HDPE/ROSIN blends: I-Morphology, thermal and dynamic-mechanical behavior

SUMMARY Morphological and thermal studies on high density polyethylene (HDPE) / glycerol ester of partially hydrogenated rosin (ester gum) blends reveal phase separation. Both thermal and dynamic-mechanical tests showed no shift of the HDPE glass transition temperature while the HDPE α_c transition appeared. The presence of an additional transition was also noticed as the second component increased in blends; this was attributed to a rosin component. The peak ascribed to this transition became broader in blends enriched with oligomer; it moved toward lower temperatures due to the dissolution of low molecular weight HDPE. The melting temperature and crystallinity of HDPE varied slightly with the amount of amorphous oligomeric component in the blends. Received: 7 May 1997/Revised version: 20 March 1998/Accepted: 14 April 1998     

Rheological and mechanical properties in polyethylene blends

Melt rheology and mechanical properties in linear low density polyethylene (LLDPE)/low density polyethylene (LDPE), LLDPE/high density polyethylene (HDPE), and HDPE/LDPE blends were investigated. All three blends were miscible in the melt, but the LLDPE/LDPE and HDPE/LDPE blends exibiled two crystallization and melting temperatures, indicating that those blends phase separated upon cooling from the melt. The melt strength of the blends increased with increasing molecular weight of the LDPE that was used. The mechanical properties of the LLDPE/LDPE blend were higher than claculated from a simple rule of mixtures, whiele those of the LLDPE/HDPE blend conformed to the rule of mixtures, but the properties of HDPE/LDPE were less than the rule of mixtures prediction.     

Radiation crosslinking of polyethylene with electron beam at different temperatures

The effect of temperature over the range ?196 to 150°C on the crosslinking of polyethylenes irradiated by electron beam has been investigated on the basis of gel content determination and Fourier transform infra-red (FTIR) spectroscopy. The crosslinking efficiency increases significantly with increasing irradiation does and at elevated irradiation temperature. The crosslinking rates of high density polyethylene (HDPE) and low density polyethylene (LDPE) samples above the melting point (T_M) are much higher than those below T_m. The FTIR data give positive evidence: (i) that trans-vinylene double bonds in cross linked HDPE and LDPE samples increase with increasing irradiation dose temperature (ii) that vinyl double bonds in HDPE decrease rapidly with increasing irradiation dose and temperature, and (iii) vinylidene groups in LDPE decrease slowly with increasing temperature at the lower dose and are almost independent of the irradiation temperature at above room temperature and the higher dose of more than 100 kGy. Gas bubbles are observed in LDPE samples irradiated at 100 and 150°C with high dose (200 to 250 kGy). The size of the bubbles increases gradually at high temperatures.     

Improvement of the polarity of polyethylene with oxidized Fischer–Tropsch paraffin wax and its influence on the final mechanical properties

The easy, low‐cost modification of the polarity of low‐density polyethylene (LDPE) and high‐density polyethylene (HDPE) through blending with oxidized Fischer–Tropsch wax was investigated. A 10 wt % concentration of the wax increased the polar component of the total surface free energy 10 times for LDPE and 4.5 times for HDPE. Modified LDPE also had significantly higher adhesion to the polar substrate, which was represented by a crosslinked epoxy‐based resin. This behavior was not observed for HDPE. The conservation of the good mechanical properties of polyethylene was observed. The wax content had only a moderate influence on the mechanical properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1164–1168, 2005     

Crystallization and melting behavior of polyethylene fractions obtained by various fractionation methods

Summary A high density polyethylene (HDPE) and a low density polyethylene (LDPE) were fractionated by means of preparative GPC, analytical GPC, direct extraction, and a crystallization/dissolution method, to enable determination of the chain branching distribution over the molar mass distribution.The non-isothermal crystallization and melting behaviour of the HDPE and LDPE fractions and of a series of linear polyethylene (LPE) fractions was studied using DSC with a scanning rate of 5 K/min. After an initial increase, the crystallization temperature of the LPE fractions started to decrease at M–20 kg/mol, to remain at a constant value from M–60 kg/mol. This is illustrative of the crystallization being hindered by entanglements. With LDPE fractions showing a constant degree of short chain branching an analogous, but greater, decrease was observed in a corresponding range of molecular dimensions. The differences found for the HDPE fractions as compared with the LPE reference values are due mainly to short chain branching.Part of this paper was presented at the Hungarian Symposium on Thermal Analysis; Budapest, 10–12 June, 1981.     

Poly(allylammonium acrylate) as a drug-releasing matrix

A comparative study was undertaken on well characterized HDPE and LDPE samples in order to obtain a better understanding of the morphology of the crystalline phase. Thickness of the lamellae was determined by WAXS. The melting points were calculated by empirical and Gibbs-Thomson equations, considering either folded or extended chains, and compared to DSC data. The results confirm that in HDPE the chains are folded, the segment between folds containing about 100 carbon atoms, while in LDPE, the chains are extended, with segments of about 73 carbon atoms in the crystalline core, linked to the paracrystalline layer and amorphous zones, which contain long folds and chain ends, as proposed in the 3-phase model by Vile et al. Received: 22 January 1997/Revised: 26 March 1997/Accepted: 31 March 1997     

Crystallization of low‐density polyethylene‐ and linear low‐density polyethylene‐rich blends

The crystallization of a series of low‐density polyethylene (LDPE)‐ and linear low‐density polyethylene (LLDPE)‐rich blends was examined using differential scanning calorimetry (DSC). DSC analysis after continuous slow cooling showed a broadening of the LLDPE melt peak and subsequent increase in the area of a second lower‐temperature peak with increasing concentration of LDPE. Melt endotherms following stepwise crystallization (thermal fractionation) detailed the effect of the addition of LDPE to LLDPE, showing a nonlinear broadening in the melting distribution of lamellae, across the temperature range 80–140°C, with increasing concentration of LDPE. An increase in the population of crystallites melting in the region between 110 and 120°C, a region where as a pure component LDPE does not melt, was observed. A decrease in the crystallite population over the temperature range where LDPE exhibits its primary melting peaks (90–110°C) was noted, indicating that a proportion of the lamellae in this temperature range (attributed to either LDPE or LLDPE) were shifted to a higher melt temperature. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1009–1016, 2000     

Self‐reinforcement of high‐density polyethylene/low‐density polyethylene prepared by oscillating packing injection molding under low pressure

This article reports the toughness improvement of high‐density polyethylene (HDPE) by low‐density polyethylene (LDPE) in oscillating packing injection molding, whereas tensile strength and modulus are greatly enhanced by oscillating packing at the same time. Compared with self‐reinforced pure HDPE, the tensile strength of HDPE/LDPE (80/20 wt %) keeps at the same level, and toughness increases. Multilayer structure on the fracture surface of self‐reinforced HDPE/LDPE specimens can be observed by scanning electron microscope. The central layer of the fracture surface breaks in a ductile manner, whereas the break of shear layer is somewhat brittle. The strength and modulus increase is due to the high orientation of macromolecules along the flow direction, refined crystallization, and shish‐kebab crystals. Differential scanning calorimetry and wide‐angle X‐ray diffraction find cocrystallization occurs between HDPE and LDPE. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 799–804, 1999     

Raman spectra of high‐density,low‐density,and linear low‐density polyethylene pellets and prediction of their physical properties by multivariate data analysis

Raman spectra have been measured for pellets of five samples of high‐density polyethylene (HDPE), seven samples of low‐density polyethylene (LDPE), and six samples of linear low‐density polyethylene (LLDPE). The obtained Raman spectra have been compared to find out characteristic Raman bands of HDPE, LDPE, and LLDPE. Principal component analysis (PCA) was applied to the Raman spectra in the 1600–650 cm^?1 region after multiplicative scatter correction (MSC) to discriminate the Raman spectra of the three different PE species. They are classified into three groups by a score plot of PCA factor 1 vs. 2. HDPE with high density and high crystallinity gives high scores on the factor 1 axis, while LDPE with low density and low crystallinity yields negative scores on the same axis. It seems that factor 1 reflects the density or crystallinity. A PC weight loadings plot for factor 1 shows six upward peaks corresponding to the bands arising from the crystalline parts or all‐trans ? (CH₂)_n? groups and seven downward peaks ascribed to the bands of the amorphous or anisotropic regions and those arising from the short branches. Partial least‐squares (PLS‐1) regression was applied to the Raman spectra after MSC to propose calibration models that predict the density, crystallinity, and melting points of the polyethylenes. The correlation coefficient was calculated to be 0.9941, 0.9800, and 0.9709 for the density, crystallinity, and melting point, respectively, and their root‐mean‐square error of cross validation (RMSECV) was found to be 0.0015, 3.3707, and 2.3745, respectively. The loadings plot of factor 2 for the prediction of melting point is largely different from those for the prediction of density and crystallinity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 443–448, 2002     

Thermal and mechanical properties of uncrosslinked and chemically crosslinked polyethylene/ethylene vinyl acetate copolymer blends

Uncrosslinked and chemically crosslinked binary blends of low‐ and high‐density polyethylene (PE), with ethylene vinyl acetate copolymer (EVA), were prepared by a melt‐mixing process using 0–3 wt % tert‐butyl cumyl peroxide (BCUP). The uncrosslinked blends revealed two distinct unchanged melting peaks corresponding to the individual components of the blends, but with a reduced overall degree of crystallinity. The crosslinking further reduced crystallinity, but enhanced compatibility between EVA and polyethylene, with LDPE being more compatible than HDPE. Blended with 20 wt % EVA, the EVA melting peak was almost disappeared after the addition of BCUP, and only the corresponding PE melting point was observed at a lowered temperature. But blended with 40% EVA, two peaks still existed with a slight shift toward lower temperatures. Changes of mechanical properties with blending ratio, crosslinking, and temperature had been dominated by the extent of crystallinity, crosslinking degree, and morphology of the blend. A good correlation was observed between elongation‐at‐break and morphological properties. The blends with higher level of compatibility showed less deviation from the additive rule of mixtures. The deviation became more pronounced for HDPE/EVA blends in the phase inversion region, while an opposite trend was observed for LDPE/EVA blends with co‐continuous morphology. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3261–3270, 2007     

Validation of Double Convected Pom‐Pom model with particle image velocimetry technique

The performance of Double Convected Pom‐Pom (DCPP) model in predicting contraction flow was examined by means of particle image velocimetry (PIV) technique. Both the velocities at the centerline and the flow patterns were investigated experimentally and numerically for low density polyethylene (LDPE) and high density polyethylene (HDPE). Comparison between predicted velocity and experimental velocity showed that the DCPP model was able to quantitatively predict the velocity of HDPE in contraction flow while only qualitative agreement was observed for LDPE. It was found that for both polyethylenes the absolute velocity discrepancy increased with the rise of flow rate. The relative velocity discrepancy of both polyethylene melts did not change much when increasing the flow rate of the melts. The flow patterns matched well for LDPE, but for HDPE numerical simulation predicted recirculation at the re‐entrant corner which did not exist in experiment. POLYM. ENG. SCI., 55:1897–1905, 2015. © 2014 Society of Plastics Engineers     

Effect of EPDM on the mechanical properties of blends of high and low density polyethylene

Summary We studied the effect of adding ethylene-propylene-diene rubber (EPDM) to blends of high (HDPE) and low (LDPE) density polyethylene. The extrusion torque of the blend without EPDM shows a deviation from the linear addition rule, but blends with rubber follow the addition rule. Two composition regions that are compatible with the torque behavior are present in the Young's modulus and extension at break curves. The EPDM content improves the extension at break of LDPE rich blends. This improvement extends to higher compositions of HDPE as the EPDM content is increased. Received: 4 September 1997/Revised version: 30 April 1998/Accepted: 13 May 1998     

Oriented structure and anisotropy properties of polymer blown films: HDPE, LLDPE and LDPE

Different types of polyethylene blown films (HDPE, LDPE, LLDPE) differ significantly in the ratio between machine and transverse direction tear resistance. In this paper, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) blown films at different draw-down ratios are studied, and the relation between crystalline structure and anisotropy of blown film properties is investigated. The crystalline morphology and orientation of HDPE, LDPE, LLDPE blown films were probed using microscopy and infrared trichroism. Significant differences in crystalline morphology were found: at medium DDR HDPE developed a row-nucleated type morphology without lamellar twisting, LDPE showed rod-like crystalline morphology and turned out to the row-nucleated structure with twisted lamellae at high draw-down ratio (DDR), while a spherulite-like superstructure was observed for LLDPEs at all processing conditions. They also showed quite different orientation characteristics corresponding to different morphologies. The morphologies and orientation structure for LDPE, LLDPE and HDPE are related to the stress applied (DDR) and their relaxations in the flow-induced crystallization process, which determine the amount of fibrillar nuclei available at the time of crystallization and therefore, the final crystalline morphology. These structure differences are shown to translate into different ratios of machine and transverse direction tear and tensile strengths.     

Modification of recycled high‐density polyethylene by low‐density and linear‐low‐density polyethylenes

The present study investigated mixed polyolefin compositions with the major component being a post‐consumer, milk bottle grade high‐density polyethylene (HDPE) for use in large‐scale injection moldings. Both rheological and mechanical properties of the developed blends are benchmarked against those shown by a currently used HDPE injection molding grade, in order to find a potential composition for its replacement. Possibility of such replacement via modification of recycled high‐density polyethylene (reHDPE) by low‐density polyethylene (LDPE) and linear‐low‐density polyethylene (LLDPE) is discussed. Overall, mechanical and rheological data showed that LDPE is a better modifier for reHDPE than LLDPE. Mechanical properties of reHDPE/LLDPE blends were lower than additive, thus demonstrating the lack of compatibility between the blend components in the solid state. Mechanical properties of reHDPE/LDPE blends were either equal to or higher than calculated from linear additivity. Capillary rheological measurements showed that values of apparent viscosity for LLDPE blends were very similar to those of the more viscous parent in the blend, whereas apparent viscosities of reHDPE/LDPE blends depended neither on concentration nor on type (viscosity) of LDPE. Further rheological and thermal studies on reHDPE/LDPE blends indicated that the blend constituents were partially miscible in the melt and cocrystallized in the solid state.     

二烯基双酚A醚接枝低密度聚乙烯的制备

介绍了二烯基双酚Ａ醚（ＤＢＡＥ）与低密度聚乙烯（ＬＤＰＥ）在Ｈａａｋｅ转矩流变仪的混炼器中进行熔融接枝反应,采用红外光谱（ＦＴ－ＩＲ）分析证实了接枝共聚物（ＬＤＰＥ－ｇ－ＤＢＡＥ）并通过对ＬＤＰＥ－ｇ－ＤＢＡＥ的接枝率（ＧＲ）和熔体流动速率（ＭＦＲ）测试,考察了制备条件（反应温度,引发剂用量和ＤＢＡＥ用量）对接枝反应及产物的影响,ＬＤＰＥ－ｇ－ＤＢＡＥ的最终目的是作为高密度聚乙烯／聚碳酸酯共混体系     

Understanding of the tensile deformation in HDPE/LDPE blends based on their crystal structure and phase morphology

The mechanisms of tensile deformation in high density polyethylene/low density polyethylene (HDPE/LDPE) blends were studied by a video-controlled tensile set-up, combined with dynamic mechanical analysis and small angle X-ray scattering. When quenching from the melt to room temperature, HDPE forms well-organized spherulits with high crystallinity and rigid amorphous layers between lamellae, and LDPE forms irregular aggregates with low crystallinity and mobile amorphous layers between lamellae. A separate lamellar stack-like structure is formed in HDPE/LDPE blends during the quenching. The deformation is affected by both the crystal structure and the phase morphology. Because the semi-crystalline polymers are made up of two interpenetrating networks, one is built up by the entangled fluid part and the other by the crystallites, at low deformations the coupling and coarse slips of the crystalline blocks dominate the mechanical properties, which allows the system to maintain a homogeneous strain distribution in the sample. The assumption of a homogeneous strain distribution can now be further proved by the tensile deformation in HDPE/LDPE blends, which shows two-step processes, with HDPE crystallites being broken down first at imposed strain of 0.4 and then LDPE crystallites being broken later, at an imposed strain of 0.6.     

Radiation-grafting of N,N-dimethylaminoethylmetacrylate onto polyethylene film by preirradiation method

Radiation-induced graft polymerization of N,N-dimethylaminoethyl-metacrylate onto low density polyethylene (LDPE) film by the preirradiation method in presence of air was investigated. The appropriate reaction conditions at which the graft polymerization was carried out are reported. Received: 4 December 1996/Revised: 5 March 1997/Accepted: 10 March 1997     

Crystallization kinetics and tensile modulus of blends of metallocene short‐chain branched polyethylene with conventional polyolefins

In this study, blends of metallocene short‐chain branched polyethylene (SCBPE) with low‐density polyethylene (LDPE), high‐density polyethylene (HDPE), polystyrene (PS), ethylene–propylene–diene monomer (EPDM), and isotactic polypropylene (iPP) were prepared in weight proportions of 80 and 20, respectively. The crystallization behaviors of these blends were studied with polarized light microscopy (PLM) and differential scanning calorimetry. PLM showed that SCBPE/LDPE, SCBPE/HDPE, and SCBPE/EPDM formed band spherulites whose band widths and sizes were both smaller than that of pure SCBPE. No spherulites were observed, but tiny crystallites were observed in the completely immiscible SCBPE/PS, and the crystallites in SCBPE/iPP became smaller; only irregular spherulites were seen. The crystallization kinetics and mechanical properties of SCBPE were greatly affected by the second polyolefin but in different way, depending on the phase behavior and the moduli of the second components. SCBPE may be phase‐miscible in the melt with LDPE, HDPE, and EPDM but phase‐separated during crystallization. A big change in the crystal morphology and crystallization kinetics existed in the SCBPE/iPP blend. The mechanical properties of the blends were also researched with dynamic mechanical analysis (DMA). DMA results showed that the tensile modulus of the blends had nothing to do with the phase behavior but only depended on the modulus of the second component. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1816–1823;2005     

Formation and characterization of polyethylene blends for autoclave‐based expanded‐bead foams

Blends of linear‐low‐density polyethylene (LLDPE), low‐density polyethylene (LDPE), and high‐ density polyethylene (HDPE) were foamed and characterized in this research. The goal was to generate clear dual peaks from the expanded polyethylene (EPE) foam beads made from these blends in autoclave processing. Three blends were prepared in a twin‐screw mixing extruder at two rotational speeds of 5 and 50 rpm: Blend1 (LLDPE with 20 wt% HDPE), Blend 2 (LLDPE with 20 wt% LDPE), and Blend 3 (LLDPE with 10 wt% HDPE and 10 wt% LDPE). The differential scanning calorimetric (DSC) measurement was taken at two cooling rates: 5 and 50°C/min. Although no dual peaks were present, the results showed that blending with HDPE has a more noticeable effect on the DSC curve of LLDPE than blending with LDPE. Also, the rotational speed and cooling rate affected the shape of the DSC curves and the percentage area below the onset point. The DSC characterization of the batch foamed blends revealed multiple peaks at certain temperatures, which may be mainly due to the annealing effect during the gas saturation process. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

烯基双酚A醚接枝LDPE对HDPE／PC相容性和结晶速率的影响

本文通过热力学曲线,对HDPE/PC体系中HDPE的熔融温度(T_m)和PC的玻璃化转变温度(T_g)的测试,考察了增容剂烯基双酚A醚接枝LDPE(LDPE-g-DBAE)对共混体系相容性的影响,同时还研究了体系中HDPE的结晶速率。