Relationships between impact performance and structures of rotationally molded crosslinked high-density polyethylene

Crosslinked high-density polyethylene (XL-HDPE) is a preferred material for chemical and fuel tanks due to its superior environmental stress crack resistance and impact strength. The impact performance of rotationally molded specimen is important for final products. In the research the drop weight impact strength (defined as ARM impact strength) of rotationally molded XL-HDPE is tested between −40°C and 25°C. The crosslinking content, crystallization characteristics, and dynamic mechanical properties (DMA) of different thickness gradients are examined to illustrate the relationships between the impact strength, brittle-ductile transition (BDT) and microstructures. The innermost surface layer (about 0.3 mm) has lower gel content, higher crystallinity, and average lamellar thickness compared with the body part. The ARM impact strength is about 1 J/mm at −40°C and −30°C, and about 29 J/mm at −20°C ~ 25°C. There is a BDT between −30°C and − 20°C. After removing the innermost surface layer, the sample breaks in ductile manner in the entire tested temperature range, and the ARM impact strength is about 24 ~ 26 J/mm. The DMA results show that the BDT is consistent with the structure transition of the innermost surface layer. The microstructures of rotationally molded XL-HDPE in the innermost surface layer dominate the low temperature impact performance.     

The effect of cooling rate on the impact performance and dynamic mechanical properties of rotationally molded metallocene catalyzed linear low density polyethylene

This article examines changes to the morphology of rotationally molded metallocene catalyzed linear low density polyethylene brought about by varying the cooling rate during processing. These changes in morphology lead to variations in the impact performance, which is reflected in the dynamic mechanical characteristics of the materials. Various analytical techniques are used in an attempt to explain the differences in impact behavior. Slow cooling is shown to result in high crystallinity, and in the formation of large spherulites, which in turn is detrimental to the impact performance of the material, particularly at low temperatures. The high crystallinity corresponds with a shift in the β transition of the material to a higher temperature, and is shown to result in a higher brittle–ductile transition. A case study was also carried out on samples from a finished part provided by an industrial molder, one section of which failed in a brittle manner when impact tested while the other failed in a ductile manner. Microscopy results showed that the brittle material had large spherulites at the inside surface, while the ductile material showed incipient degradation at this surface, which has previously been shown to be of benefit to impact strength in rotationally molded parts. Dynamic mechanical studies again showed a β transition at a higher temperature in the brittle samples. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1963–1971, 2006     

The effect of powder particle fusion on the mechanical properties of ultra-high molecular weight polyethylene

Rheo-optical and mechanical property studies with compression molded ultra-high molecular weight polyethylene specimens at different temperatures indicate that their mechanical performance is dependent on the degree of fusion of the powder particles during compression and can be enhanced by heating the polymer powder at temperatures above 220°C. Although the mechanical performance of the compression molded specimens can be improved further by solid-state drawing at a draw ratio 5, the anisotropic morphologies from molded specimen above 220°C have higher initial slope of stress to elongation, strength to break, and an outstanding elastic recovery in compreision to the compression molded specimens at 180°C.     

Toughening high density polyethylene submitted to extreme ambient temperatures

The use of polyethylene is limited due to its low impact strength among other mechanical properties at extreme ambient temperatures, for example at ?46 °C and 66 °C. In this work, different polymer components, such as ultra-high molecular weight polyethylene (UHMWPE) and ethylene-vinyl acetate (EVA), were incorporated in high density polyethylene (HDPE) to test their ability to improve toughness of HDPE at extreme ambient temperatures. The polymer blends were processed by extrusion and injection molding and characterized by rotational rheometry, electron microscopy, thermal analysis, tensile, impact and dynamic mechanical tests. The results showed that low concentrations of EVA and UHMWPE in HDPE increased substantially the impact strength of HDPE at room temperature as well as in extreme ambient temperatures (?46 °C and 66 °C). This result indicates that these HDPE blends can be considered good candidates to replace pure HDPE in applications in which high values of toughness are required at extreme ambient temperatures.     

Distributions of Crystal Size from DSC Melting Traces for Polyethylenes

Melting curves, obtained by differential scanning calorimetry, are used to estimate crystal size distributions. The proposed theoretical analysis is applied to different types of polyethylene, including high‐density polyethylene (HDPE), metallocene catalyzed linear low‐density polyethylenes (m‐LLDPE), blends of m‐LLDPEs, and Ziegler‐Natta catalyzed LLDPEs (ZN‐LLDPE). Theoretical predictions are in agreement with experimental results. A generalized melting temperature equation successfully predicts the melting temperatures of all the LLDPEs, although it was initially proposed for homogeneous copolymers with excluded comonomers. A new definition of the heat of fusion for pure crystals is proposed. This heat of fusion can be calculated from the average crystal size or the crystal size number distribution.     

Rotational molding of polycarbonate reinforced polyethylene composites: Processing parameters and properties

Rotational molding has become one of the most important polymer processing methods for producing hollow plastic articles. The goal of this report is to study the rotational molding of polycarbonate (PC) reinforced polyethylene composites. Experiments were carried out on a laboratory scale uniaxial machine, which is capable of measuring internal air temperatures in the cycle. Before molding, PC and polyethylene were blended by a twin‐screw extruder. The extrudate was cut into pellets. Polyethylene powder mixed with PC/polyethylene pellets were then mixed by a dry mixer and rotationally molded by a box mold. Characterization of molded part properties was performed after molding. It was found that the impact strength of molded composites increased with the volume fraction of PC reinforcement, whereas the tensile strengths decreased with the reinforcement. Higher cooling rates molded composites with higher impact strengths but lower tensile strengths. There exists an optimum internal peak air temperature with which composites of the highest mechanical properties can be obtained. Additionally, various mathematical models were employed to predict the tensile properties of molded composites, and the Halpin–Tsai–Nielsen model was found to match well with the measured tensile modulus of molded composites. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

A quantitative analysis of low density polyethylene and linear low density polyethylene blends by differential scanning calorimetery and fourier transform infrared spectroscopy methods

Blends of low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) are widely used for blown film applications. An accurate and rapid test scheme to identify the type and composition of α-olefin in LDPE/LLDPE blends has been developed that utilizes differential scanning calorimetery (DSC) and Fourier transform infrared (FTIR) spectroscopy techniques. The melting point of LDPE varies with density and usually is in the range of 106°C to 112°C for film grade resins. The DSC thermogram of LLDPE is characterized by a broad range of melting peaks with a lower melting peak around 106°C to 110°C and a higher one in the range of 120°C to 124°C. In a blend with LDPE, the ratio of the two endothermic peak heights changes. At a given weight percent of LDPE, this ratio depends on the type of LLDPE (i.e., the comonomer used). Separate calibrations for butene-1, hexene-1, and octene-1 LLDPEs have been developed to quantify the blend composition from DSC thermograms where the α-olefin type is successfully identified by FTIR over the entire blend composition range. The calibration curves are applicable to narrow melt index (MI) and density range conventional film grade LDPE and LLDPE resins and are not intended to be used for the metallocene type LLDPEs.     

Effects of strain rate and temperature on the mechanical behavior of high-density polyethylene

The objective of this work is to initiate the discussion about multiphysics relationships between the molten and solid states of high-density polyethylene (HDPE). The extrusion and the injection processes are employed to prepare samples, and the experimental procedures, using differential scanning calorimetry, dynamic thermomechanical analysis (DMTA), thermal gravimetric analysis, and rheological measurements, are defined to choose the optimal variables. After different characterizations, the extrusion and injection temperatures of 220 and 230 °C have been chosen. To investigate the viscoelastic behavior of HDPE, the DMTA is used. To perform the high strain rate tensile tests, tensile machine was equipped with a specific furnace. Two temperatures, −20 and 20 °C, with strain rates varying from 0.001 to 100 seconds⁻¹ were used to compare the flow characteristics. Results showed that by increasing the strain rate the molecular mobility of the HDPE chains is decreased. In addition, to the tests at −20 °C, the increase of Young's modulus can be properly observed, under high strain rates. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48778.     

Toughening effect of CPE on ASA/SAN binary blends at different temperatures

The effect of chlorinated polyethylene (CPE) on the impact toughness of acrylonitrile–styrene–acrylic (ASA) terpolymer/styrene–acrylonitrile copolymer (SAN) binary blends (25/75, w/w) was systematically investigated at three different temperatures (?30 °C, 0 °C, and 23 °C). With the addition of 60 phr CPE, the impact strength increased by 11 times at 23 °C and 10 times at 0 °C. However, the toughening effect was not obvious when the testing temperature was ?30 °C. Since the glass‐transition temperature (T_g) of CPE was about ?18.3 °C as measured with dynamic mechanical analysis tests, the polymeric chains of CPE have been “frozen out” at ?30 °C. As a result, CPE evidently cannot improve the toughness of the blend system. The morphology of impact‐fractured surfaces observed by scanning electron microscopy also confirmed the effect of CPE on the impact toughness of ASA/SAN binary blends. The heat distortion temperature remained almost unchanged, indicating that the improvement in toughness did not sacrifice heat resistance. Furthermore, other mechanical properties were evaluated, and the possible interactions among components of the blends were also analyzed by Fourier transform infrared spectra. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43353.     

Improvement in Low Temperature Izod Impact Strength of SAN/ASA/HNBR Ternary Blends Considering Competing Effects of Glass Transition Temperature and Compatibility

The competing effects of glass transition temperature (T_g) and compatibility on the low temperature Izod impact toughness of styrene–acrylonitrile copolymer/acrylonitrile–styrene‐acrylate terpolymer (SAN/ASA, 75/25, w/w) blends were investigated by using a series of hydrogenated nitrile butadiene rubbers (HNBRs) with different acrylonitrile (AN) contents. The results showed that the HNBR with AN mass content ranging from 21% to 43% had good compatibility with polymer matrix and exhibited dramatic toughening effect at 25°C. Owing to their low T_gs, only the HNBRs (AN = 21% and 25%) remained favorable toughening effect at 0 and ?30°C, respectively. Furthermore, the HNBR with 0% AN content was represented by butadiene rubber (BR). Although, BR has an extremely low T_g (?94.5°C), it is incompatible with polymer matrix, and then could not toughen the material at three temperatures (?30, 0, and 25°C, respectively). Various characterizations including solubility parameters, scanning electron microscopy (SEM), dynamic mechanical thermal analysis (DMTA), Fourier transform infrared (FTIR) spectroscopy, and so on were carried out to elucidate the toughening mechanism. J. VINYL ADDIT. TECHNOL., 25:225–235, 2019. © 2018 Society of Plastics Engineers     

Viscoelastic properties and morphological characteristics of polymer‐modified bitumen blends

The state of dispersion, the viscoelastic properties and the mechanical properties (such as Young's modulus, ductibility, penetration, and Fraas breaking point) of polymer‐modified bitumen are investigated. Bitumen was modified with low‐density polyethylene from processed bags (PE_bags) and styrene‐butadiene random block copolymer (SBR). The blends were characterized by optical microscopy, dynamic mechanical thermal analysis (DMTA), and other conventional methods. Photomicrographs indicated that different morphologies were obtained; PE_bags gave dispersions with almost spherical polymer particles; whereas in the case of SBR, fibrillar domains were observed. DMTA measurements indicated significant changes of the storage and loss moduli of modified bitumen; depending on the polymer content in the bitumen matrix, these values were three to four times higher compared with neat bitumen. Blends with SBR showed a significantly increased resistance to cracking at low temperatures due to decrease of the glass transition temperature from ?14 to ?34°C. Contrary, PE_bags gave better results at higher temperatures where as a result of the increased resistance to permanent deformation the softening point of modified bitumen was shifted from 52 to 73°C. It was also investigated the influence of mixtures of PE_bags/SBR on the properties of bitumen as function of the composition and ratio between PE_bags and SBR. It was found that the best improvement in deformation resistance, permanent deformation, and cracking of bitumen was achieved with the addition of PE_bags/SBR mixture as the rubber increased the bitumen properties at low temperatures and the polyolefin at high temperatures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of reactor blend of linear and branched polyethylene using metallocene/Ni‐diimine binary catalyst system in a single reactor

This work reports the synthesis of a series of reactor blends of linear and branched polyethylene materials using a combination of [1,4‐bis(2,6‐diisopropylphenyl) acenaphthene diimine nickel(II) dibromide] ( 1 )/MMAO, known as an active catalyst for the production of branched polyethylene, and [rac‐ethylenebis(indenyl) zirconium dichloride] ( 2 )/MMAO, which is active for the production of linear polyethylene. The polymerization runs were performed at various levels of temperature, pressure, and catalyst 2 molar fractions. At 5°C, there was very low influence of catalyst 2 molar fraction on the overall catalyst activity. However, at 30°C and 50°C, the overall catalyst activity increased linearly with catalyst 2 molar fraction. The same linear dependency was also found for the polymerization reactions carried out at 60°C and 100°C. At various levels of temperature and ethylene pressure, higher melting temperature and crystallinity were observed with an increase in catalyst 2 molar fraction. At 60°C and 100 psig, the DSC thermograms of the polymers produced with 1 / 2 /MMAO exhibited two distinct peaks with melting temperatures closely corresponding to the melting temperatures of the polymers produced with the individual catalysts, 1 /MMAO and 2 /MMAO. The GPCV analysis of all polyethylene samples showed monomodal molecular weight distributions with low polydispersities. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2212–2217, 2005     

Fracture mechanics and relaxation processes in polyvinyl chloride

Linear elastic fracture mechanics has been applied to investigate the strain rate sensitivity of polyvinyl chloride over a range of temperatures (?197 to +80°C). Three-point bend tests have been carried out at two widely different strain rates; in “static” (slow bend) conditions and in a “dynamic” (impact) situation. A specially instrumented Charpy impact hammer has been used to analyse the record of transient loads. The fracture toughness results show a close relationship to the relaxation phenomena between ?60 and +75 °C; it was observed that in this region the maximum toughness correlated with the maximum β-relaxation. It was also found that, while in the region of low temperatures the material showed a considerable degree of strain rate sensitivity, at +50° the dynamic and static toughness were of the same order of magnitude; this behavior differs substantially from that observed in metals.     

The ductile-brittle transition of low-density polyethylene

The impact behavior of a low-density polyethylene was studied with an instrumented Charpy tester. A change from elastic or ductile response to brittle fracture was observed over a small temperature interval, usually within 1°C. This characteristic impact transition temperature (ITT) was highly sensitive to shallow, sharp notches. Whereas an unnotched test bar had a very low impact transition temperature of ?94°C, a razor cut with a depth of only 5 percent of the total thickness raised it to ?4°C. The impact transition temperature was effectively reduced by increasing the cooling rate during specimen preparation and by the addition of nonpolar liquids, On the other hand, impact properties were adversely affected by aging, annealing, and adding other thermoplastics.     

Effect of natural fibers on thermal and mechanical properties of natural fiber polypropylene composites studied by dynamic mechanical analysis

The present study deals with the effects of natural fibers on thermal and mechanical properties of natural fiber polypropylene composites using dynamic mechanical analysis. Composites of polypropylene and various natural fibers including kenaf fibers, wood flour, rice hulls, and newsprint fibers were prepared at 25 and 50% (by weight) fiber content levels. One and two percent maleic anhydride grafted polypropylene was also used as the compatibilizer for composites containing 25 and 50% fibers, respectively. Specimens for dynamic mechanical analysis tests were cut out of injection‐molded samples and were tested over a temperature range of ?60 to +120°C. Frequency of the oscillations was fixed at 1 Hz and the strain amplitude was 0.1%, which was well within the linear viscoelastic region. The heating rate was 2°C/min for all temperature scan tests. Storage modulus (E′), loss modulus (E″), and mechanical loss factor (tan δ) were collected during the test and were plotted versus temperature. An increase in storage and loss moduli and a decrease in the mechanical loss factor were observed for all composites indicating more elastic behavior of the composites as compared with the pure PP. Changes in phase transition temperatures were monitored and possible causes were discussed. Results indicated that glass transition was slightly shifted to lower temperatures in composites. α transition temperature was higher in the case of composites and its intensity was higher as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4341–4349, 2006     

The rotational molding of a thermotropic liquid crystalline polymer

Thermotropic liquid crystalline polymers (TLCPs) exhibit a number of mechanical and physical properties such as excellent chemical resistance, low permeability, low coefficient of thermal expansion, high tensile strength and modulus, and good impact resistance, which make them desirable as a rotationally molded storage vessel. However, there are no reports in the technical literature of the successful rotational molding of TLCPs. In this article, conditions are identified that lead to the successful rotational molding of a TLCP, Vectra B 950. First, a technique was developed to produce particles suitable for rotational molding because TLCPs cannot be ground into a free‐flowing powder. Second, because the viscosity at low shear rates can be detrimental to the sintering process, coalescence experiments with isolated particles were carried out to determine the thermal and environmental conditions at which sintering should occur. These conditions were then applied to static sintering experiments to determine whether coalescence and densification of the bulk powder would occur. Finally, the powders were successfully rotationally molded into tubular structures in a single axis, lab‐scale device. The density of the molded structure was essentially equivalent to the material density and the tensile strength and modulus were approximately 18 MPa and 2 GPa, respectively. POLYM. ENG. SCI., 45:410–423, 2005. © 2005 Society of Plastics Engineers     

Application of di-functional organic peroxides in the polymerization of ethylene under high pressures

The suitability of difunctional organic peroxides for the synthesis of low density polyethylene (LDPE) was examined with a view to improve the results. Polymerization tests were carried out in a stirrer autoclave pilot plant using three different difunctional compounds with different levels of thermal stability at a pressure of 1700 bar and temperatures of between 180 and 290°C. The conversion and the specific peroxide consumption were measured and the average molar masses of the polymers obtained were determined. The solubility of the peroxides in isododecane was also examined.     

Microstructural and optical properties of the ZnS ceramics sintered by vacuum hot-pressing using hydrothermally synthesized ZnS powders

ZnS nanopowders annealed at low temperatures (≤550?°C) have a pure cubic structure, while a small amount of hexagonal phase formed in specimens annealed at temperatures ≥700?°C. The particle sizes of the ZnS nanopowders increased with the annealing temperature. ZnS ceramics that were sintered using ZnS nanopowders annealed at low temperatures (≤550?°C) exhibited low transmittance, because of their porous microstructure. ZnS ceramics that were synthesized using ZnS powders annealed at high temperatures (≥800?°C) containing large agglomerated particles, also exhibited low transmittance, due to the presence of a liquid phase. A carbonate absorption band was found from the ZnS ceramics with small grains, because carbon ions diffused from the graphite mold into the ZnS ceramics during sintering, probably through the grain boundaries, and formed carbonates. A ZnS ceramic that was sintered at 1020?°C using the nanopowders annealed at 750?°C exhibited dense microstructure, with a large transmittance, 68%, in the wavelength range 6.0–12?μm.     

Thermal transitions in polyimide transfer under sliding against steel,investigated by Raman spectroscopy and thermal analysis

Polyimides (PI) are known for their extremely high thermal stability and lack of a glass transition temperature below their decomposition point. Therefore, they are frequently used in high‐demanding tribological applications. The tribological characteristics of sintered polyimide (SP‐1) are presently investigated as a function of the sliding temperature that is artificially varied between 60°C and 260°C under fixed load in counterformal contact with a steel plate. For obtaining low friction and wear, a transfer film needs to develop onto the sliding counterface, induced by viscous polymer flow. As surface plastification is more difficult for high‐performance materials, for example, polyimide, a transition towards low friction and stabilized wear rates is observed at temperatures higher than 180°C in accordance with the occurrence of plate‐like transfer particles, while high friction and no transfer was observed at lower temperatures. This transition is correlated to a peak value in both friction and wear at 180°C and is further explained by Raman spectroscopy performed on the worn polymer surfaces and temperature‐modulated differential scanning calorimetry. It is concluded that the intensity of C‐N‐C related absorption bands is minimal at 180°C and is complementary to the intensity of the C?C phenylene structure that is maximal at 180°C. The orientation of the C‐O‐C structure slightly decreases relative to the sliding surface at higher bulk temperatures. The amount of C?O functional groups is the lowest at 140°C, while its orientation progressively enhances at higher bulk temperatures. At 140°C also, the lowest wear rates were measured. The 180°C transition temperature with a peak value in both friction and wear corresponds to a secondary transition measured in the specific complex heat capacity, pointing out that the overall bulk temperature is presently more important than local flash temperatures for causing transitions in tribological behavior. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1407–1425, 2006     

An experimental study of foamed polyethylene in rotational molding

Rotational molding of foamed polyethylene has increasingly become an important process in industry because of its thicker walls, low sound transfer, high stiffness and good thermal insulation. However, the foaming process of polyethylene during rotational molding has not been well studied. The focus of this article is to assess the rotomoldability of foamed polyethylene and to investigate how blowing agents can influence the process of rotational molding and the final product quality. Rotational molding experiments were carried out in a laboratory scale uniaxial machine capable of measuring internal mold temperature in the cycle. Mechanical property tests, as well as thickness distribution and density measurements, were performed on the rotationally molded parts. Differential scanning calorimetry and optical microscopy have also been employed to identify the material and structural parameters. It was found that the presence of blowing agent results in an improvement of the impact properties, which are counteracted by longer cycle times and uneven surfaces.