Study of kinematics and dynamics of film blowing of different polyethylenes

An extensive experimental study of the effects of material characteristics and processing parameters on the kinematics and dynamics of film blowing is presented. Three polyethylene resins, a high-density polyethylene (HDPE), a low-density polyethylene (LDPE), and a linear low-density polyethylene (LLDPE) were investigated. The convergent flow analysis of Cogswell was used to characterize the elongational flow behavior of the polymers. Strain rates and pressure inside the bubble (P_i) have been determined over a wide range of film blowing conditions. Moreover, on-line bubble temperature and birefringence measurements have been carried out along the length of the bubble. The experimental results reveal that the three polymers display different behaviors. The LLDPE requires the highest P_i value and the LDPE, the lowest. Consistent with this, the LLDPE shows the lowest in-plane birefringence and the LDPE, the highest. Interactions between various process parameters affecting the P_i value are characterized. Bubble instability is correlated to the apparent uniaxial elongational viscosity and P_i. The most stable polymer (LDPE) has the highest elongational viscosity and requires the lowest P_i. Stresses have been calculated with the help of the birefringence and P_i data. The stress and strain rate data were used to calculate an apparent nonuniform biaxial elongational viscosity of the melts, but could not be correlated through any simple constitutive equation.     

Transient elongational viscosity of LLDPE/LDPE blends and its relevance to bubble stability in the film blowing process

Transient elongational viscosity of linear low density polyethylene (LLDPE) and its blends with 10% and 20% of low density polyethylene (LDPE) was measured at two temperatures by a constant strain rate elongational rheometer. In addition, the performance of the blends in the film blowing process was assessed in terms of bubble stability at two processing temperatures. An operating window for stable bubble production was determined. The elongational viscosity measurements on blends revealed stronger strain hardening characteristics at a higher temperature of testing. These results correlate favorably with findings from a bubble stability investigation where it was found that the size of the operating window for stable bubble production increased with increasing extrusion temperature. This work seems to indicate that increasing processing temperature during the film blowing of LLDPE-rich blends could lead to a processability improvement of these blends as far as bubble stability is concerned.     

Effects of ABS rubber particles on rheology,melt failure,and thermoforming

The rubber particles included in rubber modified polymeric materials such as acrylonitrile‐butadiene‐styrene (ABS) polymer and impact modified polymers play an important role in determining their rheological properties, processing behavior, and mechanical properties. In this study both small strain oscillatory shear viscosity in the frequency range from 10^?2 to 10² s^?1 and uniaxial elongational viscosity behavior at two elongation rates ( = 0.1 and 1.0 s^?1) over the range of temperatures from 140°C to 200°C were measured for commercial ABS polymers with different contents and deformability of rubber particles. The influences of rubber content and deformability on rheological properties such as melt elasticity, elongational viscosity, strain hardening and/or softening, the onset of nonuniform deformation, and thermoforming performance were investigated. The Wagner two‐parameter nonlinear viscoelastic constitutive model was used to describe strain hardening behavior, while the Considère criterion was used to determine the onset point of nonuniform deformation. The part thickness distribution obtained through use of a vacuum snap‐back forming process was simulated to investigate the effects of rheological changes associated with different rubber particles on the thermoforming performance. It was found that ABS polymers with larger contents of hard rubber particles exhibited more melt elasticity, stronger strain hardening, a maximum of biaxial elongational viscosity, onset of nonuniform deformation at later time, and better thermoforming performance. Strain hardening and the Considère criterion provide simple, reliable indicators of the thermoforming performance of ABS polymers.     

High‐viscosity polylactide prepared by in situ reaction of carboxyl‐ended polyester and solid epoxy

To extend the potential applications of polylactide (PLA) in film blowing, foaming, thermal molding, and so on, the high‐viscosity PLA composites with various compositions of carboxyl‐ended polyester (CP) and solid epoxy (SE) have been successfully prepared by an in situ reaction blending process. Their rheological properties, crystallization behaviors, tensile properties, and morphologies have been investigated in detail. The results show that the complex viscosity η*, G′, and G″ at low‐frequency region and the tensile strength of PLA composites are obviously improved with the addition of CP/SE, but the nonisothermal crystallization of PLA component is hindered. SEM reveals that some microphase separations existed in the as‐prepared composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Rheology of LLDPE,LDPE and LLDPE/LDPE blends and its relevance to the film blowing process

The relevance of polymer melt rheology in film blowing process for linear low‐density polyethylene (LLDPE) and its blends with three different low‐density polyethylenes (LDPEs) has been discussed. The effect of different LDPE components as well as their concentration on shear and elongational viscosity has been investigated. A good correlation has been observed between the extensional rheological parameters of LDPEs measured by different experimental techniques. The molecular structure of parent polymers as well as blend composition play an important role in the rheology of these blends and consequently their performance in the film blowing process. © 2000 Society of Chemical Industry     

Effects of swelling on the viscoelastic properties of polyester films made from glycerol and glutaric acid

Viscoelastic properties have been determined for poly(glycerol‐co‐glutaric acid) films synthesized from Lewis acid‐catalyzed polyesterifications. The polymers were prepared by synthesizing polymer gels that were subsequently cured at 125°C to form polymer films. The polymers were evaluated for the extent of reaction before and after curing by Fourier transform infrared spectroscopy. They were subsequently immersed in dimethylsulfoxide, tetrahydrofuran, water, methanol, and hexane for 24 h. The amounts of solvent absorbed were monitored and recorded. Dependent up the solvent used, the polymers were able to absorb 9.5–261% of its weight. The effects of the solvent absorption on the viscoelastic properties of the polyester films were evaluated by determining their elastic modulus (G′), viscous modulus (G″), tan δG″/G′, and complex viscosity (η*) by performing oscillatory frequency sweep experiments. The elastic modulus (G′) and viscous modulus (G″) were both higher for the dry polymers than the solvent‐absorbed polymers. However, the polymer films were all higher in elastic (G′) character than viscous (G″) character. Therefore, tan δG″/G′ < 1 before and after immersion in solvents. Values for η* decreased with angular frequency for all of the polyesters tested in this study. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

Correlation of the melt rheological properties with the foaming behavior of immiscible blends of poly(2,6‐dimethyl‐1,4‐phenylene ether) and poly(styrene‐co‐acrylonitrile)

Immiscible blends of poly(2,6‐dimethyl‐1,4‐phenylene ether)/poly(styrene‐co‐acrylonitrile) (PPE/SAN) were batch‐foamed using CO₂ as a blowing agent as a function of foaming temperature, foaming time, and blend composition. Evaluation of the resulting cellular morphology revealed an enhanced foamability of SAN with PPE contents up to 20 wt% as indicated by a similar volume expansion but a significantly reduced mean cell size. This behavior is related to a heterogeneous nucleation activity by the dispersed PPE phase. A further increasing PPE content, however, leads to increasing foam densities as well as nonuniform foam morphologies. The changes in the foaming behavior can be correlated with the melt rheological properties and the corresponding blend morphology. Shear‐rheological investigations revealed an onset of percolation of the dispersed PPE phase between 20 and 40 wt%, and a transition towards cocontinuity at 60 wt%. The materials response under uniaxial elongational flow, as assessed by Rheotens measurements, revealed an increase in elongational viscosity scaling with the PPE content, similar to the shear data. However, the strain hardening behavior was reduced by increasing PPE contents and, at 20 wt%, the drawability revealed a significant drop‐both phenomena limiting the foamability of polymers. In summary, the present study discusses fundamental aspects of foaming immiscible PPE/SAN blends. POLYM. ENG. SCI., 48:2111–2125, 2008. © 2008 Society of Plastics Engineers     

Rheological properties of metallocene isotactic polypropylenes

Rheological properties of metallocene‐catalyzed isotactic polypropylenes (MET‐PP) were evaluated in comparison with those of Ziegler–Natta‐catalyzed isotactic polypropylenes (ZN‐PP) and MET‐PP was generally characterized in a rheological aspect. Based on the characterization, various flow processibilities and their effect on the higher order structure and product properties of the processed article were estimated. The capillary flow properties at various temperatures, elongational flow properties, and dynamic viscoelasticities of MET‐PPs and ZN‐PPs with various melt flow indexes (MFIs) were measured. Furthermore, as an example of application of rheological analysis, the selection of proper raw resin and processing conditions in the sheet‐extrusion of MET‐PP was studied. MET‐PP shows the following rheological features due mainly to the narrow molecular weight distribution in comparison with ZN‐PP with equivalent MFI to that of MET‐PP: while the viscosities at low shear rates are lower, those at high shear rates are higher. Although there is little difference in the loss modulus G″ (viscosity), the storage modulus G′ (elasticity) is very (about one decade) lower. The die swell is much smaller. The entrance pressure loss and end correction coefficient are lower. The critical shear rate at which a melt fracture begins to occur is lower. The melt tension, elongational viscosity, and melt flow index ratio are lower. The flow activation energy is slightly lower. The zero‐shear viscosity obeys the 3.4th‐power law independent of catalyst. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2157–2170, 2002     

Improvement of processability of poly(ε‐caprolactone) by radiation techniques

Improvement of processability of Poly(ε‐caprolactone) (PCL) was achieved by introduction of a branch structure using gamma‐irradiation from a ⁶⁰Co source. Irradiated PCL has higher molecular weight by producting a branch structure. Hence, the irradiation at a lower dose, such as 3 Mrad, leads to a higher melt viscosity. The branched structure gave improved properties for dynamic viscoelasticity and elongational viscosity. High elongational viscosity was observed by entanglement due to branch chain formed during irradiation, and the elongational viscosity for 3 Mrad is higher than 1.5 Mrad. Due to a higher elongational viscosity, PCL foam can be produced by a molding process. Foam produced from irradiated PCL pellets at 3 Mrad has honeycomb‐like structure, and the foam showed higher enzymatic degradation compared to film samples. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1815–1820, 1999     

Rheological properties of poly(methyl methacrylate)/rigid ladderlike polyphenylsilsesquioxane blends

A series of poly(methyl methacrylate) (PMMA) blends with rigid ladderlike polyphenylsilsesquioxane (PPSQ) were prepared at weight ratios of 100/0, 95/5, 90/10, 85/15, and 80/20 by solution casting and then hot‐pressing. Their rheological properties have been studied under both dynamic shear and uniaxial elongation conditions. Their rheological properties depend on the compositions. The storage modulus, G′, loss modulus, G″, and dynamic shear viscosity, η*, of the PMMA/PPSQ 95/5 blend were slightly lower than those of pure PMMA. However, the values of G′, G″, and η* for the other PMMA/PPSQ blends are higher than those of PMMA. The G′ values increase with an increase in PPSQ content from 5% through 15% PPSQ at low frequencies and then drop as the PPSQ content increases to 20%. Uniaxial elongational viscosity (η_E) data demonstrate that PMMA/PPSQ blends exhibit slightly weaker (5% PPSQ) and much weaker (10% PPSQ) strain‐hardening than PMMA. In contrast, the PMMA/PPSQ 85/15 blend shows strain‐softening. Neither strain‐hardening nor strain‐softening was observed in the 80/20 blend. The special rheological properties for the 95/5 blend is probably due to a decrease in PMMA entanglements brought by the specific PMMA–PPSQ interactions. Rheological properties of PMMA/PPSQ blends with higher PPSQ content (≥10%) are mainly affected by formation of hard PPSQ particles. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 352–359, 2007     

The effect of recycling on LDPE foamability: Elongational rheology

The purpose of this work was to investigate changes in the elongational rheology of low density polyethylene (LDPE) when recycled. Both foamed and unfoamed LDPE were submitted up to 10 generations in a closed loop using constant extrusion conditions and azodicarbonamide as a chemical blowing agent. For both foamed and unfoamed polymers, decreasing elongational properties in terms of strain hardening was observed, indicating progressive loss of foamability with the number of time the polymer is recycled. It was also found that the elongational properties of the foamed polymer decreased more rapidly than its unfoamed counterpart. It is believed that higher mechanical degradation of polymer may be the result of higher deformation rates (biaxial) associated with foaming and the accumulation of blowing agent residues limiting polymer chain mobility and entanglement. POLYM. ENG. SCI., 48:11–18, 2008. © 2007 Society of Plastics Engineers     

Rheological behavior of ethylene–octene copolymer vulcanizates: Effect of blowing agent and precipitated silica filler

An experimental study of the rheological behavior of ethylene–octene copolymer vulcanizates in extrusion containing blowing agent has been carried out. The cell morphology development has been studied through a scanning electron microscope. Rheological properties of unfilled and precipitated silica‐filled systems with variations of blowing agent, extrusion temperature, and shear rate have been studied by using a Monsanto processibility tester (MPT). The total extrusion pressure (P_T), apparent shear stress (τ_wa), apparent viscosity (η_a), and die swell (%) of the unfilled and silica‐filled compounds have been determined by using MPT. The effect of blowing agent (ADC) on the rheological properties of the vulcanizates has also been investigated. There is a reduction of stress and viscosity with blowing agent loading. It was observed that the incorporation of a blowing agent led to decreased shear thinning behavior resulting in an increase in power law index. The viscosity reduction factor (VRF) of unfilled vulcanizates is found to be dependent on the concentration of the blowing agent, shear rate, and temperature, whereas VRF of silica‐filled vulcanizates is found to be dependent on shear rate, temperature, and blowing agent concentration. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1132–1138, 2003     

Rheological investigation of a random copolymer of polyacrylamide and polyacryloyl hydrazide (PAM‐ran‐PAH) for oil recovery applications

In this article, we synthesize and investigate the rheological properties of a random copolymer PAM‐ran‐PAH of polyacrylamide (PAM) and polyacryloyl hydrazide (PAH) and compare with the results of PAM at different temperature (30 and 80 °C) and salinity (0 and 1.0 wt %). At 30 °C, both PAM and PAM‐ran‐PAH exhibited non‐Newtonian rheology with both shear thinning and shear thickening responses. The rheological properties such as viscosity and moduli (G′ and G″) of PAM significantly deformed at elevated temperature (80 °C) and salinity (1.0 wt %), resulting no recovery in viscosity and moduli. On the other hand, the effect of temperature and salinity was found to be least on PAM‐ran‐PAH and showed better stability with the possibility of recovering its original rheological properties. The performance of PAM and PAM‐ran‐PAH was also characterized by enhanced oil recovery tests. The use of PAM‐ran‐PAH for polymer flooding, due to its stable rheology, resulted in an increase in the oil recovery than PAM. In general, the rheological behavior of PAM‐ran‐PAH as a chemical agent proved to be thermally stable than PAM, which clearly supports its use for saline environment and high temperature applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44648.     

Rheological and thermal properties of saponified cassava starch‐g‐poly(acrylamide) superabsorbent polymers varying in grafting parameters and absorbency

Cassava starch‐graft‐poly(acrylamide) superabsorbent polymers (SAPs) with varying absorbencies were synthesized. Weight average molecular weight (M_w) of the hydrolyzed starch‐graft‐copolymers ranged from 1.6 × 10⁶ to 2.8 × 10⁶ g/mol, the largest being shown by the sample with highest percentage grafting. The storage (G′) and loss modulus (G″) of hydrogels were determined as a function of frequency. G″ was larger than G′ for the hydrogels with higher absorbencies and exhibited a liquid‐like behavior. However, hydrogels with lower absorbencies showed a reverse viscoelastic behavior. The viscosity of hydrogels determined using a Brookfield viscometer at different shear rates was found to be larger for the hydrogels with higher absorbencies. The melting temperature (T_m) and enthalpy change of fusion (ΔH_f) of the SAPs ranged from 149.7 to 177.7°C and 65 to 494.9 J/g, respectively and showed a positive correlation with grafting parameters and M_w. Heavy metal ion removal capacity of hydrogel followed the order Cu²⁺ > Pb²⁺ > Zn²⁺. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40368.     

Linear low‐density polyethylene/poly(ethylene terephthalate) blends compatibilization prepared by an eccentric rotor extruder: A morphology,mechanical, thermal,and rheological study

In this study, various poly(ethylene terephthalate) (PET) and linear low‐density polyethylene (LLDPE) with maleic anhydride‐grafted LLDPE (LLDPE‐g‐MAH) compatibilizer were melt blended under an elongational flow. A novel extrusion device, eccentric rotor extruder (ERE), was developed to supply such flow during the process. Including morphology, mechanical properties, melting behavior, and rheological behavior were studied. The morphological study showed that the compatibility between LLDPE and PET was greatly improved with LLDPE loading up to 80 wt %. Mechanical tests indicated that LLDPE could toughen PET to some extent. Moreover, a comparison of samples prepared between ERE and conventional extruder was made and demonstrated the sample prepared by ERE can exhibit better mechanical properties. Differential scanning calorimetry results revealed that PET can promote the crystallinity of LLDPE. Rheological behavior indicated that the complex viscosity of the blends exhibited strong shear thinning phenomenon with increasing LLDPE content, particularly in high‐frequency range blend with the LLDPE weight ratio of 80 wt % was more sensitivity to shear rate than neat LLDPE. The G′‐G″ curves of the blends also revealed that the microstructure of the blends changed significantly with the addition of LLDPE which was consistent with the scanning electron micrographs that PET particles became smaller and distributed more uniform with increasing LLDPE content. Furthermore, the blends showed similar stress relaxation mechanism with adding LLDPE content from 60 to 100 wt %. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46489.     

Rheological properties of PLGA-PEG-PLGA copolymers for ophthalmic injection

Polymer rheological property is one of intrinsic properties for the design and preparation of intravitreal injection systems. Rheological behaviors of thermosensitive poly(lactic acid-co-glycolic acid)-poly(ethylene glycol)-poly(lactic acid-co-glycolic acid) (PLGA-PEG-PLGA) triblock copolymers were investigated in this article. The rigidity phase angle (δ), elastic modulus (G′), viscous modulus (G″), and complex viscosity (η*) were determined. The injectability of polymers was evaluated as well. The results indicated both temperature and concentration were key parameters influencing elasticity of polymers. Owing to low complex viscosity (below 1 Pa s), PLGA-PEG-PLGA polymers can be successfully injected at room temperature. When the temperature was raised to 37°C, the complex viscosity increased (over 4 Pa s). Thus, suitable rheological properties (G′ > G″; tan δ < 1) were obtained for injection administration. Elastic modulus (G′), viscous modulus (G″), and complex viscosity (η*) were diminished when polymer solutions were ejected through syringe needles (25 gauge, G). Ejection force (from 4.21 to 19.42 N) was required in the process of injecting administration through syringe needles (24, 25, and 26 G) for polymer solutions at 20, 25, and 30% (w/v) concentration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Rheology-processing-property relationships in tubular blown film extrusion. I. High-pressure low-density polyethylene

Three different grades of high-pressure low-density polyethylene resin were used to establish relationships between tubular film blowability and the molecular parameters, namely, the molecular weight distribution (MWD) and the degree of long-chain branching (LCB), and also between the processing conditions and the mechanical properties of the tubular blown films produced. For the study, both the shearing and elongational flow properties of the resins were determined. During the tubular film blowing experiment we measured the freeze-line position, the tubular bubble diameter, the takeup speed, the axial tension, the pressure inside the tubular bubble, and the mass flow rate of the resin. The thickness of the tubular blown films was measured from the samples collected. In order to determine the tubular film blowability, we measured the maximum takeup speed at which the tubular blown bubble broke, for various blowup ratios. The measurements described above permitted us to calculate the tensile stresses at the freeze line, in both the machine and transverse directions, and they were found to be correlatable to the processing conditions employed. It has been found that the tubular film blowability is increased as the resin's MWD becomes narrower and the degree of LCB is less. It has been found further that a resin having lower elongational viscosity tends to give a greater draw-down ratio, indicating a better tubular film blowability. Finally, the tensile properties of the tubular blown films were found correlatable to the processing variables, namely, blowup and takeup ratios.     

Rheology-processing-property relationships in tubular blown film extrusion. II. Low-pressure low-density polyethylene

An experimental investigation was undertaken to establish rheology-processing-property relationships in the tubular blown film extrusion of low-pressure low-density polyethylene (LP-LDPE). For the study, three commercial LP-LDPE resins, each from a different resin manufacturer, were used in producing tubular films, by employing the apparatus described in Paper I of this series. Both molecular and rheological characterizations of the resin were conducted, enabling us to interpret the tubular film blowing characteristics of the resins. Correlations were obtained between the processing variables (namely, blowup and takeup ratios) and the tensile properties of the films. The tubular film blowing characteristics of LP-LDPE and HP-LDPE resins are compared. Differences in the rheological properties (namely, elongational viscosity) of the two types of resin are used in explaining the experimentally observed differences in their tubular film blowability.     

Dispersive mixing efficiency of an elongational flow mixer on PP/EPDM blends: Morphological analysis and correlation with viscoelastic properties

Polypropylene and ethylene‐propylene‐diene terpolymer (PP/EPDM) blends were melt compounded in a new mixing device, designed in our laboratory under the trademark of RMX®, which predominantly generates elongational flows. Dispersion of the EPDM minor phase in PP was carried out in both RMX® and in an internal mixer (Haake Rheomix 600) at equivalent specific mixing energies and the resultant morphologies obtained by SEM were analyzed and compared. A better dispersive mixing efficiency of the RMX® mixer, i.e., lower D_n and D_v of the dispersed EPDM phase was observed. The impact of elongational flow was more pronounced for blends having a high viscosity ratio p, indicating an enhanced droplet break‐up mechanism, which was attributed to the combination of high shear rates inside the mixing element and important elongational flows in the convergent/divergent zones. The morphology of the blends was correlated with their linear viscoelastic properties by using the Palierne model. Very good agreement was found for the PP/EPDM 80/20 blends but for higher EPDM content, the Palierne model failed to describe the rheological behavior, which was attributed to percolation of the minor phase with increasing the concentration. Higher elasticity at low frequencies was observed for blends processed in the RMX®, which was attributed to a higher generated interfacial area. POLYM. ENG. SCI., 54:1444–1457, 2014. © 2013 Society of Plastics Engineers