Elongational rheology of LLDPE / LDPE blends

The objective of this study is to investigate the effect of low density polyethylene (LDPE) content in linear low density polyethylene (LLDPE) on the crystallinity and strain hardening of LDPE / LLDPE blends. Three different linear low density polyethylenes (LL‐1, LL‐2 and LL‐3) and low density polyethylenes (LD‐1, LD‐2 and LD‐3) were investigated. Eight blends of LL‐1 with 10, 20, 30 and 70 wt % of LD‐1 and LD‐3, respectively, were prepared using a single screw extruder. The elongational behavior of the blends and their constituents were measured at 150°C using an RME rheometer. For the blends of LL‐1 with LD‐1, the low shear rate viscosity indicated a synergistic effect over the whole range of concentrations, whereas for the blends of LL‐1 with LD‐3, a different behavior was observed. For the elongational viscosity behavior, no significant differences were observed for the strain hardening of the 10–30% LDPE blends. Thermal analysis indicated that at concentrations up to 20%, LDPE does not significantly affect the melting and crystallization temperatures of LLDPE blends. In conclusion, the crystallinity and rheological results indicate that 10–20% LDPE is sufficient to provide improved strain hardening in LLDPE. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 3070–3077, 2003     

Elongational rheology of polyethylene melts

Effective elongational viscosities were measured for high‐ and low‐density polyethylene samples using a capillary rheometer fitted with semihyperbolic dies. These dies establish a purely elongational flow field at constant elongational strain rate. The effective elongational viscosities were evaluated under the influence of the process strain rate, Hencky strain, and temperature. Enthalpy and entropy changes associated with the orientation development of semihyperbolic‐processed melts were also estimated. The results showed that elongational viscosities were primarily affected by differences in the weight‐average molecular weight rather than in the degree of branching. This effect was process‐strain‐rate‐ as well as temperature‐dependent. An investigation of the melt‐pressure relaxation and the associated first decay time constants revealed that with increasing strain rate the molecular field of the melt asymptotically gained orientation in approaching a limit. As a result of this behavior, molecular uniqueness became much less distinct at high process strain rates, apparently yielding to orientation development and the associated restructuring of the melt's molecular morphology. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2170–2184, 2001     

Elongational rheology of polymer melts and solutions

Elongational rheological properties of polymer melts and solutions may be measured using nonlubricated flow characteristics through a semihyperbolic converging die. The effects of body forces related to developing orientation in the fluid during converging extensional flow are so strong that the shearing contribution become negligible in comparison, eliminating the need for lubrication to achieve an essentially pure elongational flow. The effective elongational viscosities of polypropylene melts and lyocell solutions correlated with shear-flow determinations were used to estimate the enthalpy and entropy changes as function of processing conditions. The flow of lyocell solutions through a converging die had, as a result, not only phase separation and cellulose crystallization, but also microfibers formation and high orientation. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 69: 2357–2367, 1998     

Shear and elongational rheology of polyethylenes with different molecular characteristics. II. Elongational rheology

The elongational viscosities of polyethylenes with different molecular characteristics were measured at different Hencky strains and temperatures with a capillary rheometer by the replacement of the capillary cylindrical die with a hyperbolic converging die. The hyperbolic shape of the die established a purely elongational flow field at a constant elongational strain rate throughout the die. The effects of molecular characteristics such as the molecular weight, molecular weight distribution, and long‐chain branching and processing conditions such as the temperature and Hencky strain on the elongational rheology of the polyethylene samples were studied. Good master curves were generated for temperature and Hencky strain shifting and simultaneous shifting with respect to both the temperature and Hencky strain. Both the molecular weight distribution and long‐chain branching seemed to promote strain rate thinning and reduce the elongational viscosity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1184–1194, 2007     

The effect of reaction conditions on LDPE oxidation

Summary The formation kinetics of functional groups and the kinetics of the molecular mass change were investigated in low density polyethylene oxidized under different conditions in static and dynamic equipments. The processes studied were found highly sensitive to the oxygen supply. With the increase of [O₂] higher rate of oxidation and increasing fragmentation can be observed. If [O₂] is reduced, crosslinking will dominate. Mechanical effect was significant only during the melting of the polymer. Under dynamic conditions, diffusion control was always found.     

Understanding the foamability and mechanical properties of foamed polypropylene blends by using extensional rheology

In this article, the influence of the rheological behavior of miscible blends of a linear and a high melt strength, branched, polypropylene (HMS PP), on the cellular structure and mechanical properties of cellular materials, with a fixed relative density, has been investigated. The rheological properties of the PP melts were investigated in steady and oscillatory shear flow and in uniaxial elongation in order to calculate the strain hardening coefficient. While the linear PP does not exhibit strain hardening, the blends of the linear and the HMS PP show pronounced strain hardening, increasing with the concentration of HMS PP. Related to the cellular structure, in general, the amount of open cells, the cell size, and the width of the cell size distribution increase with the amount of linear PP in the blends. Also mechanical properties are conditioned by the extensional rheological behavior of PP blends. Cellular materials with the best mechanical properties are those that have been fabricated using large amounts of HMS PP. The results demonstrate the importance of the extensional rheological behavior of the base polymers for a better understanding and steering of the cellular structure and properties of the cellular materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42430.     

Basic and applied rheology of m-LLDPE/LDPE blends: Miscibility and processing features

The linear viscosity of m-LLDPE/LDPE blends is adjusted to a free volume model, conceived for miscible blends. A deviation from the model is observed at 47.5% m-LLDPE/52.5% LDPE blend, suggesting immiscibility in the molten state at this composition. Time-temperature superposition method is used to confirm miscible and immiscible cases. The effect of miscibility on practical rheological features is analysed using extrusion rheometry. The results indicate a core-sheet morphology in the immiscible blend, as the less viscous LDPE encircles the m-LLDPE phase. Miscible blends with a high LDPE content and immiscible 47.5% m-LLDPE/52.5% LDPE blend, show ‘melt fracture’, but not ‘sharkskin’. The latter is observed in miscible blends of a high m-LLDPE content. ‘Sharkskin’ is postponed in 87.5% m-LLDPE/12.5% LDPE blend, a result which is associated to the elongational viscosity enhancement, due to the presence of long chain branches. The correlation between melt spinning and blown film extrusion results is investigated, showing evidences of the technical limitations caused by immiscibilty.     

Enhancement of processability and foamability of ground tire rubber powder and LDPE blends through solid state shear milling

The foamed composites made from low-density polyethylene(LDPE) and ground tire rubber(GTR) powder using azodicarbonamide as chemical blowing agent have been investigated. Solid state shear milling was used to enhance the processability and foamability of LDPE/GTR blends by a pan-mill type mechanochemical reactor. First the blends of LDPE/GTR were prepared by co-milling, then the samples were melt-mixed in a Brabender Plasti-Corder, saturated with blowing agent, crosslinking agent and blowing co-agent, and finally the saturated specimens were expanded during the pressure-quench process. The results indicated that the mechanical properties of the LDPE/GRT foamed composites were improved, and the blends of co-milled GTR and LDPE powder showing better processability and foamability than those obtained in a conventional melt-mixing manner, as indicated by the rheological and morphological studies.     

The effect of some foam boosters on the foamability and foam stability of anionic systems

The foaming properties of anionic surfactant solutions containing a nonionic surfactant, fatty acid N-methyl-ethanolamide (NMEA), were investigated. Foamability, which is the foam-generating power at the initial stage of foaming, was measured by a laboratory-built foam-testing apparatus, and also by the conventional Ross-Miles test NMEA synergistically increased the foamability of anionic surfactant solutions, particularly when small amounts of NMEA were added. Shorter hydrocarbon chain lengths of NMEA, such as N-octanoyl-N-methylethanol (NMEA-08) and N-decanoyl-N-methylethanol (NMEA-10), showed better performance in the laboratory-built foam tester. The results of the Ross-Miles evaluation, however, were completely opposite. Compared with commercial nonionic boosters, such as fatty acid monoethanolamide, fatty acid diethanolamide, and lauramidopropyldimethylbetaine (LPB), NMEA was the most effective for increasing foamability of the solution at the initial stage. The most popular amphoteric foam booster, LPB, did not increase foamability but likely generated the initial foam volume on the Ross-Miles test as a result of foam film stabilization. From these results, a foam-boosting mechanism of NMEA different from that of LPB is suggested.     

Recycled and virgin LDPE as rheology modifiers of lithium lubricating greases: A comparative study

In this work, a new application for recycled low‐density polyethylene (LDPE), as rheology modifier of standard lithium lubricating grease formulations, was studied. The effectiveness of this additive was compared with that achieved with a virgin LDPE. With this aim, both types of polymers were added to the formulation during the manufacturing process of greases, following the same standard protocol, to reinforce the role of the thickening agent, the lithium 12‐hidroxystearate. The effect that both lithium soap and LDPE concentrations exert on the rheology of lubricating grease formulations and its relationship with grease microstructure were discussed. Lubricating greases were rheologically characterized through small‐amplitude oscillatory shear and viscous flow measurements. In addition to these, scanning electron microscopy observations and mechanical stability tests were also carried out. In all cases, an increase in soap concentration yields higher values of apparent viscosity and linear viscoelasticity functions. On the other hand, the values of the rheological functions obtained for recycled LDPE‐based lubricating greases are, in general, higher than those obtained for virgin LDPE‐based grease formulations. However, the structural skeleton developed in greases containing recycled LDPE demonstrates less resistance to severe working conditions, showing lower mechanical stability than virgin LDPE‐based grease formulations. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

The effect of molecular weight blending on PVC melt rheology

The effect of molecular weight blending on melt flow characteristics has been studied with a 50/50 mixture of suspension PVC resins with the respective M _w of 56,300 and 123,000. The dynamic shear measurements were made with the Rheometrics Visco-Elastic Tester at angular frequencies of 0.1 to 40 radians/s. In the temperature range of 160 to 215° C, all samples showed three distinct flow regions marked by three different values of the activation energy. The high molecular weight fraction introduced a relatively strong influence on the melt flow characteristics of the blend due to the effect of its relatively high crystalline content. These samples also failed to show a Newtonian flow behavior at 190°C at an extremely low shear rate corresponding to 10^?4 radians/s., possibly reflecting the effect of the remnant crystallinity of the material.     

The effect of moisture on the rheology of brown coal-oil suspensions

The rheological properties of brown coal-oil suspensions were investigated using both a Contraves rheometer and a Weissenberg rheogoniometer. The aging characteristic of the suspensions was found to be due to the moisture in the coal and the presence of large numbers of micropores. Moisture in the suspension caused aggregation of coal particles and diffusion of oil in the pores was responsible for the reduction in the volume fraction of free carrier oil. Both the yield stress and apparent viscosity were found to increase sharply if the coal contained more than 10 wt% moisture. Photomicrographs were also used to identify the cause of aggregation in brown coal-oil suspensions.     

Elongational behavior of polyethylene melts—effect of deformation

Transient elongational viscosity of linear low density polyethylene (LLDPE) and two low density polyethylenes (LDPE1 and LDPE2) was measured at one temperature and different deformation rates in constant strain rate elongational rheometer. The elongational viscosity measurements revealed stronger strain hardening characteristics for LDPEs than that observed for LLDPE. The different response to stretching of these polymers is thought to relate to the presence of long chain branches in LDPEs, which affect the elongation viscosity profoundly. The onset of strain hardening for all long chain branched LDPEs as well as for linear LLDPE occurs at the same value of the critical strain, which is independent of temperature or deformation rate. An attempt has been made to explain this phenomenon in terms of the changes that occur in the macromolecular network upon stretching.     

Processing,rheology, and storage stability of recycled EVA/LDPE modified bitumen

The optimum processing conditions for the manufacture of polymer‐modified bitumens (PMBs), as well as the rheological properties of the final polymer‐bitumen blends, strongly depend on the characteristics of the mixing device used. The present work is focused on the comparison among the kinetics of the mixing process and the rheological properties and microstructural characteristics of PMBs manufactured in two different mixers. Thus, blends of 60/70 penetration grade bitumen and recycled EVA/LDPE were processed in both high and low‐shear devices. Knowledge on the evolution of shear viscosity and microstructure with time, as well as on the mechanical properties of the final polymer‐bitumen blends, was gained from rheological and modulated DSC tests, and optical microscopy. The results obtained demonstrate that processing in the high‐shear device yields a significant decrease in the time needed for the polymer‐bitumen blend to reach the final stage of the manufacturing process, as well as an important reduction in bitumen oxidation and enhanced properties in a wide range of in‐service temperatures. However, polymer‐bitumen blends manufactured in the high‐shear device are not stable during its storage at high temperature. POLYM. ENG. SCI., 47:181–191, 2007. © 2007 Society of Plastics Engineers     

Elongational Rheology of Polymer/Clay Dispersions: Determination of Orientational Extent in Elongational Flow Processes

The purpose of the present contribution is to provide an efficient method that would help to quantify the orientational levels occurring in polymer/clay dispersions subjected to elongational flow. The extent of internal orientation developed in salt containing montmorillonite/poly(ethylene oxide) gels is investigated, combining shear and elongational rheology methods. Entropic changes indicate that the strength of the transient network present in each gel affects the orientational ability of clay particles and polymer chains. We found that an increased Hencky strain of the hyperbolic die leads to a higher variation of the calculated entropy of the material.

     

Interfacially compatibilized LDPE/POE blends reinforced with nanoclay: investigation of morphology,rheology and dynamic mechanical properties

Morphological, melt rheological and dynamic mechanical properties of low-density polyethylene (LDPE)/ethylene–octene copolymer (POE)/organo-montmorillonite (OMMT) nanocomposites, prepared via melt compounding were studied. The XRD traces indicated different levels of intercalated structures for the nanocomposites. Addition of a compatibilizer (PE-g-MA) improved the intercalation process. TEM results revealed existence of clay layers in both phases but they were mainly localized in the elastomeric POE phase. Addition of 5 wt% OMMT to the LDPE/POE blend led to reduction in the size of the elastomer particles confirmed by AFM. The complex viscosity and storage modulus showed little effect of the presence of the clay when no compatibilizer was added. As the extent of exfoliation increased with addition of compatibilizer, the linear viscoelastic behavior of the composites gradually changed specially at low-frequency regions. The interfacially compatibilized nanocomposites with 5 wt% OMMT had the highest melt viscosity and modulus among all the studied nanocomposites and blends. Also, this particular composition showed the best improvement in dynamic storage modulus. The results indicated that clay dispersion and interfacial adhesion, and consequently different properties of LDPE/POE/clay nanocomposites, are greatly affected by addition of compatibilizer.     

The effect of temperature and moisture on the rheology of black coal-oil suspensions

Rheological properties of black coal-KC220 oil suspensions have been investigated using a Contraves rheometer over a temperature and coal volume fraction range of 18–200°C and 0.247-0.385, respectively. The suspensions behaved as Newtonian fluids. Variation of viscosity with temperature does not follow any regular trend and peak viscosity values occur in the temperature range of 80–140°C for dry coal and 70–130°C for moist coal, depending upon the concentrations of coal in the suspension. Freshly prepared suspensions of moist coal exhibit viscosity peaks at a temperature lower than that of the corresponding suspension with dry coal. However, when aged, the suspensions of moist coal exhibit very small peak viscosity and follow an Arrhenius type behavior. For both dry and moist coal, the maximum volume fraction, ?_m, continues to decrease with an increase in temperature.     

Assessment of hindered phenol antioxidants on processing stability of peroxide‐cure LDPE by rheology and DSC analysis

Influence of commercial phenol antioxidants Irganox 300, 1010, 1035, and 1076 on peroxide‐cure reaction of low‐density polyethylene (LDPE) was evaluated through isothermal dynamic rheological and nonisothermal differential scanning calorimetry (DSC) testing. The results indicated that phenol antioxidants could reduce storage modulus of LDPE completely crosslinked at 175°C while they have a neglectable effect on gel fracture and activity energy of crosslinking reaction. On the other hand, time sweep dynamic rheological test revealed the antioxidants 1035 and 1076 with low molecular weight and low melting point could significantly depress scorch of crosslinkable LDPE at 135°C. The isothermal time sweep dynamic rheology test method was more sensitive than nonisothermal DSC test for characterizing the influence of phenol antioxidants on crosslinking kinetics of peroxide‐cure reaction of LDPE. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The effect of SEBS on interfacial tension and rheological properties of LDPE/PS blend

The effects of SEBS as a compatibilizer on the interfacial tension and rheological properties of LDPE/PS blend have been studied. Interfacial tension was measured by the breaking thread method. The measured interfacial tension of the LDPE/PS blend was 8.26 dyn/cm. It decreased rapidly with SEBS contents to 1 wt % and then leveled off to a saturation value, 3.6 dyn/cm. Dynamic oscillatory shear, elongational viscosity, and recovery after elongation were measured as the rheological properties. Storage modulus at low frequencies decreased with SEBS contents to 1 wt %. More addition of SEBS, however, increased the storage modulus at low frequencies. Similar behaviors could be observed in elongation viscosity and recovery after elongation. Hardening of elongational viscosity and recovery after elongation were reduced with 1 wt % SEBS, and they enhanced again with more SEBS contents. This means that there is a critical concentration of SEBS that acts as a compatibilizer and reduces the interfacial tension. More SEBS than the critical concentration saturates the interface and increases the elasticity of the LDPE/PS blend, while maintaining the interfacial tension between LDPE and PS constant. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 905–911, 2005     

The effect of electric field on the creep characteristics of low-density polyethylene (LDPE)

Summary The effect of electric field on the creep characteristics and the corresponding parameters such as instantaneous strain, strain rate, activation energy, activation volume, stress-sensitivity parameter and viscosity was investigated.