Melt shear viscosity of PP/Al(OH)3/Mg(OH)2 flame retardant composites at high extrusion rates

The melt apparent shear viscosity (η_a) of polypropylene (PP) composites filled with aluminum hydroxide [Al(OH)₃] and magnesium hydroxide [Mg(OH)₂] was measured by means of a capillary rheometer under experimental conditions of temperature ranging from 180 to 200°C and apparent shear rate varying from 10 to 2 × 10³ s⁻¹, to identify the effects of the filler particle content and size on the melt viscosity. The results showed that the melt shear flow of the composites obeyed the power law and presented pseudoplastic behavior. The dependence of η_a on temperature was consistent with the Arrhenius equation. The sensitivity of η_a for the composite melts to temperature was greater than that of the unfilled PP, and weakened with increasing apparent shear rate. The η_a increased linearly with an increase of the weigh fraction of the flame retardant, especially in the low apparent shear rate region. The η_a of the composites decreased slightly with an increase of particle size of flame retardant. Moreover, the variation for the η_a with particle size of flame retardant was much less than with apparent shear rate under these test conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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.     

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     

Effect of polymer matrix on the rheology of hydroxyapatite‐filled polyethylene composites

The effect of matrix polymer and filler content on the rheological behavior of hydroxyapatite‐filled injection molding grade high‐density polyethylene (HDPE) has been studied. Studies of the flow curves revealed that the matrix and the composite exhibit three distinct regions in the flow curve, namely, a pseudoplastic region at low to moderate shear rates, a plateau and a second pseudoplastic region at high shear rates. The shear stress corresponding to the plateau (τ_c) is dependent on both the filler concentration and the melt temperature. Addition of HA in the HDPE matrix increases the value of τ_c and decreases compressibility of the melt. An increase in temperature also raises the value of τ_c. From the nature of flow curves it is concluded that the matrix polymer largely decides the rheology of the composite.     

The influence of titanium dioxide on the rheological and extrusion properties of polymer melts

An experimental study of the influence of titanium dioxide (TiO₂) on the rheological and extrusion properties of five polymer melts (two low-density polyethylenes, two high-density polyethylenes, and a polystyrene) has been carried out. Increasing TiO₂ loading increases the shear viscosity η, with the extent of increase being greater at lower shear rates. At moderate and high TiO₂ loadings, the filled melts may possess yield values. Empirical equations relating viscosity to filler loading have been developed. The first normal stress difference was measured for the melts and found to increase with increasing TiO₂ loading. However, the extent of increase was less than found for the viscosity function and interpretation in terms of the theory of viscoelasticity suggests that the characteristic relaxation time of the melts decreases with increasing TiO₂ level. Empirical equations relating the first normal stress difference coefficient to volume fraction of the filler have been developed. Addition of TiO₂ is found to decrease extrudate swell and retard the occurrence of extrudate distortion.     

Shear viscosity of nylon 6 melts reinforced with microfibrous calcium silicate hydrate

Steady shear viscosity of nylon 6 melts reinforced with xonotlite, microfibrous calcium silicate hydrate (6CaO · 6SiO₂ · H₂O), is investigated. The highly filled nylon 6 melt tends to exhibit a yield value, resulting in remarkable viscosity increase particularly at low shear rates. Addition of the xonotlite significantly increases activation energy of viscous flow of the nylon 6 melt, leading the viscosity to be strongly temperature dependent. Comparisons with the melts filled with glass fibers and wollastonite are made. Flow-induced orientation becomes more important at low volume fractions. Shortening of the xonotlite during shear flow measurement can also be observed.     

Rheological properties of the blends of polychloroprene with poly[ethylene(vinyl acetate)]

Blends of poly[ethylene(vinylacetate)] (EVAc-45; 45% VAc content) and polychloroprene (CR) have been studied with respect to capillary and dynamic flow. It is found that EVAc-45, CR, and their blends are shear thinning (pseudoplastic) in nature. Though shear viscosity (η_a) and dynamic out-of-phase viscosity (η′_E) obeys power law, dynamic elongational viscosity (η′_E) does not follow it due to the synchronization of molecular vibration with the applied frequency at around 11 Hz. Both η_a and η′_E of the blends show positive deviation with respect to their additive values. The relative positive deviation (RPD) in shear flow increases with increasing temperature and shear rate. In the case of dynamic flow, RPD increases with increasing temperature but exhibits a decreasing trend with increasing frequency. RPD can be fitted well into a fifth-order equation with a weight fraction of CR (W_CR) in EVAc-45—CR blends. From rheological point of view, this relative positive deviation indicates blend compatibility between EVAc-45 and CR. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1759–1765, 1997     

Rheological behavior of semi‐aromatic transparent polyamide

The rheological behaviors of semi‐aromatic transparent polyamide (SATPA) melt are investigated using a capillary rheometer. The effects of shear rate, shear stress, and temperature on the apparent viscosity η_a of SATPA are discussed. A correlation of non‐Newtonian index with temperature is obtained. The results show the shear thinning of SATPA; meanwhile η_a decreases with increasing temperature and shear rate, and the viscous flow activation energy is further obtained from temperature dependence of the samples. It was concluded that the apparent viscosity η_a is sensitive to temperature at lower shear rate owing to the higher viscous flow activation energy; on the contrary, the influence of temperature effect on the apparent viscosity becomes minor at higher shear rate due to the lower viscous flow activation energy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1586–1589, 2005     

Melt flow behavior in capillary extrusion of nanosized calcium carbonate‐filled poly(L‐lactic acid) biocomposites

Nanosized calcium carbonate (nano‐CaCO₃)‐filled poly‐L ‐lactide (PLLA) biocomposites were compounded by using a twin‐screw extruder. The melt flow behavior of the composites, including their entry pressure drop, melt shear flow curves, and melt shear viscosity were measured through a capillary rheometer operated at a temperature range of 170–200°C and shear rates of 50–10³ s^?1. The entry pressure drop showed a nonlinear increase with increasing shear stress and reached a minimum for the filler weight fraction of 2% owing to the “bearing effect” of the nanometer particles in the polymer matrix melt. The melt shear flow roughly followed the power law, while the effect of temperature on the melt shear viscosity was estimated by using the Arrhenius equation. Hence, adding a small amount of nano‐CaCO₃ into the PLLA could improve the melt flow behavior of the composite. POLYM. ENG. SCI., 52:1839–1844, 2012. © 2012 Society of Plastics Engineers     

Stress–strain behavior of SAN/glass bead composites above the glass transition temperature

Relaxation and stress–strain behavior of SAN–glass bead composites are studied above the glass transition temperature. The strain imposed on the polymeric matrix of the composite is defined as ?_p = ?_c/(1 ? ?^?). Stress relaxation data for the filled polymer which is independent of strain can be calculated by multiplying the relaxation modulus (at a certain strain) by (1 + ?_p). Stress–strain curves at constant strain rate and for different concentrations of the filler can be shifted to form a master curve independent of filler content if the tensile stress is plotted versus ?^p. The relaxation modulus increases with increasing the filler concentration and can be predicted by a modified Kerner equation at 110°C.     

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     

Melt viscosity of poly(vinyl chloride) formulations

Commercial, suspension-type PVC resin, poly (vinyl chloride), molecular weight M_w × 10^?4 = 8.6 ± 0.9, polydispersity M_w/M_n = 2.26, was mixed with plasticizer di(2-ethyl hexyl)phthalate (DOP) and organo-tin stabilizer in four different proportions. The mixtures were milled and pressed into sheets for testing. The polymer content in these samples was 97, 80, 60, and 40 wt percent. The viscoelastic properties of the materials were investigated using a Weissenberg rheogoniometer in a cone-and-plate, steady-state shearing mode. The viscosities and primary normal stress difference coefficients were measured at shear rates of 10^?2 ≤ \documentclass{article}\pagestyle{empty}\begin{document}$ \mathop \gamma \limits^. $\end{document} (sec^?1) ≤ 10² and at temperatures from 151 to 246°C. The zero shear viscosities, plotted as log η₀ vs 1/T (T is the absolute temperature) did not follow either a straight line dependence, reported for PVC melts at low shear rates at 170–190°C, nor was any discontinuity found near 195°C as by others; the data follows a continuous concave curve. The apparent activation energy of flow increases steeply with decreasing temperature. The data can be represented by a WLF type of equation, but the magnitudes of the parameters of this relation differ from expected values. A crossplot of log η₀ (T = const.) vs log w (where w is the polymer content) also demonstrates a faster increase of η₀ with w than expected from the straight line dependence. The primary normal stress difference coefficient was found to increase with w and decrease with T, paralleling the observed dependencies of η₀.     

The rheology of filled polymers

The flow properties of polymer melts containing fillers of various shapes and sizes have been examined. If there is no failure of either the filler or polymer in the solid state, then the modulus enhancement for randomly distributed filler is equal to the melt viscosity enhancement under medium shear stress conditions (10⁴ Nm^?2) in simple shear flow or in oscillatory shear flow. Submicron-size fillers, in particular, can form weak structures in the melt that greatly increase the low shear rate viscosity without changing the modulus of the solid proportionately. The highly pseudo-plastic nature of polymer melts at shear stresses of 10⁶ Nm^?2 means that, even without orientation of filler particles toward the flow direction, the viscosity enhancement is less than at lower shear stresses.     

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.     

The development of the velocity field in polymer melts in a reservoir approaching a capillary die

Color motion pictures have been made of the flow of low-density polyethylene, polystyrene, and isotactic polypropylene at 180°C in the reservoir approach to a capillary extrusion rheometer. Detailed observations of the variation of flow patterns with extrusion rate were made. At low flow rates, essentially radial flow into the capillary entrance was observed in all polymers. With increasing flow rate, the included entrance angle α for the polyethylene and polystyrene decreased from 180°C and a “wine glass” structured velocity field was observed with stagnant circulating regions in the corners and the melt channeling in through the wine glass to the capillary entrance. The angle α was related to entrance pressure drop Δp_e and capillary wall shear stress σ_w data through the semilogarithmic equation where α is in degrees; Δp_e/σ_w is interpreted as a Weissenberg number. The breakdown of stable laminar flow of the melts in the reservoir and the distortion of extrudates was observed. These phenomena seemed to be initiated by the formation of a spiralling motion in the reservoir.     

A single-mode rheological model for steady flows of polymer melts

The steady shear viscosity (η_s), the steady first normal stress coefficient (Ψ₁), the steady second normal stress coefficient (Ψ₂), and extensional viscosity (η_e) are four important parameters for polymer melts during polymer processing. In this article, we propose a stress and rate-dependent function to describe creation and destruction of polymer junctions. Moreover, we also introduce a movement expression to describe nonaffine movement of network junctions. Based on network theory, a nonaffine single-mode rheological model is presented for the steady flow of polymeric melts, and the equations of η_s, Ψ₁, Ψ₂, and η_e are derived from the model accordingly. Furthermore the dependences of η_s and η_e on model parameters are discussed for the model. Without a complex statistical simulation, the single-mode model with four parameters yields good quantitative predictions of the steady shear and extensional flows for two low density polyethylene melts reported from previous literature in very wide range of deformation rates. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Role of Sulfur and Its Diffusion in Silicate Glass Melts

Sulfur diffusion D_S is reported on a technical alkali-poor barium alumoborosilicate glass melt at 900–1400°C and on three further Na₂O-modified glass melts at 900°C, using a radioactive tracer method. Whereas D_S for the base glass melt amounts to ≈1 × 10⁻¹⁵m²/s at 900°C, it increases nearly exponentially with increasing Na₂O content from 0 to 15 mol% by almost three orders of magnitude. Similar to other glass melts, the sulfur diffusion obtained in these melts is also closely related to the Eyring diffusivity D_n derived from viscosity. The diffusion controlling species in oxidized melts seems to be SO₄²⁻, in reduced melts S²⁻. SO₃²⁻ does obviously not play any role in this transport process.     

Melt rheological properties of polypropylene–wood flour composites

This article presents study of melt rheological properties of composites of polypropylene (i-PP) filled with wood flour (WF), at filler concentrations of 3–20 wt%. Results illustrate the effects of (i) filler concentration and (ii) shear stress or shear rates on melt viscosity and melt elasticity properties of the composites. Incorporation of WF into i-PP results in an increase of its melt viscosity and a decrease of melt elasticity such as die swell and first normal stress differences; these properties, however, depend on filler concentration. Processing temperature of the filled i-PP increases as compared to the nonfilled polymer.     

Compatibility,steady and dynamic rheological behaviors of polylactide/poly(ethylene glycol) blends

Understanding the rheological behavior of plasticized polylactide (PLA) contributed to the optimization of processing conditions and revealed the microstructure–property relationships. In this study, the morphological, thermal, steady and dynamic rheological properties of the PLA/poly(ethylene glycol) (PEG) blends were investigated by scanning electron microscope, differential scanning calorimeter, and capillary and dynamic rheometers, respectively. The results illuminated that the melt shear flow basically fitted the power law, whereas the temperature dependence of the apparent shear viscosity (η_a) or complex viscosity (η*) followed the Arrhenius equation. Both the neat PLA and PLA/PEG blends exhibited shear‐thinning behavior. Because the incorporation of PEG reduced the intermolecular forces and improved the mobility of the PLA chains, the η_a, η*, and storage and loss moduli of the PLA/PEG blends decreased. The PEG content (W_PEG) ranged from 0 to 10 wt %, both η_a and η* decreased significantly. However, the decrements of η_a and η* became unremarkable when W_PEG exceeded 10 wt %. The reason was attributed to the occurrence of phase separation, which resulted in the decrease in the plasticization and lubrication efficiencies. This study demonstrated that the addition of the right amount of PEG obviously improved the flow properties of PLA. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42919.     

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