(l‐lactic acid) to improve their melting processability

Poly(3‐hydroxybutyrate) (PHB) and poly(l ‐lactic acid) (PLLA) were individually cross‐linked with dicumyl peroxide (DCP) (0.25–1 wt %) by reactive melt processing. The cross‐linked structures of the polymer gel were investigated by nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopies. The size of the polymer crystal spherulites, glass transition temperature (T_g), melting transition temperature (T_m), and crystallinity were all decreased as a result of cross‐linking. Cross‐linking density (ν_e) was shown to increase with DCP concentration. Based on parallel plate rheological study (dynamic and steady shear), elastic and viscous modulus (G″ and G′), complex viscosity (η^*) and steady shear viscosity (η) were all shown to increase with cross‐linking. Cross‐linked PHB and PLLA showed broader molar mass distribution and formation of long chain branching (LCB) as estimated by RheoMWD. Improvements in melt strength offer bioplastic processors improved material properties and processing options, such as foaming and thermoforming, for new applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41724.     

Experimental study of the rheological,mechanical, and dielectric properties of MgO/LDPE nanocomposites

The properties of the polymer nanocomposites (PNCs), consisting low density polyethylene (LDPE) and magnesium oxide nanoparticles (MgO‐NPs), were systematically discussed in this paper. The shear mixing time and MgO concentration were considered as the two factors affecting the dispersion state, which was found to be effective to change the crystallinity and the mechanical performance of MgO/LDPE PNCs. A reduction in the dynamic shear viscosity was observed when the concentration of MgO‐NPs at a relative low level, which was also dominant by the dispersion states of MgO‐NPs. Evident enhancement of the static yield stress was revealed only by introducing a minute amount of MgO‐NPs (0.25 wt %). Meanwhile, the elastic and loss modulus were also found to be dependent on the dispersion state of MgO‐NPs. A positive increase in dielectric permittivity was identified by uniaxial stretching the MgO/LDPE PNCs strips owing to the orientation enhancement of internal microstructure. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43038.     

Melt rheology of nanometre‐calcium‐carbonate‐filled acrylonitrile–butadiene–styrene (ABS) copolymer composites during capillary extrusion

The melt flow properties during capillary extrusion of nanometre‐calcium‐carbonate‐filled acrylonitrile–butadiene–styrene (ABS) copolymer composites were measured by using a Rosand rheometer to identify the effects of the filler content and operation conditions on the rheological behaviour of the sample melts. The experiments were conducted under the following test conditions: temperature varied from 220 to 240 °C and shear rate ranged from 10 to 10⁴ s^?1. The filler volume fractions were 0, 10, 20, 30, 40 and 50%. The results showed that the shear flow did not strictly obey the power law under the test conditions, and that the entry pressure drop (ΔP_en) and the extension stress (σ_e) in entry flow increased nonlinearly, while the melt shear viscosity (η_s) and extension viscosity (η_e) decreased with increasing the wall shear stress (τ_w) at constant test temperature. The dependence of the melt shear viscosity on the test temperature was approximately consistent with the Arrhenius expression at fixed τ_w. When τ_w was constant, η_s and η_e increased while ΔP_en and σ_e decreased with the addition of the filler volume fraction. © 2002 Society of Chemical Industry     

Rheological equation for polymer melt under the action of vibration

Abstract

The entire extrusion process of a polymer melt within a capillary was analyzed thoroughly when a sinusoidal vibration of small amplitude was superimposed in parallel on the flow direction of the polymer melt. On the basis of rheological measurement, an equation for a polymer melt under parallel vibration, i.e. the apparent viscosity, was obtained. Calculation of the apparent viscosity was established by making use of novel experimental equipment. After collecting and analyzing the instantaneous data of capillary entry pressure, capillary volume flux and their phase difference in a superimposed vibration, the apparent viscosity of low-density polyethylene (LDPE) within a capillary was calculated. Meanwhile, the relationship of shear stress vs. shear rate for a LDPE melt with and without imposed vibration was presented.     

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     

Reactive compatibilization of poly(butylene terephthalate)/low‐density polyethylene and poly(butylene terephthalate)/ethylene propylene diene rubber blends with a bismaleimide

The reactive compatibilization effect of a small molecule, bismaleimide (BMI), on poly(butylene terephthalate) (PBT)/low‐density polyethylene (LDPE) and PBT/ethylene propylene diene (EPDM) rubber blends were investigated. All the blends were prepared by melt blending in the mixing chamber of a Haake Rheocord. The particle size of dispersed phase was reduced by >ten times by adding 1.2 wt % of BMI as observed with scanning electron microscopy. The torque‐time curve recorded during mixing showed that the addition of BMI leads to a significant increase in the viscosity of PBT, LDPE, EPDM, and the blends. This indicates that a chemical reaction has taken place. It was confirmed that free radicals are involved in the reactions because the addition of a stabilizer to the blends has removed all the compatibilizing effect, and the torque‐time curve does not show any increase in viscosity. A possible mechanism of compatibilization is proposed. The shear forces during melt mixing cause the rupture of chemical bond in the polymers, which form macroradicals of PBT, LDPE, or EPDM. These macroradicals react with BMI to form PBT‐BMI‐LDPE or PBT‐BMI‐EPDM copolymers. These in situ‐formed copolymers act as compatibilizers to give a significant refinement of the blend morphology. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2049–2057, 1999     

Flaring dies to suppress die drool

Die lip build‐up is the unwanted material accumulation on extrusion die lips. Here, flared dies are shown experimentally to suppress die lip build‐up. A semiempirical method for flared die design is also provided. Nonlinear viscoelastic constitutive equations are used to calculate the wall shear stress and first normal stress difference in flared dies. By incorporating melt memory, a promising design method for die flaring is presented. The stress history upstream of the die exit governs the die design. The upstream gap is selected to maximize undershoot of the first normal stress difference N₁ at the die wall caused by flaring. The flare length, on the other hand, is selected to ensure a steady N₁ at the die lips.     

Influence of side‐chain structures on the viscoelasticity and elongation viscosity of polyethylene melts

Metallocene‐catalyzed, low‐density and linear low‐density polyethylenes with similar melt indexes were used to investigate how side‐chain structures influence the elongation viscosity and viscoelastic properties. The viscoelastic properties were determined with a rotation rheometer, while the elongation viscosities were acquired by using isothermal fiber spinning. The Phan‐Thien‐Tanner (PTT) model was also used to understand how the side‐chain structure affects the elongation behavior. Experimental results demonstrate that the log G′ vs. log G″ plot can qualitatively describe the effects of the side chain branch on the rheological properties of polyethylene melts. According to the results determined by the PTT model, low‐density polyethylene (LDPE) has low elongation viscosities at high strain rates. This low elongation viscosity can be attributed to the fact that LDPE has high shear thinning behavior. The long‐chain branching tends to increase entanglements, thereby enhancing the storage modulus, elongation viscosity and shear‐thinning behaviors. Uniform side‐chain distribution lowers the entanglements, which results in a low storage modulus, elongation viscosity and shear‐thinning behavior.     

Structure‐property relationships of blends of polycarbonate

Three grades of bisphenol‐A polycarbonate—high molecular weight linear, high molecular weight branched and low molecular weight linear—and their blends have been studied by GPC, DMTA, DSC, rheometry and impact measurements. The molecular weight distribution of the blends agred with that predicted from the component's distributions, indicating that no transesterification reactions had occurred during melt blending. The T_g of the blends varied with blend composition according to the Fox equation and was related to the reciprocal molecular weight predicted by the Flory‐Fox equation. The low shear rate viscosity of the blends agreed with a logarithmic rule of mixtures and showed power‐law dependence on the weight average molecular weight. At higher shear rates, shear thinning was observed. The steady shear viscosity correlated well with the dynamic viscosity, as suggested by the Cox‐Merz relation. The stress relaxation behavior of the melt was very sensitive to the blend composition and molecular weight and correlated well with the real modulus. Temperature studies of the dart impact energy showed that only the low molecular weight polymer underwent a brittle‐duetile transition at ea ?30°C and that all the blends were tough at room temperature. The enhanced stress triaxiality inherent in the notched lzod test caused the impact strenght at room temperature to decrease almost linealy with blend composition.     

Melt Flow Properties During Capillary Extrusion of Linear Low-Density Polyethylene

Abstract

The melt flow properties of a linear low-density polyethylene (LLDPE) were measured by means of a capillary rheometer under the experimental conditions of temperatures from 220° to 260°C and apparent shear rates varying from 12 to 120 s^?1. The end pressure drop (ΔP _end) was determined by employing the Bagley's plotting method. The results showed that ΔP _end increased nonlinearly with increasing shear stress. The end pressure fluctuation phenomenon was observed at lower shear stress level, and several plateau regions were generated in the end pressure drop-shear stress curves, suggesting onset of the wall-slip phenomenon during die extrusion of the resin melt. The critical shear stress with onset end pressure fluctuation phenomenon increased with a rise of temperature. Furthermore, the melt shear flow did not strictly obey the power law. The melt shear viscosity decreased nonlinearly with increasing shear stress and with a rise of temperature, whereas the dependence of the melt shear viscosity on the test temperature accorded with a formula similar to the Arrhenius expression.     

Nonlinear rheological behavior of a novel oil displacing agent

In this work, the shear and elongational rheologies have been investigated for a newly developed oil displacing agent, polymeric surfactant‐PSf. It was found that the PSf solutions exhibited Newtonian, shear‐thinning, and shear‐thickening behavior, respectively, depending on the polymer concentration and shear rate, and Cox–Merz rule was not applicable to these systems. The first normal stress difference (N₁) versus shear rate plots for PSf were complicated, which varied with the composition of the solutions. The uniaxial elongation in capillary breakup experimental results indicated that Exponential model could be used to fit the experimental data of the PSf solutions at lower polymer concentrations. In addition, it was found that PSf was more effective in improving shear viscosity than partially hydrolyzed polyacrylamide, but not in the case of elongational viscosity. The experimental results indicated that the microstructural mechanisms are responsible for the rheological behavior of the polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40813.     

Rheological characterization of cellulose solutions in N‐methyl morpholine N‐oxide monohydrate

Three different modes of rheological properties were measured on 11 and 13 wt % solutions of cellulose in N‐methyl morpholine N‐oxide (NMMO) monohydrate, in which concentration range lyocell fibers of much reduced fibrillation are preferably produced. The dynamic rheological responses revealed that the Cox–Merz rule did not hold for these cellulose solutions. Both cellulose solutions showed a shear thinning behavior over the shear rate measured at 85, 95, 105, and 115°C. However, 13 wt % solution gave rise to yield behavior at 85ºC. The power law index ranged from 0.36 to 0.58. First normal stress difference (N₁) was increased with lowering temperature and with increasing concentration as expected. Plotting N₁ vs shear stress (τ_ω) gave almost a master curve independent of temperature and concentration, whose slope was about 0.93 for both cellulose solutions over the shear rate range observed (τ_ω > 500 Pa). In addition, the cellulose solutions gave high values of recoverable shear strain (S_R), ranging from 60 to 100. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 216–222, 2002     

Studies on the polyblends of poly(vinyl chloride) with various methacrylate copolymers,melt rheological properties. II

Studies have been made on the melt rheological properties of poly(vinyl chloride) (PVC) with copolymers of methyl methacrylate (MMA) and methyl acrylate (MA), ethyl acrylate (EA), butyl acrylate (BA), and 2-ethyl hexyl acrylate (EHA) at a blending ratio of 80:20. Effect of blend composition on shear stress–shear rate, melt viscosity, melt elasticity, and extrudate distortion have been studied. A significant decrease in the melt viscosity is observed on incorporation of low T_g, acrylate copolymers such as those with BA and EHA, thereby reducing the processing temperature. First normal stress and die swell ratio also decreases with an increase in the side chains of acrylate copolymer. PVC blended with P(MMA-co-BA) and P(MMA-co-EHA) is sensitive to both temperature and shear stress.     

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.     

An improved basis for characterizing the suitability of fly ash as a cement replacement agent

Fly ash is a critical material for partial replacement of ordinary portland cement (OPC) in the binder fraction of a concrete mixture. However, significant compositional variability currently limits fly ash use. For example, the performance of OPC‐fly ash blends cannot be estimated a priori using current characterization standards (eg, ASTM C618). In this study, fly ashes spanning a wide compositional range are characterized in terms of glassy and crystalline phases using a combination of X‐ray fluorescence (XRF), X‐ray diffraction (XRD), and scanning electron microscopy with X‐ray energy‐dispersive spectroscopy (SEM‐EDS) techniques. The compositional data are distilled to a unitless parameter, the network ratio (N_r), which represents the network behavior of atoms that form alkali/alkaline earth‐aluminosilicate glasses that make up fly ashes. N_r is correlated with known composition‐dependent features, including the glass transition temperature and amorphous XRD peak (“hump”) position. Analysis of heat release data and compressive strengths are used to evaluate the impact of fly ash compositions on reaction kinetics and on the engineering properties of cement‐fly ash blends. It is shown that fly ashes hosting glasses with a high network ratio (ie, having a less stable glass structure) are more reactive than others.