Thermal analysis of high‐density polyethylene and low‐density polyethylene with enhanced biodegradability

The thermal properties of high‐density polyethylene (HDPE) and low‐density polyethylene (LDPE) filled with different biodegradable additives (Mater‐Bi AF05H, Cornplast, and Bioefect 72000) were investigated with thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The DSC traces of the additives indicated that they did not undergo any significant phase change or transition in the temperature region typically encountered by a commercial composting system. The TGA results showed that the presence of the additive led to a thermally less stable matrix and higher residue percentages. The products obtained during the thermodegradation of these degradable polyolefins were similar to those from pure polyethylenes. The LDPE blends were thermally less stable than the HDPE blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 764–772, 2002     

Photo‐induced scission and crosslinking in LDPE,LLDPE, and HDPE

The molecular degradation characteristics of three different polyethylenes were determined by deriving chain scission and crosslinking concentrations from gel permeation chromatography molecular weight distributions obtained after 3 weeks and 6 weeks laboratory ultraviolet exposure. Injection‐molded bars (3 mm thick) made from a low‐density polyethylene (LDPE), a linear low‐density polyethylene (LLDPE), and a high‐density polyethylene (HDPE) were used and all showed strong depth variations in degradation. Degradation was rapid near the exposed surfaces but very little change occurred in the bar centers, due to oxygen starvation. The most rapid rises in scission and crosslink concentrations were observed with LDPE, for which the concentrations after 6 weeks exposure were approximately double those measured after 3 weeks. With LLDPE and HDPE the scission and crosslink concentrations after 6 weeks exposure were very much greater than twice those after 3 weeks. Scission dominated over crosslinking at all depths and for all materials the scission/crosslink ratio was always ≥3, with a value of ～9 recorded for HDPE near the exposed surface after 6 weeks exposure. POLYM. ENG. SCI., 45:579–587, 2005. © 2005 Society of Plastics Engineers     

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.     

Degradation of polyethylene during extrusion. II. Degradation of low‐density polyethylene,linear low‐density polyethylene,and high‐density polyethylene in film extrusion

The degradation of different polyethylenes—low‐density polyethylene (LDPE), linear low‐density polyethylene (LLDPE), and high‐density polyethylene (HDPE)—with and without antioxidants and at different oxygen concentrations in the polymer granulates, have been studied in extrusion coating processing. The degradation was followed by online rheometry, size exclusion chromatography, surface oxidation index measurements, and gas chromatography–mass spectrometry. The degradations start in the extruder where primary radicals are formed, which are subject to the auto‐oxidation when oxygen is present. In the extruder, crosslinking or chain scissions reactions are dominating at low and high melt temperatures, respectively, for LDPE, and chain scission is overall dominating for the more linear LLDPE and HDPE resins. Additives such as antioxidants react with primary radicals formed in the melt. Degradation taking place in the film between the die orifice, and the quenching point is mainly related to the exposure time to air oxygen. Melt temperatures above 280°C give a dominating surface oxidation, which increases with the exposure time to air between die orifice and quenching too. A number of degradation products were identified—for example, aldehydes and organic acids—which were present in homologous series. The total amount of aldehydes and acids for each number of chain carbon atoms were appeared in the order of C5>C4>C6>C7?C2 for LDPE, C5>C6>C4>C7?C2 for LLDPE, and C5>C6>C7>C4?C2 for HDPE. The total amounts of oxidized compounds presented in the films were related to the processing conditions. Polymer melts exposed to oxygen at the highest temperatures and longest times showed the presence dialdehydes, in addition to the aldehydes and acids. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1525–1537, 2004     

Mechanical properties and biodegradability of LDPE blends with fatty‐acid esters of amylose and starch

In the present article a series of low‐density polyethylene (LDPE) blends with different amounts of fatty esters of amylose and starch, were prepared in a Haake‐Buchler Reomixer. The tensile as well as the dynamic thermomechanical (DMTA) properties of the blends were measured. It was found that as the amount of the esters increases in the blends, the tensile strength and especially the elongation at break decrease nonlinearly. Scanning electron microscopy (SEM) was used to assess the interfacial adhesion between LDPE and the corresponding esters. The incompatibility of the blends was also verified with DMTA and differential scanning calorimetry (DSC). From the biodegradation studies of the blends during exposure in activated sludge, it was found that all esters are biodegradable, although to a much lesser degree compared to pure strach. The biodegradation rate of the composites is relatively small due to the low biodegradation rate of the pure esters. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1089–1100, 1999     

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.     

A molecular dynamics study of the effects of branching characteristics of LDPE on its miscibility with HDPE

The effects of branching characteristics of low-density polyethylene (LDPE) on its melt miscibility with high-density polyethylene (HDPE) were studied using molecular simulation. In particular, molecular dynamics (MD) was applied to compute Hildebrand solubility parameters (δ) of models of HDPE and LDPE with different branch contents at five temperatures that are well above their melting temperatures. Values computed for δ agreed very well with experiment. The Flory-Huggins interaction parameters (χ) for blends of HDPE and different LDPE models were then calculated using the computed δ values. The level of branch content for LDPE above which the blends are immiscible and segregate in the melt was found to be around 30 branches/1000 long chain carbons at the chosen simulation temperatures. This value is significantly lower than that of butene-based linear low-density polyethylene (LLDPE) (40 branches/1000 carbons) in the blends with HDPE computed by one of the authors (polymer 2000; 41:8741). The major difference between LDPE and LLDPE models is that each modeled LDPE molecule has three long chains while each modeled LLDPE molecule had only one long chain. The present results together with those of the LLDPE/HDPE blends suggest that the long chain branching may have significant influence on the miscibility of polyethylene blends at elevated temperatures.     

Physical properties of straw lignin-based polymer blends

Lignin powder, obtained from an abundant and low cost source, straw, through a low environmental impact process, the steam explosion, is used for the preparation of blends with low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), high-density polyethylene (HDPE) and atactic polystyrene (PS).The obtained blends are processable through the conventional techniques used for thermoplastics; the modulus slightly increases for most lignin-polymer blends, while the tensile stress and elongation reduce. Moreover, lignin acts as a stabilzer against the UV radiation for PS, LDPE and LLDPE.     

Structure–property behavior of polyethylene exposed to different types of radiation

A detailed study was performed on unirradiated low‐ and high‐density polyethylene (LDPE and HDPE) films as well as irradiated films with different types of radiation such as ⁶⁰Co γ rays, thermal and fast neutrons, and electron beam irradiation. The structural changes of PE films were characterized by Fourier transform infrared (FTIR), Fourier transform Raman (FT–Raman), and ultraviolet (UV) spectrometric techniques. The results showed significant radiation degradation, crosslinking, and changes in the crystalline and amorphous regions. The influence of γ‐radiation on the structure of PE was found to be more prominent compared to that of thermal neutrons and electron beam irradiation. However, LDPE film was found to be more sensitive to these types of radiation in accordance with HDPE because of its lesser degree of crystallinity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 179–200, 2000     

Phase structural analyses of polyethylene coatings on high‐density papers. III. Determination of the crystallite thicknesses by T1 measurements

Two different extrusion‐coating qualities of polyethylene, namely LDPE and HDPE, were coated on high‐density papers. Differences were observed with respect to their response to storage and low temperature heat treatment. HDPE does not respond to storage at ambient temperature and heat treatment in the same way as LDPE. The LDPE‐coating exhibits an increase in the monoclinic crystalline fraction at the paper surface as a result of heat treatment. The nature of this response appears to be a result of adhesion to a paper surface, the properties of this surface, orientation of polymer chains, and chain mobility differences. The increase of the monoclinic fraction is shown to relate to an increase of the mean crystallite thickness and initiation of new crystallites at the paper surface. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 235–241, 2004     

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     

Rheology, Morphology and Estimation of Interfacial Tension of LDPE/EVA and HDPE/EVA Blends

Summary Rheological characteristics and morphology of low-density polyethylene (LDPE) /ethylene vinyl acetate copolymer (EVA) and high-density polyethylene (HDPE)/EVA blends were compared. Morphological examinations clearly reveal a two-phase morphology in which the LDPE/EVA blends have smaller dispersed domain size than HDPE/EVA Furthermore, LDPE/EVA shows a finely interconnected morphology at 50wt% of EVA while HDPE/EVA exhibits a coarse co-continuous morphology at the same composition. The morphological observations can be attributed to the lower viscosity ratio and lower interfacial tension in the LDPE/EVA system. The Palierne model also successfully fits to the experimental data giving higher values for interfacial tension of HDPE/EVA system as compared to LDPE/EVA.     

Carbon-Dioxide-Based Microsortation of Postconsumer Polyolefins and its Effect on Polyolefin Properties

Postconsumer polyolefin flake has been sorted using liquid carbon dioxide as a float-sink medium. This separation of PP and LDPE from HDPE was conducted at ambient temperature and a pressure that yielded a CO₂ specific gravity of 0.955, causing the HDPE to sink and the LDPE and PP to float. Although this process provided a high-purity (99+%) HDPE product stream, the effect of immersing the plastics in liquid carbon dioxide at these conditions was not previously measured. Therefore, six HDPE samples, two LDPE samples, and five PP samples were exposed to high-pressure carbon dioxide for 20 min. After this exposure, the polyolefins did not foam when the carbon dioxide was rapidly vented from the vessel. The weight reduction averaged 0.17%, which was attributed to the dissolution of low-molecular-weight additives or contaminants present on the surface of the plastics. No significant change in the melting point or latent heat of melting was observed, indicating that the degree of crystallinity was not affected by the exposure to carbon dioxide. No reduction was observed in the temperature at which the onset of thermal degradation occurred, because of the low solubility and degree of extraction of thermal stabilizers during the immersion in carbon dioxide. These results indicated that no deleterious effects on the polyolefin properties were associated with this separation technique.     

Mechanical properties-structure relationships of crosslinked blends based on LDPE/HDPE waste

Low-density polyethylene (LDPE) waste was blended with high-density polyethylene (HDPE) waste of different degrees of degradation. Structural, mechanical and rheological properties of these blends were investigated. It was found that 2 wt.-% of dicumyl peroxide improves simultaneously the tensile strength and elongation at break without serious decrease of the melt elasticity of separate PE wastes and their binary blends in comparison with unmodified PE. It was shown by DSC analyses that modification of the blends leads to better compatibility between LDPE and HDPE.     

Analysis of the flow behavior of irradiated polyethylene through transient network models

The chemical and physical properties of polymers can be dramatically affected by exposure to high-energy radiation. Two polyethylene samples (HDPE and LDPE) were irradiated with a ⁶⁰Co source. Radiated samples with doses ranging between 0.5 and 5 Mrad were melted and their viscoelastic properties characterized. Results show the normal drastic changes in their flow behavior: higher viscosity and interesting changes induced in their elasticity, particularly in the case of LDPE. An explanation of the change in flow behavior is forwarded in terms of transient network models using the concept of creation and destruction of entanglements.     

Some aspects of structural electrophysics of irradiated polyethylenes

In the case of the insulation polymeric materials, such as polyethylenes, it is of essential interest to understand correlations between structural changes and (di)electric properties. The dielectric behavior of different polyethylenes, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE), irradiated to different absorbed doses of gamma radiation, was studied through dielectric loss (tan δ) analysis. Dielectric relaxation behavior is related to the changes in the initial structure of different polyethylenes and to the radiation-induced processes of oxidative degradation and crosslinking. Differential scanning calorimetry (DSC), IC spectroscopy and gel measurements were used to determine the changes in the crystal fraction, oxidative degradation and degree of network formation, respectively.     

Biodegradation of oxo‐biodegradable polyethylene

Biodegradation of polyethylene and oxo‐biodegradable polyethylene films was studied in this work. Abiotic oxidation, which is the first stage of oxo‐biodegradation, was carried out for a period corresponding to 4 years of thermo‐oxidation at composting temperatures. The oxidation was followed by biodegradation, which was achieved by inoculating the microorganism Pseudomonas aeruginosa on polyethylene film in mineral medium and monitoring its degradation. The changes in the molecular weight of polyethylene and the concentration of oxidation products were monitored by size exclusion chromatography and Fourier transform infrared (FTIR) spectroscopy, respectively. It has been found that the initial abiotic oxidation helps to reduce the molecular weight of oxo‐biodegradable polyethylene and form easily biodegradable product fractions. In the microbial degradation stage, P. aeruginosa is found to form biofilm on polymer film indicating its growth. Molecular weight distribution data for biodegraded oxo‐biodegradable polyethylene have shown that P. aeruginosa is able to utilize the low‐molecular weight fractions produced during oxidation. However, it is not able to perturb the whole of the polymer volume as indicated by the narrowing of the polymer molecular weight distribution curve toward higher molecular fractions. The decrease in the carbonyl index, which indicates the concentration of carbonyl compounds, with time also indicates the progress of biodegradation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Rheological and mechanical properties of composites made from wood flour and recycled LDPE/HDPE blend

The effect of compounding method is studied with respect to the rheological behavior and mechanical properties of composites made of wood flour and a blend of two main components of plastics waste in municipal solid waste, low-density polyethylene (LDPE) and high-density polyethylene (HDPE). The effects of recycling process on the rheological behavior of LDPE and HDPE blends were investigated. Initially, samples of virgin LDPE and HDPE were thermo-mechanically degraded twice under controlled conditions in an extruder. The recycled materials and wood flour were then compounded by two different mixing methods: simultaneous mixing of all components and pre-mixing, including the blending of polymers in molten state, grinding and subsequent compounding with wood flour. The rheological and mechanical properties of the LDPE/HDPE blend and resultant composites were determined. The results showed that recycling increased the complex viscosity of the LDPE/HDPE blend and it exhibited miscible behavior in a molten state. Rheological testing indicated that the complex viscosity and storage modulus of the composites made by pre-mixing method were higher than that made by the simultaneous method. The results also showed that melt pre-mixing of the polymeric matrix (recycled LDPE and HDPE) improved the mechanical properties of the wood–plastic composites.     

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.     

Non-isothermal degradation kinetics of virgin linear low density polyethylene (LLDPE) and biodegradable polymer blends

The thermal degradation kinetics of several polymers, including biodegradable blends were investigated in non-isothermal thermogravimetry using several analytical methods. Virgin linear low density polyethylene (LLDPE) and LLDPE blends with polystarch-N (PSN), a prodegradant starch additive material used in 20 and 40 wt%., were investigated to determine the degradation behaviour of such materials in pyrolysis conditions. The results were compared to those obtained with virgin low (LDPE) and high density polyethylene (HDPE). An analytical solution model was also developed to assess the two degradation steps of the biodegradable blends which enabled the assessment of the apparent activation energy (E_a) of each material in the blend on its own based on the initial and final degradation temperatures. It was observed that the thermal behaviour and E_a value didn’t change significantly with the increase of biodegradable prodegradant, which shows that biodegradable blends can be treated with similar conditions regardless of the content of the biodegradable masterbatch present in the blend.