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     

Thermal decomposition kinetics of poly(nButMA‐b‐St) diblock copolymer synthesized by ATRP

The reaction mechanism of decomposition process and the kinetic parameters of the poly(n‐butyl methacrylate‐b‐styrene), poly(nButMA‐b‐St), diblock copolymer synthesized by atom transfer radical polymerization (ATRP) were investigated by thermogravimetric analysis (TGA) at different heating rates. TGA curves showed that the thermal decomposition occurred in one stage. The apparent activation energies of thermal decomposition for copolymer, as determined by the Kissinger's, Flynn–Wall–Ozawa and Tang methods, which does not require knowledge of the reaction mechanism (RM), were 112.52, 116.54, and 113.41 kJ/mol, respectively. The experimental results were compared with master plots, in the range of the Doyle approximation. Analysis of experimental results suggests that in the conversion range studied, 3–18%, the actual RM is an A₂ sigmoidal type. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal degradation kinetics of poly(N‐adamantyl‐exo‐nadimide) synthesized by addition polymerization

The thermal decomposition behavior and degradation kinetics of poly(N‐adamantyl‐exo‐nadimide) were investigated with thermogravimetric analysis under dynamic conditions at five different heating rates: 10, 15, 20, 25, and 30°C/min. The derivative thermogravimetry curves of poly(N‐adamantyl‐exo‐nadimide) showed that its thermal degradation process had one weight‐loss step. The apparent activation energy of poly(N‐adamantyl‐exo‐nadimide) was estimated to be about 214.4 kJ/mol with the Ozawa–Flynn–Wall method. The most likely decomposition process was an F1 deceleration type in terms of the Coats–Redfern and Phadnis–Deshpande results. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3003–3009, 2007     

Poly(ethylene‐co‐methacrylic acid)–lithium ionomer as a compatibilizer for poly(ethylene terephthalate)/linear low‐density polyethylene blends

Poly(ethylene terephthalate) (PET)/linear low‐density polyethylene (LLDPE) blends (75/25), with contents of poly(ethylene‐co‐methacrylic acid) partially neutralized with lithium (PEMA–Li) that were systematically changed from 0 to 45% relative to the LLDPE, were obtained by direct injection molding in an attempt to (1) ameliorate the performance of the binary blend and (2) find the best compatibilizer content. PEMA–Li did not modify the PET or LLDPE amorphous‐phase compositions or the crystalline content of PET. However, PEMA–Li did lead to a nucleation effect and to the presence of a second smaller and less perfect crystalline structure. PET induced a fractional crystallization in LLDPE that remained in the presence of PEMA–Li and reduced the crystallinity of LLDPE. The ternary blends showed two similar dispersed LLDPE and PEMA–Li phases with small subparticles, probably PET, inside. The compatibilizing effect of PEMA–Li was clearly shown by the impressive increase in the break strain, along with only small decreases in the modulus of elasticity and in the tensile strength. With respect to the recycling possibilities of LLDPE, a ternary blend with the addition of 22.5% PEMA–Li, which led to very slight modulus and yield stress decreases with respect to the binary blend and a break strain increase of 480%, appeared to be the most attractive. However, the highest property improvement appeared with the addition of 37.5% PEMA–Li, which led to elasticity modulus and tensile strength decreases of only 9%, along with a very high break strain increase (760%). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1322–1328, 2003     

Flame retardation of dibromoneopentyl glycol on intumescent flame‐retardant/low‐density polyethylene composites

On the basis of ammonium polyphosphate (APP) microencapsulated with pentaerythritol/dibromoneopentyl glycol (DBNPG) mixed phosphate melamine salt as an intumescent flame retardant (IFR), the influence of DBNPG on the flame retardancy of IFR/low‐density polyethylene was investigated. The results prove that DBNPG could influence the combustion heat and the thermal barrier properties of the char layer in combustion. The intumescent degree (ID), compactness, and closure were the determinants of the thermal barrier properties of the char layer. A greater ID below 500°C and then a more compact and closed char layer above 500°C contributed to the better thermal barrier properties. An appropriate DBNPG reduced the combustion heat and promoted the formation of a compact and closed char layer by increasing of the melting viscosity of the composites. However, excessive DBNPG destroyed the closure of the char layer and increased the combustion heat because of a decrease in the melting viscosity of the composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41244.     

Study of heat shrinkability of crosslinked low‐density polyethylene/poly(ethylene vinyl acetate) blends

In this study, the heat‐shrinkage property in polymer was induced by first compounding low‐density polyethylene/poly(ethylene vinyl acetate) (LDPE/EVA) blends with various amounts of peroxide in a twin‐screw extruder at about 130°C. The resulting granules were molded to shape and chemically crosslinked by compression molding. A process of heating–stretching–cooling was then performed on the samples while on a tensile machine. Shrinkability and effective parameters were also investigated using thermal mechanical analysis. The results showed that the gel fraction was higher for the sample of higher EVA content with the same amount of dicumyl peroxide (DCP). A decrease in the melting point and heat of fusion (ΔH_f), as determined from DSC, was observed with an increase in the DCP content. Studies on the heat shrinkability of the samples showed that samples stretched above the melting point had a higher shrinkage temperature than those stretched around the crystal transition temperature. The results showed that by increasing the peroxide content, the shrinkage temperature was decreased. These could be attributed to the formation of new spherulites as well as changes in the amount and the size of crystals. Furthermore, in samples elongated at 120°C (above the melting point), the rate of stretching had no effect on the shrinkage temperature. The results showed that the extent of strain had no effect on the temperature of shrinkage, but rather on the ultimate shrinkage value. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1389–1395, 2004     

Synthesis,characterization, and thermal degradation kinetics of the copolymer poly(4‐methoxybenzyl methacrylate‐co‐isobornyl methacrylate)

A copolymer of 4‐methoxybenzyl methacrylate and isobornyl methacrylate was synthesized by atom transfer radical polymerization. The structure of poly(4‐methoxybenzyl methacrylate‐co‐isobornyl methacrylate) was confirmed by means of Fourier transform infrared, ¹H‐NMR, and ¹³C‐NMR techniques. The molecular weight distribution values of the copolymer were determined with gel permeation chromatography. The number‐average molecular weight and polydispersity index values of poly(4‐methoxybenzyl methacrylate‐co‐isobornyl methacrylate) were found to be 12,500 and 1.5, respectively. The kinetics of the thermal degradation of the copolymer was investigated with thermogravimetric analysis at different heating rates. The activation energy values obtained with the Kissinger, Flynn–Wall–Ozawa, and Tang methods were determined to be 166.38, 167.54, and 167.47 kJ/mol, respectively. Different integral and differential methods were used, and the results were compared with these values. Doyle approximation was also used for comparing the experimental results to master plots. An analysis of the experimental results suggested that the reaction mechanism was an R₁ deceleration type in the conversion range studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis,characterization, and thermal degradation kinetics of poly(decamethylene 2‐oxoglutarate)

Poly(decamethylene 2‐oxoglutarate) [poly (DMOG)] was synthesized by a melt polycondensation reaction. The structure of poly(DMOG) was confirmed by means of Fourier transform infrared, ¹H‐NMR, and ¹³C NMR spectroscopies. The molecular weight distribution values of poly(DMOG) were determined with size exclusion chromatography. The number‐average molecular weight, weight‐average molecular weight, and polydispersity index values of poly(DMOG) were found to be 13,200, 19,000, and 1.439, respectively. Also, characterization was made by thermogravimetry (TG)–dynamic thermal analysis. The kinetics of the thermal degradation of poly (DMOG) was investigated by thermogravimetric analysis at different heating rates. TG curves showed that the thermal decomposition of poly(DMOG) occurred in one stage. The apparent activation energies of thermal decomposition for poly(DMOG), as determined by the Tang method, the Flynn–Wall–Ozawa method, the Kissinger–Akahira–Sunose method, and the Coats–Redfern method were 122.5, 126.8, 121.4, and 122.9 kJ/mol, respectively. The mechanism function and pre‐exponential factor were also determined by the master plots method. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal degradation of poly(dimethylsilylene) and poly(tetramethyldisilylene‐co‐styrene)

Thermal degradation of poly(dimethylsilylene) homopolymer (PDMS) and poly(tetramethyldisilylene‐co‐styrene) copolymer (PTMDSS) was investigated by pyrolysis‐gas chromatography and thermogravimetry (TG). PDMS decomposes by depolymerization, producing linear and cyclic oligomeric products, whereas PTMDSS decomposes by random degradation along the chain resulting in each monomeric product and various other combination products. The homopolymer was found to be much less stable than the copolymer. The decomposition mechanisms leading to the formation of various products are shown. The kinetic parameters of thermal degradation were evaluated by different integral methods using TG data. The activation energies of decomposition (E) for the homopolymer and the copolymer are found to be 122 and 181 kJ/mol, respectively, and the corresponding values of order of reaction are 1 and 1.5. The observed difference in the thermal stability and the values of the kinetic parameters for decomposition of these polymers are explained in relation with the mechanism of decomposition. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Chemorheological study of compatibilized blends of low‐density polyethylene and polydimethyl siloxane rubber

Compatibilization of the blends of polydimethyl siloxane (PDMS) rubber and low‐density polyethylene (LDPE) was achieved through reactive processing during extrusion in a Monsanto Processability Tester (MPT). The chemorheological characteristics of 50 : 50 LDPE : PDMS blends with varying proportions (0–8 wt %) of ethylene comethyl acrylate (EMA) were investigated at three different temperatures (170, 190, and 210°C) and four different shear rates (61.3, 122.6, 306.6, and 613.1 s^?1). It was found that EMA reacts with vinyl groups of PDMS rubber at a temperature of 190°C during extrusion through the capillary of MPT, forming EMA‐grafted‐PDMS rubber (EMA‐g‐PDMS), which acts as the compatibilizer for the blend systems. The results are based on IR spectroscopy, melt rheology, and phase morphology of the blends. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 12: 2810–2817, 2003     

The phase behavior and thermal stability of blends of poly(styrene‐co‐methacrylic acid)/poly(styrene‐co‐ 4‐vinylpyridine)

The hydrogen bonding and miscibility behaviors of poly(styrene‐co‐methacrylic acid) (PSMA20) containing 20% of methacrylic acid with copolymers of poly(styrene‐co‐4‐vinylpyridine) (PS4VP) containing 5, 15, 30, 40, and 50%, respectively, of 4‐vinylpyridine were investigated by differential scanning calorimetry, thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy (FTIR). It was shown that all the blends have a single glass transition over the entire composition range. The obtained T_gs of PSMA20/PS4VP blends containing an excess amount of PS4VP, above 15% of 4VP in the copolymer, were found to be significantly higher than those observed for each individual component of the mixture, indicating that these blends are able to form interpolymer complexes. The FTIR study reveals presence of intermolecular hydrogen‐bonding interaction between vinylpyridine nitrogen atom and the hydroxyl of MMA group and intensifies when the amount of 4VP is increased in PS4VP copolymers. A new band characterizing these interactions at 1724 cm⁻¹ was observed. In addition, the quantitative FTIR study carried out for PSMA20/PS4VP blends was also performed for the methacrylic acid and 4‐vinylpyridine functional groups. The TGA study confirmed that the thermal stability of these blends was clearly improved. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Melt strength of linear low‐density polyethylene/low‐density polyethylene blends

Linear low‐density polyethylenes and low‐density polyethylenes of various compositions were melt‐blended with a batch mixer. The blends were characterized by their melt strengths and other rheological properties. A simple method for measuring melt strength is presented. The melt strength of a blend may vary according to the additive rule or deviate from the additive rule by showing a synergistic or antagonistic effect. This article reports our investigation of the parameters controlling variations of the melt strength of a blend. The reciprocal of the melt strength of a blend correlates well with the reciprocal of the zero‐shear viscosity and the reciprocal of the relaxation time of the melt. An empirical equation relating the maximum increment (or decrement) of the melt strength to the melt indices of the blend components is proposed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1408–1418, 2002     

Degradation behaviors of linear low‐density polyethylene and poly(L‐lactic acid) blends

In this study, the degradability of linear low‐density polyethylene (LLDPE) and poly(L ‐lactic acid) (PLLA) blend films under controlled composting conditions was investigated according to modified ASTM D 5338 (2003). Differential scanning calorimetry, X‐ray diffraction, and Fourier transform infrared spectroscopy were used to determine the thermal and morphological properties of the plastic films. LLDPE 80 (80 wt % LLDPE and 20 wt % PLLA) degraded faster than grafted low‐density polyethylene–maleic anhydride (M‐g‐L) 80/4 (80 wt % LLDPE, 20 wt % PLLA, and 4 phr compatibilizer) and pure LLDPE (LLDPE 100). The mechanical properties and weight changes were determined after composting. The tensile strength of LLDPE 100, LLDPE 80, and M‐g‐L 80/4 decreased by 20, 54, and 35%, respectively. The films, as a result of degradation, exhibited a decrease in their mass. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Use of zinc‐neutralized ethylene/methacrylic acid copolymer ionomers as blend compatibilizers for nylon 6 and low‐density polyethylene

The effect of the composition on the morphologies and properties of uncompatibilized and compatibilized blends of nylon 6 and low‐density polyethylene were studied over a wide range of weight fractions. The uncompatibilized blends had substantially reduced mechanical properties after mixing, and this was almost certainly due to poor interfacial adhesion between the two polymers. The addition of a zinc‐neutralized poly(ethylene‐co‐methacrylic acid) ionomer (Surlyn® 9020) as a compatibilizer improved the mechanical properties in comparison with those of the material blended without the compatibilizer. The clearest evidence of this improvement came from dynamic mechanical studies; for selected blends with high polyethylene contents, the drop in the modulus corresponding to the transition of a solid to a melt occurred at higher temperatures with the added compatibilizer. This improvement in the properties was accompanied by a reduction in the dispersed‐phase size due to the interaction between the ionic part of the ionomer and the amide groups of nylon 6, especially when nylon 6 was the dispersed phase of the blend. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 620–629, 2003     

Essential work of fracture of low‐filled poly(methyl methacrylate)/starch composites

In this study, poly(methyl methacrylate) (PMMA)/starch composites were prepared by a simple solvent casting method. The morphologies of the PMMA/starch composites were studied by scanning electron microscopy. The intermolecular interaction between PMMA and starch was investigated with Fourier transform infrared spectroscopy. The thermal properties of the PMMA/starch composites were compared with those of the pure PMMA sample. Thermogravimetric analysis showed that the thermal stability increased as the starch content increased in the composites. The biodegradability of the PMMA/starch composites was studied with a soil burial test. The degradability was measured in terms of mechanical strength, which increased as the starch content increased. The essential work of fracture (EWF) of the PMMA/starch composite films was investigated by the application of EWF theory under in‐plane (mode I) conditions, and we found that the toughness, in terms of the EWF of composites, increased compared to that of pure PMMA. The fracture of the composites was also evaluated by ANSYS software, and the results were compared to the experimental output. The increased toughness of these PMMA/starch composites may enable their application in the automobile and packaging industries. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Bioactive efficacy of low‐density polyethylene films with natural additives

Active packaging can be defined as packaging that includes additives that help to extend the shelf life of food; among the advantages of its use is the possibility to reduce the amount of additives added to the food during processing. The aim of this study was to develop, characterize, and apply active films of low‐density polyethylene, incorporating carotenoid and yerba mate extracts as active additives. Active films were obtained by extrusion and were characterized for water vapor permeability, thickness, color, and mechanical and thermal properties. The effectiveness of the films was evaluated using butter packed in the formulated films. There was a significant reduction in thickness, and mechanical, thermal, and water vapor barrier parameters of the films compared to the control. The concentration of additives directly influenced coloration and antioxidant and antimicrobial action of the films. The formulated films provided protection against oxidative action and inhibition of microbial growth. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46461.     

Improving low‐density polyethylene/poly(ethylene terephthalate) blends with graft copolymers

Blends of low‐density polyethylene (LDPE) and poly(ethylene terephthalate) (PET) were prepared with different weight compositions with a plasticorder at 240°C at a rotor speed of 64 rpm for 10 min. The physicomechanical properties of the prepared blends were investigated with special reference to the effects of the blend ratio. Graft copolymers, that is, LDPE‐grafted acrylic acid and LDPE‐grafted acrylonitrile, were prepared with γ‐irradiation. The copolymers were melt‐mixed in various contents (i.e., 3, 5, 7, and 9 phr) with a LDPE/PET blend with a weight ratio of 75/25 and used as compatibilizers. The effect of the compatibilizer contents on the physicomechanical properties and equilibrium swelling of the binary blend was investigated. With an increase in the compatibilizer content up to 7 phr, the blend showed an improvement in the physicomechanical properties and reduced equilibrium swelling in comparison with the uncompatibilized one. The addition of a compatibilizer beyond 7 phr did not improve the blend properties any further. The efficiency of the compatibilizers (7 phr) was also evaluated by studies of the phase morphology (scanning electron microscopy) and thermal properties (differential scanning calorimetry and thermogravimetric analysis). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetic study of the thermal decomposition of (2‐phenyl‐1,3‐dioxolane‐4‐yl) methyl methacrylate and 2‐hydroxyethyl methacrylate copolymers

The kinetics of nonisothermal decomposition of (2‐phenyl‐1,3‐dioxolane‐4‐yl) methyl methacrylate (PDMMA), 2‐hydroxyethyl methacrylate (HEMA), and vinyl‐pyrrolidone (VPy) copolymers were investigated by thermogravimetry (TG) and differential thermal analysis (DTA). The data indicated that the major weight loss occurs in the range of 270 to 450°C. The decomposition characteristics showed essentially two regimes and varied depending on the temperature and the copolymer composition. The apparent kinetic parameters of the decompositions were estimated from both TG and DTA data by using the alternative calculation methods. The results suggest that the weight loss rates may be represented, depending on the type of sample, by a reaction model of overall order 1.0 to 1.6, with an activation energy of approximately 65–95 kJ mol^?1. The DTA data estimated considerably higher values for the overall activation energies, around 198–240 kJ mol^?1. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1500–1508, 2005     

Novolac resin–poly(ethyl methacrylate) interpenetrating polymer networks: Morphology and mechanical and thermal properties

Full interpenetrating networks (IPNs) and semi‐IPNs of Novolac (phenolic) resin and poly(ethyl methacrylate) (PEMA) were prepared by the sequential mode of synthesis. These were characterized with respect to their mechanical properties, that is, ultimate tensile strength (UTS), percentage elongation at break, modulus, and toughness. Thermal properties were studied by DSC and thermogravimetric analysis (TGA). The morphological features were studied through polarizing light microscopy (PLM). The effects of variation of the blend ratios on the above‐mentioned properties were examined. There was a gradual decrease of modulus and UTS with consequent increases in elongation at break and toughness for both types of IPNs with increasing proportions of PEMA. An inward shift and lowering (with respect to pure phenolic resin) of the glass‐transition temperatures of the IPNs with increasing proportions of PEMA were observed, thus indicating a plasticizing influence of PEMA on the rigid and brittle matrix of crosslinked phenolic resin. The TGA thermograms exhibit two‐step degradation patterns. Although there was an apparent increase in thermal stability at the initial stages, particularly at lower temperatures, a substantial decrease in thermal stability was observed in the regions of higher temperatures. The surface morphology as revealed by PLM clearly indicates two‐phase structures in all the full and semi‐IPNs, irrespective of PEMA content. The matrix–PEMA domain interfaces are quite sharp at higher concentrations of PEMA. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 412–420, 2003     

Phase dispersion–crosslinking synergism in binary blends of poly(vinyl chloride) with low‐density polyethylene: Entrapping phenomenon in PVC/LDPE/DCP blend

The co‐crosslinked products and the entrapping phenomenon that may exist in a poly(vinyl chloride)/low density polyethylene/dicumyl peroxide (PVC/LDPE/DCP) blend were investigated. The results of selective extraction show that unextracted PVC was due to not being co‐crosslinked with LDPE but being entrapped by the networks formed by the LDPE phase. SBR, as a solid‐phase dispersant, can promote the perfection of networks of the LDPE phase when it is added to the PVC/LDPE blends together with DCP, which leads to more PVC unextracted and improvement of the mechanical properties of PVC/LDPE blends. Meanwhile, the improvement of the tensile properties is dependent mainly on the properties of the LDPE networks. Finally, the mechanism of phase dispersion–crosslinking synergism is presented. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1296–1303, 2003