Comparison of superimposed effects in high‐shear‐rate capillary rheology of polystyrene,polypropylene, and linear low‐density polyethylene melts

Polymer melts exhibit unique rheological behaviors at high shear rate up to 10⁶ s^?1, which is a common phenomenon in micro‐injection molding. Both online and commercial capillary rheometers, which were modified to allow regulation of back pressure, were used for measuring the melt shear viscosities of polystyrene (PS), polypropylene (PP), and linear low‐density polyethylene (LLDPE) under high shear rates. The rheological characteristics of the three melts were compared through the systematical analyses for three significant effects, namely the end pressure loss, pressure dependence, and dissipative heating in capillary flow. Pronounced end effect begins to appear at the shear rates of 1.6 × 10⁵, 8.0 × 10⁵, and 2.8 × 10⁶ s^?1 for the PS, PP, and LLDPE melts, respectively. The significance of the end effect can be ordered as PS > PP > LLDPE. It seems that the polymers with more complex molecular structures exhibit a higher degree of divergence between the comprehensively corrected and uncorrected melt viscosity curves. Moreover, the dissipation effect begins to predominate over the pressure effect under the lowest shear rate of 10⁵ s^?1 for the PS melt among the three melts. POLYM. ENG. SCI., 55:506–512, 2015. © 2014 Society of Plastics Engineers     

Rheology of poly(vinyl chloride) plastisol for super‐high‐shear‐rate processing. II

Capillary flow of poly(vinyl chloride) plastisol was examined at low, high, and superhigh shear rates. At the low to intermediate shear rates, the flow was pseudo‐plastic, but the measured viscosity was not reproducible and widely scattered. The flow behavior was explained as the breakup of the particle network into network‐fragments of varying size. At high shear rates, the measured viscosity was reproducible and increased with shear rate, indicating that the particles were, by and large, separated from each other. At superhigh shear rates, the viscosity decreased with the increase of shear rate. The particles cease to participate in flow because rotation becomes more difficult. A plug‐flow ensues with a thin layer of lubricating plasticizer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A unifying approach for melt rheology of linear polystyrene

Several studies of melt rheological properties of polystyrene have been conducted over the past 50 years. Several approaches, including empirical models, have been developed to understand the behavior of materials using simple equations. The existing melt rheology models are best suited for high‐molecular‐weight polymers whose T_g does not vary. In this work, a semiempirical viscosity equation has been derived, including the effect of T_g dependence on molecular weight, to describe the melt rheology of low‐molecular‐weight polymers. The equation is derived based on a combination of well‐known concepts, such as the effects of free volume and molecular dynamics on polymer rheology. This provides a better understanding of the rheological behavior in the low‐molecular‐weight regime with respect to temperature and molecular weight. Because of the industrial trend towards lower molecular weight materials for applications such as high solids coatings, this unifying approach, based on the free volume theory with a simple expression, is of extreme practical significance. This equation can predict the zero shear viscosity behavior for different molecular weights, including low‐molecular‐weight regions, and temperatures. Viscosity calculations using the empirical equation agree with published experimental data. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2597–2607, 2007     

Shear and extensional rheology and flow‐induced orientation of carbon nanofiber/polystyrene melt composites

The rheological behavior and morphology of polystyrene/carbon nanofiber (PS/CNF) composites in their melt phase have been characterized through experimental measurements. Viscosity measurements of the PS/CNF composites in the linear viscoelastic regime show the ratio of the transient extensional viscosity to the transient shear viscosity to be greater than three, the Trouton ratio. This behavior is due to differences in the flow‐induced orientation of CNFs in shear and extensional flow. The orientation development of the CNFs in shear and extensional flow was analyzed through a method utilizing transmission electron microscopy and was used to explain observed rheological phenomena. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Pressure effects in polymer melt rheology

Wide ranges of pressure and temperature are encountered in polymer processing operations, as, for example, in injection molding. While the temperature dependence of viscosity has been widely studied, the pressure dependence has not. The present work focuses on the measurement of the melt viscosity of polystyrene at high pressures (up to 124 MPa or 18,000 psi) and high shear rates (1–100 s^?1) at 180°C. The apparatus was a capillary rheometer with the downstream chamber being held at a high back pressure by means of a needle valve. The data so obtained were combined with zero shear viscosity data from the literature; and then correlated with a shear-dependent rheological model of the authors, using a shift factor suggested by Utracki (based on the Simha–Somcynsky equation of state). The final correlation calls for making both the elastic modulus and the time constant dependent on pressure, with the modulus being the dominant factor at high shear rates.     

Characterization of the free volume in high‐impact polystyrene/polypropylene and high‐impact polystyrene/high‐density polyethylene blends probed by positron annihilation spectroscopy

The free‐volume properties of high‐impact polystyrene (HIPS)/polypropylene (PP) and HIPS/high‐density polyethylene (HDPE) blends were investigated by means of positron annihilation lifetime spectroscopy (PALS). The measured results show that the free‐volume holes in the semicrystalline polymers, such as PP and HDPE, were not large enough to accommodate the branched chains and the end groups of the macromolecular chains in HIPS to produce favorable interactions between the semicrystalline polymers and the HIPS polymer in these blends; thus immiscible blends were formed. The weak interaction between two dissimilar polymer molecules only took place in the regions between two amorphous phases. In addition, the observed negative deviations of the longest lifetime intensity and the free‐volume fraction were attributed to the influence of the interfacial polarization during PALS measurement. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1507–1514, 2003     

Toughening study of fire‐retardant high‐impact polystyrene

Fire‐retardant high‐impact polystyrene (HIPS) was modified by melt blending with varying amounts of three types of tougheners. The effects of the tougheners on the properties of the fire‐retardant HIPS were studied by mechanical, combustion tests, and thermogravimetric analysis. The morphologies of fracture surfaces and char layers were characterized through scanning electron microscopy. The results show that the impact properties of styrene–butadiene–styrene (SBS)‐containing composites were better than those of ethylene–propylene–diene monomer (EPDM)‐containing or ethylene–vinyl acetate copolymer (EVA)‐containing composites. The tensile strength and flexural modulus of the fire‐retardant HIPS decreased evidently with the addition of tougheners. It is found that the compatibility between SBS copolymer and HIPS matrix was best among the three types of tougheners. The addition of SBS had little influence on the thermal property, residue, flammability, and morphology of char layer of the fire‐retardant HIPS, but the addition of EPDM rubber or EVA brought adverse influence on the residue, flammability, and morphology of char layer of the fire‐retardant HIPS, especially for EPDM. Copyright © 2009 John Wiley & Sons, Ltd.     

Photochemical aging and processability of life‐time‐controlled polystyrene/high‐impact polystyrene blends

This work investigated the influence of the addition of acetophenone and benzophenone (2.5 and 5%) on the photodegradability of polystyrene/high‐impact polystyrene blends (50/50 w/w) prepared by sheet extrusion, aiming to improve their decomposition during exposure to a natural environment. The modified materials were submitted to photodegradation under controlled conditions, and the extent of degradation was monitored by suitable characterization techniques, such as infrared and ultraviolet–visible spectroscopy, viscosimetry, and measurements of the mechanical properties. The processability of the modified blends was also studied by capillary and oscillatory rheometry. Evidence for the formation of hydroperoxides and carbonyl groups, the occurrence of chain scission, and the loss of mechanical properties was achieved, being greater for samples with benzophenone. It was also observed that for the same ketone level, benzophenone caused greater changes in the mechanical properties, and this was in agreement with the decrease in the molecular weight observed. Thus, the addition of this type of chemical compound could enhance the photodegradability of polystyrene/high‐impact polystyrene blends without a significant effect on their processability and mechanical performance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Dynamic mechanical behavior of atactic and high‐impact polystyrene

Results of the dynamic mechanical behavior of atactic polystyrene (PS) and high‐impact polystyrene (HIPS) for temperatures between 300 and 425 K at a frequency of the order of 50 kHz are presented. The storage Young's modulus, (E′), of the HIPS is lower than the PS value, being the relationship between them a function of the rubber phase volume fraction, independent of the measurement frequency. The glass transition temperature (T_g) of HIPS is shifted to lower temperature in respect to the PS. The γ relaxation appears at 308 K in PS at 50 kHz, while it seems to move toward lower temperatures in the HIPS. Both shifts are attributed to the presence of mineral oils in the HIPS. The values of E′, T_g, and the temperature of the γ relaxation at 50 kHz are discussed within the scope of the theory of viscoelasticity. Finally, the effect of thermal treatments, using different annealing times, on the behavior of both materials is shown. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 865–873, 2000     

Specific energy dissipation rate for super‐high‐rate anaerobic bioreactor

BACKGROUND: Specific energy dissipation rate (?) is an important performance parameter of the super‐high‐rate anaerobic bioreactor (SAB) and is closely linked with power matching and operation optimization. The ? value was investigated for a SAB using anaerobic granular sludge and simulating gas production. The ? models for separation, reaction and water distribution units were established. RESULTS: Experimental results showed that the model predictions agreed well with the experimental data and, thus, they may be used for power matching and operation optimization of similar high‐rate anaerobic bioreactors. The ? value for the separation unit was so low as to be neglected. The maximum ? values for the reaction unit during nonfluidization, granular sludge agglomeration, liquid‐solid two‐phase fluidization and gas‐liquid‐solid three‐phase fluidization states were 0.143 W m^?3, 4.449 W m^?3, 2.173 W m^?3 and 11.132 W m^?3, respectively. The maximum ? value for the water distribution unit was 8.37 W m^?3. ? for the reaction unit was significantly influenced by ρ_p, u_l and V_p, u_g and d_p. CONCLUSION: The maximum ? value of 11.132 W m^?3 was the basic parameter for power matching for the SAB. Some measures were introduced to reduce the ? values based on parametric sensitivity analyses. The present investigation will further assist in optimizing the operation and design of SABs. Copyright © 2011 Society of Chemical Industry     

Creep resistance of wood‐filled polystyrene/high‐density polyethylene blends

Creep, the deformation over time of a material under stress, is one characteristic of wood‐filled polymer composites that has resulted in poor performance in certain applications. This project was undertaken to investigate the advantages of blending a plastic of lower‐creep polystyrene (PS) with high‐density polyethylene (HDPE) at ratios of 100:0, 75:25, 50:50, 25:75, and 0:100. These various PS–HDPE blends were then melt blended with a short fiber‐length wood flour (WF). Extruded bars of each blend were examined to measure modulus of elasticity and ultimate stress. Increasing the ratio of WF increased modulus of elasticity in all composites, except between 30 and 40% WF, whereas the effect of WF on ultimate stress was variable, depending on the composite. Scanning electron microscopic images and thermal analysis indicated that the wood particles interacted with the PS phase, although the interactions were weak. Finally, creep speed was calculated by using a three‐point bending geometry with a load of 50% of the ultimate stress. Creep decreased only slightly with increasing WF content but more significantly with increasing PS content, except at pure PS. The WF/75PS–25HDPE blend showed the least creep. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 418–425, 2001     

Foaming behavior of high‐melt strength polypropylene/clay nanocomposites

The foaming behavior of high‐melt strength polypropylene (HMS‐PP) and HMS‐PP/Cloisite 20A nanocomposites (PPNC) was studied in a batch process. PPNCs with 2, 4, 8, and 10 wt% clay were prepared in a twin screw extruder. The morphology of the nanocomposites was studied using XRD and TEM. Subsequently, foaming experiments were conducted using supercritical CO₂ as the blowing agent in a batch process, and foams with cell sizes varying from the sub micrometer to the micro meter range were prepared. The effect of variation in saturation pressure and temperature, foaming temperature, foaming time, and quench temperature was determined experimentally. Dynamic rheological measurements were conducted to relate the influence of nanocomposites morphology with foam cell growth and nucleation. Extensional rheological measurements were also conducted to detect the presence of strain hardening effect at the foaming temperatures used in the experiment. It was found that the nucleation efficiency of clay reduces with increase in clay loading. Also, the optimum amount of filler for generation of fine celled foams was found to be around the percolation threshold of the polymer. The extended strain hardening effect shown by the polymer in presence of clay plays an important role in stabilizing foam cell sizes. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Colloidal stability of high‐solids polystyrene and polyvinyl acetate latices

Commercial emulsion polymerization processes are often done with high‐solids recipes (e.g., about 50 wt % monomer), resulting in relatively viscous, pseudoplastic reaction mixtures. The change in rheological behavior during high‐solids emulsion polymerization complicates the operation in terms of imperfect mixing, increasing heat transfer resistance and reactor fouling. In this article, we report the influence of solids content on the colloidal stability of polystyrene (PS) and polyvinyl acetate (PVAc) latex systems. For the systems investigated, solids content up to 50 wt % had no influence on the colloidal stability of the latex. The influence of recipe on colloidal stability is more pronounced than the influence of operating conditions. Brownian coagulation dominates over shear coagulation for both low‐ and high‐solids systems, although in some cases the operating conditions appear to have some effect on the course and outcome of high‐solids emulsion polymerization. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1780–1791, 1999     

Dynamic and capillary shear rheology of natural fiber‐reinforced composites

An extended dynamic and capillary rheological study of molten flax and sisal polypropylene (PP) composites was performed. Fiber concentration varied from 20 to 50 wt% and shear rate from 0.1 rad s^?1 to 10,000 s^#142;?1. Maleic anhydride‐grafted‐PP was used as compatibilizer; it strongly reduces PP and composite viscosity. Composites are yield‐stress shear‐thinning fluids with solid‐like behavior being more pronounced at high fiber content. Composites do not obey Cox–Merz rule, which was explained by different macrostructures of the molten composites in parallel plates and capillary die geometries: random fiber orientation versus strong alignment in the flow direction, respectively. Theories describing the viscosity of suspensions of solid particles were applied to the composites studied and rheological parameters and maximal packing fiber volume fraction were calculated. POLYM. ENG. SCI., 53:2582–2593, 2013. ©2013 Society of Plastics Engineers.     

Effect of styrene‐butadiene‐styrene addition on polystyrene/high‐density polyethylene blends

In order to prepare an ideal mixture, the physical and chemical properties of the constituent polymers must be known in detail. Thus, selection of the polymers that will constitute the mixture and a thorough study of the mixing methods and the economic factors become important. A rigid plastic is toughened by dispersing a small amount of rubbery material (generally 5–20%) in the rigid plastic matrix. Such a mixture of plastics is characterized by its impact resistance. Among thermoplastics toughened in this way are polystyrene (PS), poly(vinyl chloride), poly(methyl methacrylate), polypropylene, polycarbonate, and nylons, and recently thermoset resins such as epoxies, unsaturated polyester resins, and polyamids. In this study PS and high‐density polyethylene polymers were mixed in various ratios. In order to increase the compatibility of the mixtures, 5, 7.5, and 10% SBS copolymer was also added. The mixing operation was conducted by using a twin‐screw extruder. The morphology and the compatibility of the mixtures were examined by using SEM and DSC techniques. Furthermore, the elastic modulus, yield and tensile strengths, percent elongation, Izod impact resistance, hardness, and melt flow index values of the polymer alloys of various ratios were determined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2967–2975, 2002; DOI 10.1002/app.2325     

Blends of polyamide1010 with unmodified and maleic‐anhydride‐grafted high‐impact polystyrene

The crystallization behaviors, dynamic mechanical properties, tensile, and morphology features of polyamide1010 (PA1010) blends with the high‐impact polystyrene (HIPS) were examined at a wide composition range. Both unmodified and maleic‐anhydride‐(MA)‐grafted HIPS (HIPS‐g‐MA) were used. It was found that the domain size of HIPS‐g‐MA was much smaller than that of HIPS at the same compositions in the blends. The mechanical performances of PA1010–HIPS‐g‐MA blends were enhanced much more than that of PA1010–HIPS blends. The crystallization temperature of PA1010 shifted towards higher temperature as HIPS‐g‐MA increased from 20 to 50% in the blends. For the blends with a dispersed PA phase (≤35 wt %), the T_c of PA1010 shifted towards lower temperature, from 178 to 83°C. An additional transition was detected at a temperature located between the T_g's of PA1010 and PS. It was associated with the interphase relaxation peak. Its intensity increased with increasing content of PA1010, and the maximum occurred at the composition of PA1010–HIPS‐g‐MA 80/20. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 857–865, 1999     

Modification of PET in high‐speed melt spinning by blending with PEN

Blends of polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) were melt spun using a high‐speed winding process in a single‐screw extruder combined with a spinning setup. The filaments had a single T_m and T_g, which indicates excellent compatibility in both the amorphous and crystalline phases. Birefringence and wide angle X‐ray measurements indicated that compounding PEN into PET suppresses stress‐induced orientation and decreases the stressinduced crystallization in the filaments. Adding PEN to PET relaxes the formation of skin‐core structures for as‐spun fibers and reduces the occurrence of broken filaments. Although the addition of PEN reduced crystallinity, it did not affect the tenacity and the shrinkage of the compounded filaments. The elongation of the fibers could be reduced by 30% to 40%, eliminating the need for a further drawing. These results are attributed to PEN's rigid backbone. Adding PEN to PET improves PETs spinnability during high‐speed spinning.     

Structure and melt rheology of long‐chain branching polypropylene/clay nanocomposites

Long‐chain branching polypropylene (LCB‐PP)/clay nanocomposites were prepared by melt blending in a twin‐screw extruder. The microstructure and melt rheology of these nanocomposites were investigated using x‐ray diffraction, transmission electron microscopy, oscillatory shear rheology, and melt elongation testing. The results show that, the clay layers are intercalated by polymer molecular chains and exfoliate well in LCB‐PP matrix in the presence of maleic anhydride grafted PP. Rheological characteristics, such as higher storage modulus at low‐frequency and solid‐like plateau in tan‐ω curve, indicate that a compact and stable filler network structure is formed when clay is loaded at 4 phr (parts per hundred parts of) or higher. The response of the nanocomposite under melt extension reveals an initial decrease in the melt strength and elongational viscosity with increasing clay concentration up to 6 phr. Later, the melt strength and elongational viscosity show slight increases with further increasing clay concentration. These results might be caused by a reduction in the molecular weight of the LCB‐PP matrix and by the intercalation of LCB‐PP molecular chains into the clay layers. Increases in the melt strength and elongational viscosity for the nanocomposites with decreasing extrusion temperature are also observed, which is due to flow‐induced crystallization under lower extrusion temperature. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of the high‐density polyethylene melt index on the microcellular foaming of high‐density polyethylene/polypropylene blends

The effect of high‐density polyethylene (HDPE)/polypropylene (PP) blending on the crystallinity as a function of the HDPE melt index was studied. The melting temperature and total amount of crystallinity in the HDPE/PP blends were lower than those of the pure polymers, regardless of the blend composition and melt index. The effects of the melt index, blending, and foaming conditions (foaming temperature and foaming time) on the void fractions of HDPEs of various melt indices and HDPE/PP blends were also investigated. The void fraction was strongly dependent on the foaming time, foaming temperature, and blend composition as well as the melt index of HDPE. The void fraction of the foamed 30:70 HDPE/PP blend was always higher than that of the foamed 50:50 HDPE/PP blend, regardless of the melt index. The microcellular structure could be greatly improved with a suitable ratio of HDPE to PP and with foaming above the melting temperature for long enough; however, using high‐melt‐index HDPE in the HDPE/PP blends had a deleterious effect on both the void fraction and cell morphology of the blends. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 364–371, 2004