A comparison of measurements of the viscoelastic properties of polymer melts by means of the Han slit/capillary rheometer and the Weissenberg rheogoniometer

Measurements were taken of the viscoelastic properties of six polymer melts by mean of the Weissenberg rheogoniometer and the Han slit/capillary rheometer. Polymers in vestigated were three high-density polyethylenes of different polydispersity, a low-density polyethylene, a polypropylene, and a polystyrene. The range of shear rates tested was from about 5.0 × 10^?3 to 10 sec^?1 with the Weissenberg rheogoniometer, from about 10 to 10² sec^?1 with the slit rheometer, and from about 10² and 10³ with the capillary rheometer: the temperature of measurement was 200°C. The three different apparatuses give consistent results over almost six decades of shear rates, yielding satisfactory correlations of shear viscosity to shear rate and of normal stress difference to shear rate.     

Recoverable shear strain of liquid crystal‐forming concentrated hydroxypropyl cellulose solutions

The recoverable shear strain (S_R) for the liquid crystal‐forming hydroxypropyl cellulose solutions was determined by means of a concentric cylinder rotational apparatus as functions of shear stress prior to recovery and concentration of the solutions at 30°C. S_R greatly depended on shear stress and concentration; the phase of the solution (the single phase or biphase) governed the dependences of S_R on stress and concentration. S_R increased with increasing stress for the single phase and decreased for the biphase. S_R seemed to be related to the die swell (B): S_R ∝ Bⁿ. S_R exhibited a maximum and a minimum with respect to concentration. S_R for the cellulosic cholesteric liquid crystalline solutions was greater than that for the isotropic solutions. A model was proposed for explaining the greater S_R. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 865–872, 2002     

On the use of PET-LCP copolymers as compatibilizers for PET/LCP blends

Copolyesters of poly(ethylene terephthalate) (PET) with a liquid crystalline polymer (LCP), SBH 1:1:2, have been synthesized by the polycondensation, carried out in the melt at temperatures up to 300°C of sebacic acid (S), 4,4′-dihydroxybiphenyl (B), and 4-hydroxybenzoic acid (H) in the presence of PET. The PET-SBH copolyesters have been characterized by differential scanning calorimetry, scanning electron microscopy, X-ray diffraction, etc., and the relationships between properties and preparation conditions are discussed. The copolyesters show a biphasic nature, which is more evident for the products synthesized with a thermal profile comprising relatively lower temperatures (220–230°C) in the initial stages of the polycondensation. Another procedure, whereby the addition of PET to the monomer charge was made at a later stage of the reaction, has also been devised to prepare copolyesters with enhanced blockiness. The compatibilizing effect of the PET-SBH copolymers toward PET/SBH blends has been investigated. PET/SBH blends (75/25, w/w) have been prepared in a Brabender mixer at 270°C and 30 rpm, with and without the addition of appropriate amounts (2.5, 5, and 10%, w/w) of 50-50 PET-SBH copolyesters. Different blending techniques have been used according to whether the three components were fed into the mixer at the same time, or one of them was added at a later stage. The effect of the type and the amount of added copolyester has been studied through morphological, thermal, and mechanical characterizations. The results show that the addition of small amounts ∼5 wt% of copolyesters leads to improved dispersion and adhesion of the minor SBH phase. Moreover, while the tensile modulus of the blends is practically unaffected by the addition of the copolymer, a substantial increase of both tensile strength and elongation to break is found for a concentration of added copolyester of ∼5wt%. Slightly better results were apparently obtained by the use of a block copolyester.     

Aromatic liquid crystalline copolyesters with low Tm and high Tg: Synthesis,characterization, and properties

In this study, a series of aromatic copolyesters P‐BPAx with lower melting temperature and higher glass transition temperature derived from hydroxybenzoic acid (HBA), 6‐hydroxy‐2‐naphthoic acid (HNA), bisphenol A (BPA) and terephthalic acid (TA) were synthesized via melt polymerization. The copolyesters were characterized by FTIR, solid state ¹³C NMR, DSC, TGA, polarized optical microscopy, X‐ray diffraction, and rheometry measurements. With addition of BPA, the resulting copolyester's melting temperature decreased from 260 to 221°C and its glass transition temperature increased from 70 to 135°C, compared with the parent copolyester P‐HBA70 (HBA/HNA copolymer). With exception of copolyester P‐BPA5.0 (225–280°C), the copolyesters could maintain liquid crystalline behavior in a broad temperature range from 230°C to higher than 410°C. The ability to form nematic liquid crystalline phase disappeared when BPA concentration became higher than 15 mol %. X‐ray diffraction analysis showed crystallinity decreased as the BPA content increased. A slightly distorted O" and a substantially distorted O′ orthorhombic phase was observed for P‐BPA2.5. Upon annealing at 220°C, the O" phase disappeared and the O′ phase became stronger gradually. Rheology study data showed the ability to process the copolyesters improved in those compositions containing <2.5 mol % BPA. Continuing to increase concentrations of BPA, they became intractable. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40487.     

The rheological characterization of a series of thermotropic liquid crystalline polymers

Dynamic rheological experiments were performed on a series of two copolymers and a homopolymer based on units of terephthaloyl chloride and isophthaloyl chloride at 90/10 and 75/25 mole ratios combined with 1,10-bis(4-hydroxyphenyl)-decane. Optical microscopy and wide angle X-ray diffraction (WAXD) confirmed that all of the polyesters in the present series formed nematic liquid crystals with nematic-to-isotropic temperatures in the range of 270 to 320°C with increasing terephthaloyl unit content. Broad nematic-to-isotropic transitions observed by differential scanning calorimetry (DSC) were indicative of biphasic regions where the nematic and isotropic phases coexist. The rheological behavior of each polymer was more complex in the nematic phase than in the isotropic phase with shear thinning occurring in the former but Newtonian behavior in the latter. There were also some indications that nematic flow behavior could be induced in these polymers by dynamic oscillatory shear flow above the nematic-to-isotropic transition, T_i. A form of hysteresis was observed with the homopolymer in that measurements of the dynamic viscosity, η*, taken with ascending frequency sweeps were higher than those taken with descending frequency sweeps.     

The effect of TLCP melt structure on the bulk viscosity of high molecular mass polyethylene

A thermotropic liquid crystalline polyester (TLCP), denoted as TCLP3 and based on hydroxybenzoic acid, hydroquinone and sebacic acid, was used as a processing aid in the extrusion of high molecular mass polyethylene (HMMPE). This TLCP is in the nematic phase at 179.6–182°C. Capillary rheometry experiments were carried out at two processing temperatures: 190°C and 230°C. At 190°C TLCP3 is predominantly nematic and at 230°C it is predominantly isotropic. It is an effective processing aid for HMMPE, particularly at 190°C, with viscosity reductions in excess of 90% with a 1 wt% TLCP3/HMMPE blend. The rheological characteristics of the blends have been linked to the optical textures of the TLCP3 using hot-stage optical microscopy. From the experimental observations speculations are made about the mechanisms of viscosity reduction. Initial viscosity reductions are caused by TLCP3 structure effects (fibrillation and phase change), giving rise to fibrillation-induced molecular orientation in the neighboring HMMPE phase. This is only effective when nematic structures are present. Above a critical wall shear stress value the lubrication effect due to TLCP3 migration is dominant.     

Enhancement of rheological and mechanical properties of bitumen using styrene acrylonitrile copolymer

In this research, styrene acrylonitrile copolymer as a novel additive is used to modify rheological, mechanical and thermal properties of the base bitumen 70 penetration grade. Styrene acrylonitrile copolymer combines the rigidity of polystyrene with the hardness and thermal resistance of polyacrylonitrile to enhance viscoelastic property of the bitumen. To investigate the performance of the proposed mixture, shear complex module, phase angle, penetration, softening point, and reversibility of prepared samples are measured at different additive content and compared with the base bitumen. The results show that softening point of the base and modified samples are 49–86°C, respectively. The rheological properties of the base bitumen and modified samples are measured by a dynamic shear rheometer (DSR). The phase angle as elasticity measure decreases from 55° to 35° in the modified bitumen compared to the base bitumen. Generally, the experimental results showed that styrene acrylonitrile copolymer makes bitumen to be more stable at high temperatures and more flexible at low temperatures. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41875.     

Rheological properties of a liquid crystalline copolyester

Rheological studies of an experimental liquid crystalline (LC) copolyester were carried out using a capillary rheometer and a cone and plate rheometer. Rheological characteristics of the polymer in the nematic state were observed. The nematic melt was found to be pseudoplastic and the degree of pseudoplasticity varied with shear rate. Melt viscosity was found to decrease with shear rate. Negative die swelling was observed at the exit of the capillary rheometer at temperatures marginally above the solid-nematic transition temperature of the polymer and was also found to be a function of shear rate. The dynamic mechanical properties of the polymer were studied as a function of temperature. The activation energies of flow and of dynamic mechanical deformation were calculated.     

Thermal degradation of polypropylene in a capillary rheometer

Melt viscosity of a polypropylene (PP) resin was measured in a capillary rheometer between 220 and 260°C. The melt viscosity showed a power law behavior with strong shear rate dependence. The effects of temperature and shear rate on the degradation were studied in the rheometer by heating at 260 and 280°C, and extruding at shear rates up to 10000 sec ?1 . Melt flow index (MFI) of samples after shearing and heating treatment was measured to characterize the molecular weight change. An increase in MFI was found for PP sheared at high temperature. Heating for longer time also increased MFI. Increase of shear rate had a small effect on increasing MFI at 260°C but produced a larger effect at 280°C. A constant increment in MFI was observed in PP subjected to high temperature processing and was attributed to degradation due to oxygenated products.     

A new rheometer measuring infrared dichroism in molten polymers subjected to transient and steady shear flow

A rotational parallel plate rheometer that enables simultaneous measurement of the transient or steady-state rheological properties and infrared dichroism was designed and constructed to study orientation in molten polymers. Measurements can be carried out at shear rates between 0.05 and 300 s⁻¹ and at temperatures between 20 and 300°C. Both shear stress and axial normal force together with dichroism are continuously measured during shear flow. Infrared dichroism data for polypropylene showed excellent agreement with data obtained with a FTIR-instrument. The Hermans orientation function for molten poly(dimethyl siloxane) at steady state showed a strong shear-rate dependence in the region 0.1−20 s⁻¹. Rheological data for molten poly(dimethyl siloxane) agrees with data obtained from a conventional rheometer.     

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.     

Comparisons of the rheological behaviors of polypropylene and polymethyl methacrylate in a capillary die

In this study, the rheological characteristics of polypropylene (PP) melt at 210, 220, and 230 °C and polymethyl methacrylate (PMMA) melt at 230, 240, and 250 °C in a micro die were investigated. The experiments were performed over a shear rate range of 3 × 10² to 5 × 10³ s^?1 using an advanced twin‐bore capillary rheometer. Dies with diameters of 1.0, 0.5, and 0.25 mm were used. The results indicated that the geometric dependences of the PP and PMMA viscosities were not identical at different shear rates and temperatures and that the micro size effect had a profound influence on the PP viscosity. The analysis demonstrated that the variations in the shear viscosity of the PP and PMMA melts in the micro die were partially attributed to the contribution of the pressure applied to the polymer melts. Additionally, the effect of wall slip on the PP and PMMA viscosities in the tested dies was investigated based on the modified Mooney method. The results implied that wall slip easily occurred in the PP melt flowing through the 0.25 mm die at 210 °C due to the distinct size effect. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44617.     

The viscosity reducing effects of very low concentrations of a thermotropic copolyester in a matrix of HDPE

A thermotropic liquid crystalline polymer (TLCP), denoted as TLCP(1), was used as a processing aid for high density polyethylene (HDPE). The TLCP was a copolyester of hydroxybenzoic acid, hydroquinone and sebacic acid and was blended with HDPE to give 0.2, 0.5 and 2 wt% TLCP(1) blends. At a temperature of 185°C, when TLCP(1) is in the nematic regime, the processing window for HDPE was increased tenfold from a maximum shear rate of 100 s^?1 for pure HDPE to 1170 s^?1 for a 2 wt% TLCP(1) blend. There were large viscosity reductions of between 85% and 90% compared with the pure HDPE when the blended material was used at a wall shear stress value of approximately 2.4 × 10⁵ Pa. This viscosity reduction was attributed to the TLCP(1) droplets changing shape from spheres to slender fibrils under shear flows.     

Glass-fiber-reinforced polypropylene/EPDM blend. I. Melt rheological properties

Melt rheological properties of the blend of isotactic polypropylene (PP) and ethylene propylene diene rubber (EPDM) at varying ratios and of the glass fiber (GF) filled PP and PP/EPDM blend by varying both GF loading and blending ratio of the polyblend matrix are studied. Rheological measurements at 220°C in shear rate range 10¹?10⁴s^?1 were made on a capillary rheometer. Scanning electron micrographs of the extrudates are presented to show the morphology and the alignment of the glass fibers with respect to the flow direction. Variations of pseudoplasticity index, melt viscosity, and melt elasticity with EPDM content in PP/EPDM blend, and with varying GF content at any given composition of the matrix in PP/EPDM/GF ternary system, in the studied range are presented and discussed. Resultes on melt viscosity and melt elasticity show (i) reduced effect of GF at high shear rates on these properties and (ii) upward deviation of melt viscosity versus shear rate curve at low shear rates. A change in flow behavior in presence of GF is observed around a critical shear rate 2 × 10³ s^?1 and is attributed to the difference of interaction of GF and the dispersed rubber droplets at high and low shear rates. Elastic recovery showed nonequilibrium behavior at low shear rates.     

Rheological properties of liquid crystalline solutions of ethyl celluloses with different molecular weight in m-cresol

Steady-state shear rheological properties of liquid crystalline solutions of four ethyl celluloses (ECs) were determined at a low shear rate (1 s^?1) and at relatively high shear rates by using two rheometers (cone-plate and capillary types), and were compared with those of liquid crystalline hydroxypropyl cellulose (HPC). The effect of molecular weight (MW) on the viscoelastic behavior was also determined. The viscoelastic behavior was also determined. The viscometric behavior of EC solutions was similar to that of HPC solutions: (1) with respect to temperature, the shear viscosity (η) at shear rate of 1 s^?1 exhibited a minimum (η_min) and a maximum (η_max), and the concentration–temperature superposition for η could be applied; (2) the behavior of η at relatively high shear rates as a function of shear rate or polymer concentration was typical of lyotropic liquid crystals. The MW dependence of η_min was greater than that of η_max for EC solutions. The behavior of the elastic parameters such as Bagley correction factor (v), entrance pressure drop (ΔP_ent), and die swell (B) at relatively high shear rates for EC solutions was essentially similar to that for HPC solutions: (1) the shear rate or stress dependence of the elastic parameters was greatly dependent on whether the polymer solution was in a single phase or biphase; (2) with respect to concentration the elastic parameters showed a maximum and a minimum and the maximum or minimum point for each parameter was not always identical to each other. η for the isotropic or fully anisotropic solutions at a given concentration (C) increased, whereas η for the solutions in the vicinity of the biphasic region showed a minimum, with respect to MW. The slope of η at a given shear rate vs. CM _w depended on shear rate, and this slope for the isotropic solutions appeared to be greater than that for fully anisotropic solutions. ΔP_ent and v at a given concentration showed either a monotonical increase or a maximum or minimum with MW, and this behavior was not fully consistent with that of η. B for the isotropic solutions increased and B's for both biphasic and fully anisotropic solutions were almost constant, with MW.     

Effect of SBS Content on Low Temperature Impact Strength,Morphology and Rheology of PP-cp/SBS Blends

Izod impact strength of PP impact copolymer/Styrene-Butadiene-Styrene blends were evaluated at varied sub-zero temperatures and demonstrated 12 times enhancement in impact strength of 40% SBS containing blend over pure PP-cp at ?40°C. SBS content played a vital role in morphology development as it changes from droplet morphology to elongated ellipsoid to a seemingly networked structure leading towards different fracture mechanisms. Rheological properties of blends evaluated on capillary rheometer showed pseudoplastic behavior at varied shear rates (50 ? 10⁴ s^?1) at 220°C and good agreement between experimental shear viscosity and theoretical values as per log additivity principle at high shear rates.     

A polypropylene/high density polyethylene blend compatibilized with an ethylene‐propylene‐diene monomer block copolymer: Fitting dynamic rheological data by emulsion models with a physical scheme

The dynamic rheological behaviors at 210, 230, and 250 °C are measured by small amplitude oscillatory shear on a rotational rheometer for a polypropylene(PP)/ ethylene‐propylene‐diene monomer(EPDM) block copolymer/ high density polyethylene (HDPE)/blend. The scanning electron microscope (SEM) photomicrographs show the blend has a droplet/matrix, semi‐co‐continuous, co‐continuous morphology respectively at different weight ratios. The Cole–Cole (G″ vs. G′) data of the blends can be fitted by the simplified Palierne's model only for very narrow weight ratios. A physical scheme is proposed that the dispersed droplets are enclosed by EPDM, thus an equivalent dispersed phase is made up of “expanded” EPDM. With this physical scheme the G″ vs. G′ data of the HDPE‐rich blends at 210 °C can be fitted well by Palierne's model. Also with the physical scheme the G″ vs. G′ data of the PP‐rich blends at three temperatures can be fitted well by G–M's model with G* of interface equals to zero. This means the proposed physical scheme is reasonable. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43709.     

The degradation of polystyrene during extrusion

An investigation was made of the magnitude and mechanism of shear degradation of a narrow distribution, high molecular weight (M_w = 670,000) polystyrene. An Instron rheometer was used to perform the extrusion at temperatures from 164° to 250°C. The change in molecular weight distribution was studied by gel permeation chromatography. The maximum shear stress employed was 5.83 kg/cm². It was found that degradation could be induced at high stress at temperatures of 50°C lower than degradation of polystyrene would occur exclusively due to thermal forces. An activation energy for the degradation, calculated at constant shear rate, was +20.2 kcal/mole. The direction and magnitude of this value are consistent with degradation induced through a mechanical reduced activation for thermal degradation.     

Melt rheology of polyarylate/polybutylene terephthalate blends

The viscosity, the activation energy of flow, and the exchange reactions of bisphenol A 50/50 isophthalic/terephthalic acid and poly(butylene terephthalate) blends are studied by means of an extrusion capillary rheometer, covering a range of 10 s^?1 to 300 s^?1 shear rate and 280°C to 300°C temperature. The results are interpreted in terms of compatibility and free volume additivity. The decrease in viscosity with time is explained as a result of transesterification rather than degradation.     

Thermal behavior and laser marking of a novel nematic liquid crystalline polymer

The thermal behavior and laser marking of a novel nematic liquid crystalline polymer is explored in this report. The glass transition and mesophase transition temperatures of this material are at 45 and 68°C, respectively, and allow the ready annealing of the nematic phase as well as conversion of the nematic to the isotropic phase by pulsed laser irradiation of metallized or dyed films of the polymer.