The role of chain scission and chain branching in high density polyethylene during thermo-mechanical degradation

The mechanical and thermo-oxidative degradation of high density polyethylene (HDPE) was measured in a twin-screw extruder using various processing conditions. Two types of HDPE, Phillips and Ziegler-Natta, having different levels of terminal vinyl unsaturation were analysed. Mild screw profiles, having mainly conveying elements, have short mean residence times then profiles with kneading discs and left hand elements. Carbonyl and traps-vinylene group concentrations increased, whereas vinyl group concentration decreased with number of extrusions. Higher temperature profiles intensified these effects. The thermo-mechanical degradation mechanism begins with chain scission in the longer chains due to their higher probability of entanglements. These macroradicals then react with the vinyl terminal unsaturations of other chains producing chain branching. Shorter chains are more mobile, not suffering scission but instead are used for grafting the macroradicals, increasing the molecular weight. Increase in the levels of extrusion temperature, shear and vinyl end groups content facilitates the thermo-mechanical degradation reducing the amount of both, longer chains via chain scission and shorter chains via chain branching, narrowing the polydispersity. Phillips HDPE produces a higher level of chain branching than does the Ziegler-Natta type. (C) 2004 Elsevier Ltd. All rights reserved.

Evaluation of Philips and Ziegler-Natta high-density polyethylene degradation during processing in an internal mixer using the chain scission and branching distribution function analysis

The oxidative and thermo-mechanical degradation of HDPE was studied during processing in an internal mixer under two conditions: totally and partially filled chambers, which provides lower and higher concentrations of oxygen, respectively. Two types of HDPEs, Phillips and Ziegler-Natta, having different levels of terminal vinyl unsaturations were analyzed. Materials were processed at 160, 200, and 240 degrees C. Standard rheograrns using a partially filled chamber showed that the torque is much more unstable in comparison to a totally filled chamber which provides an environment depleted of oxygen. Carbonyl and transvinylene group concentrations increased, whereas vinyl group concentration decreased with temperature and oxygen availability. Average number of chain scission and branching (n(s)) was calculated from MWD curves and its plotting versus functional groups' concentration showed that chain scission or branching takes place depending upon oxygen content and vinyl groups' consumption. Chain scission and branching distribution function (CSBDF) values showed that longer chains undergo chain scission easier than shorter ones due to their higher probability of entanglements. This yields macroradicals that react with the vinyl terminal unsaturations of other chains producing chain branching. Shorter chains are more mobile, not suffering scission but instead are used for grafting the macroradicals, increasing the molecular weight. Increase in the oxygen concentration, temperature, and vinyl end groups' content facilitates the thermo-mechanical degradation reducing the amount of both, longer chains via chain scission and shorter chains via chain branching, narrowing the polydispersity. Phillips HDPE produces a higher level of chain branching than the Ziegler-Natta's type at the same processing condition. (c) 2006 Elsevier Ltd. All rights reserved.

Kinetic evaluation of the pyrolysis of high density polyethylene over H-AlMCM-41 material

The AlMCM-41 material with Si/Al=50 was synthesized by hydrothermal method, using cethyltrimethylammonium as template. The protonic H-AlMCM-41 acid form was obtained by ion exchange with ammonium chloride solution and subsequent calcination. The characterization of the material by several techniques showed that a good-quality MCM-41 material was obtained. High-density polyethylene (HDPE) has been submitted to thermal degradation alone, and in presence of the exchanged H-AlMCM-41 catalyst at a concentration of 1: 1 in mass (H-AlMCM-41/HDPE). The reactor was connected on line to a gas chromatograph connected to a mass spectrometer. This process was evaluated by thermogravimetry (TG), from 350 to 600degreesC, under helium dynamic atmosphere, with heating rates of 5.0; 10.0 and 20.0 degreesC/min. From TG curves, the activation energy, calculated using a multiple heating rate integral kinetic method, decreased from 225.5 KJ.mol(-1), for the pure polymer (HDPE), to 184.7 KJ.mol(-1), in the presence of the catalyst (H-AlMCM-41/HDPE).

Synthesis and properties of branched polyethylene/high-density polyethylene blends using a homogeneous binary catalyst system composed of early and late transition metal complexes

Branched polyethylene/high-density polyethylene blends (BPE/HDPE) with a wide range of molecular weights, melt flow indexes (MFI), and intrinsic viscosity were prepared using the homogeneous binary catalyst system composed by Ni(alpha-diimine)Cl-2 (1) (alpha-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {Tp(Ms*)} TiCl3 (2) (Tp(Ms*)=hydridobis(3-mesitylpyrazol-1-yl)(5-mesityl-pyrazol-1-yl)) activated with MAO and/or TIBA in hexane at two different polymerization temperatures (30 and 55 degreesC) and by varying the nickel loading molar fraction (x(Ni)). At all Temperatures, a non-linear correlation between the x(Ni) and the productivity was observed, suggesting the occurrence of a synergistic effect between the nickel and the titanium catalyst precursors, which is more pronounced at 55 degreesC. The molecular weight of the BPE/HDPE blends considerably decreases with increasing Al/M molar ratio. The melt flow indexes (MFI) and intrinsic viscosities (eta) are strongly affected by x(Ni), but the melting temperatures are nearly constant, 132 +/- 3 degreesC. Dynamic mechanical thermal analysis (DMTA) shows the formation of different polymeric materials where the stiffness vanes according, to the x(Ni) and temperature used in the polymerization reaction. The surface morphology of the BPE/HDPE blends studied by scanning electron microscopy (SEM) revealed a low miscibility between the PE phases resulting in the formation of a sandwich structure after etching with o-xylene.

Linear low density polyethylene (LLDPE) from ethylene using Tp(Ms)NiCl (Tp(Ms) = hydridotris(3-mesitylpyrazol-1-yl)) and CP2ZrCl2 as a tandem catalyst system

Linear low density polyethylene (LLDPE) with different branching contents were prepared from ethylene, without the addition of alpha-olefin comonomer, using a combination of catalyst precursors {Tp(Ms)}NiCl (1) (Tp(Ms) = hydridotris(3-mesitylpyrazol-1-yl)) and Cp2ZrCl2 (2) activated with MAO/TMA (1:1) in toluene at 0degreesC and by varying the nickel loading mole fraction (x(Ni)). The polymerization results showed that the turnover frequencies are strongly dependent on the x(Ni) varying from 6.6 x 10(3) to 32.1 x 10(3) mol[C2H4]/mol[Zr] h. The C-13 NMR spectra of the copolymers showed that the branch contents of the polymers increase as the x(Ni) increase in the medium promoting the production of polymers with a wide range of melting point (T-m) (C) 2004 Elsevier B.V. All rights reserved.

Influence of the degradation on the stress cracking values of high density polyethylene (HDPE) geomembranes after different exposures

This paper presents results from stress cracking (SC) tests performed in both fresh and exposed high density polyethylene (HDPE) geomembranes (GM). The HDPE GMs were exposed to ultraviolet radiation, thermal aging (air oven) and tested for chemical compatibility with sodium hydroxide. Stress cracking tests in both fresh and degraded samples were performed in accordance to ASTM D5397: Notched Constant Tensile Load Test (NCTL) and Single Point-Notched Constant Tensile Load Test (SP-NCTL). The results of the NCTL showed that the geomembrane degradation process can be considered to be a catalyst for the phenomenon of SC because it caused a 50% to 60% reduction in stress crack resistance. The most resistance reduction was observed for the sample under chemical compatibility with sodium hydroxide. For the SP-NCTL, the results showed that the samples maintain the same trend verified in the NCTL. The largest resistance reduction was evidenced in samples undergoing ultraviolet degradation. © 2012 ejge.

Thermo-gravimetric analysis (TGA) after different exposures of high density polyethylene (HDPE) and poly vinyl chloride (PVC) geomembranes

This paper presents the results of thermogravimetric analysis (TGA) tests in PVC (1.0; 2.0 mm) and HDPE (0.8; 2.5 mm) geomembranes exposed to weathering and leachate after 30 months. The aim of this paper is the comparison of fresh and exposed samples to assess the degradation process concerning the total loss of mass of geomembranes. The exposure was conducted in accordance with the recommendations of ASTM standards. The TGA tests were carried out according to ASTM D6370 and E2105. Results show, for instance, that for PVC geomembrane the largest reductions of plasticizers occurred for samples exposed to weathering. The loss of plasticizers after the exposure contributed to the decrease of deformation and consequent increase in stiffness. TGA tests shows to be a valuable tool to control the quality of the materials. © 2012 ejge.

Characterization of high density polyethylene (HDPE) reinforced with banana peel fibers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The Effects of Weathering Exposure on the Physical, Mechanical, and Thermal Properties of High-density Polyethylene and Poly (Vinyl Chloride)

This paper presents results describing the physical, mechanical, and thermal properties (melt flow index - MFI and oxidative induction time - OIT) of high density polyethylene and poly (vinyl chloride) after weathering exposure (6, 12, 18, and 30 months). The materials exposed were geomembranes of two thicknesses: 1.0 and 2.0 mm (PVC) and 0.8 and 2.5 mm (HDPE). The climate parameters (average) obtained were 25 degrees C (temperature), 93 mm (precipitation), 66% (relative humidity), and 19 MJ/m(2). day (intensity of global radiation). Some results showed, for instance, that the behavior of the geomembranes changed after the exposures. A few minor variations in physical properties occurred. The density and thickness, for instance, varied 0.5-1.0% (average) for both the PVC and HDPE geomembranes. The mechanical properties changed as a function of the period of exposure. In general, some decreases were verified by the deformation of PVC. The samples became more rigid. In contrast, HDPE geomembranes became more ductile. Despite the variations in elasticity, some increases in deformability were verified. An MFI test showed some degradation in HDPE geomembranes. OIT tests revealed small values for both intact and exposed samples.

Biodegradation of films of low density polyethylene (LDPE), poly(hydroxibutyrate-co-valerate) (PHBV), and LDPE/PHBV (70/30) blend with Paecilomyces variotii

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

On the characterisation of electrically stressed polyethylene before and after chemical treatment

Low-density polyethylene (LDPE) was characterised for its dielectric and electrical properties before and after chemical treatment. A reduction in the permittivity and dielectric loss was observed in the polymer after treatment with hexane. The intensity in the Raman Spectrum in the disordered longitudinal acoustic mode region (DLAM) also was reduced due to a hexane treatment. Using thermally stimulated discharge current (TSDC) and laser-intensity-modulated method (LIMM) techniques it was observed that charge injection can be enhanced in the polymer matrix in the empty sites, created by the removal of the low molecular weight impurities with chemical treatment. (C) 2002 Kluwer Academic Publishers.

Melão amarelo (CAC) minimamente processado submetido a diferentes cortes e concentrações de cloreto de cálcio armazenado em atmosfera modificada passiva

The aim of this work was to evaluate the quality of yellow melon inodorus Valenciano Amarelo (CAC) fresh cut submitted to two cut types and with application postharvest of calcium chloride. After preparation cubes and slices melon were immersed in solution with different calcium chloride (CaCl2) concentrations for two minutes, afterwards they were conditioned in trays of expanded polystyrene (EPS), covered by plastic film of low density polyethylene (PEBD), stored in cold camera to 5 degrees C +/- 1 and analyzed for 8 days. They were evaluated pH, firmness, tritable acidity (AT), soluble solids (SS) sugar reducer and ratio. The pH values varied from 5.27 to 5.68. The sugars reducers content and the ratio were superior in the slices compared to the cubes. The melon slices maintained larger firmness values compared to the cubes and in general there was reduction in the values of this parameter along the storage period for all treatments. Concentrations of 1.0 and 1.5% of CaCl2, result in larger values of firmness. The storage temperature and modified passive atmosphere they contributed to quality maintenance of MP melon. Concentrations of up to 1.0% of CaCl2 they could be recommended to maintain the melon quality MP melon yellow inodorus (CAC).

Avaliação de diferentes tipos de atmosferas modificadas na vida útil de carambolas minimamente processadas

Este trabalho teve por objetivo a avaliação da vida útil potencial de carambolas cv. Golden Star, minimamente processadas, armazenadas em diferentes tipos de embalagens plásticas, para a concepção da atmosfera modificada. Os frutos colhidos fisiologicamente maturos apresentaram coloração verde-amarelada, sólidos solúveis (SS) médios de 6,8 ºBrix e massa média de 185 g. Antes da aplicação dos tratamentos, os frutos foram selecionados, higienizados em solução de hipoclorito de sódio (NaOCl) a 100 mg. L-1, resfriados por 12 horas a 15 ± 0,5 °C, seccionados transversalmente, sendo então novamente higienizados em solução de NaOCl a 10 mg.L-1, por 3 minutos. em seguida, os pedaços em forma de estrelas foram acondicionados em bandejas rígidas de poliestireno, com capacidade para 250 g, e revestidas com os seguintes materiais: T1: filme plástico perfurado de polietileno de baixa densidade (PEBD), de 0,006 mm; T2: filme plástico poliolefínico com antiembassamento da Dupont® (AGF), de 0,015 mm; T3: filme plástico poliolefínico da Dupont® (HF), de 0,015 mm; T4: filme plástico de PEBD, de 60 µm; T5: filme plástico de PEBD, de 80 µm; T6: filme plástico de polipropileno (PP), de 22 µm, e T7: bandeja rígida de polietileno tereftalato (PET), com capacidade para 500 mL, com tampa do mesmo material. As embalagens foram então armazenadas em câmara frigorífica a 12 ± 0,5 °C e 90 ± 3% de U.R, por 18 dias. Observou-se que não houve diferença significativa quanto aos sólidos solúveis (SS) e acidez titulável (AT). O maior número de microrganismos e valor de pH foram observados nos frutos embalados nos filmes plásticos de PEBD de 0,006 mm, AGF e HF de 0,015 mm da Dupont®. Entretanto, os frutos acondicionados nas embalagens PET apresentaram o maior teor de ácido ascórbico. da mesma forma, somente nas embalagens PET é que se conseguiu modificação atmosférica eficiente do ponto de vista da manutenção dos atributos de qualidade durante o AR. Assim, esse tratamento proporcionou adequado controle microbiológico e manutenção das características de qualidade por 18 dias para as carambolas minimamente processadas.

Radiação gama e atmosfera modificada passiva na qualidade de goiabas 'Pedro Sato'

O objetivo deste trabalho foi avaliar o efeito da irradiação gama associada à atmosfera modificada passiva na qualidade pós-colheita de goiabas 'Pedro Sato', verificando suas características físico-químicas. Foram utilizadas goiabas provenientes da região de Vista Alegre do Alto-SP,Brasil. Após a colheita, as goiabas foram imediatamente transportadas ao Laboratório de Frutas e Hortaliças, pertencente ao Departamento de Gestão e Tecnologia Agroindustrial, da Faculdade de Ciências Agronômicas - UNESP - Câmpus de Botucatu-SP, onde foram armazenadas a 10ºC e 90-95%UR, em câmara frigorífica, por 28 dias. Os tratamentos foram: controle 1 (sem embalagem e sem irradiação); controle 2 (embalagem de poliestireno (PS) + polietileno de baixa densidade (PEBD) e sem irradiação); tratamento 1 (PS+PEBD e 0,2kGy); tratamento 2 (PS+PEBD e 0,6kGy), e tratamento 3 (PS+PEBD e 1,0kGy). As análises realizadas foram: firmeza, sólidos solúveis (SS), acidez titulável (AT) e índice de maturação. Foi utilizado o delineamento inteiramente casualizado, com esquema fatorial 5 x 5 (tratamento x tempo). Concluiu-se que as altas doses de irradiação promoveram efeito negativo nas características físico-químicas da goiaba 'Pedro Sato', e que apenas a menor dose utilizada (0,2kGy) associada à atmosfera modificada conservou frutos com maior qualidade e aceitabilidade, indicado por maiores índice de maturação e teor de sólidos solúveis obtidos.

Qualidade pós-colheita de mangas, não-refrigeradas, e submetidas ao controle da ação do etileno

O presente trabalho objetivou-se na caracterização físico-química de mangas cv. Tommy Atkins e Haden, submetidas ao controle da ação do etileno, através da exposição dos frutos à ação de adsorvedores de etileno. Os frutos colhidos em estádio de fisiologicamente maturos foram embalados em filmes de polietileno de baixa densidade (PEBD) de 0,006 mm de espessura, com ou sem o sachê de adsorção de etileno, e acondicionados em embalagens de papelão (0,65 x 0,52 m), sem o controle da temperatura e da umidade relativa (30 ± 3 ºC e 70 ± 5 % de U.R.). Os tratamentos ficaram constituídos dessa maneira: T1 - mangas cv. Tommy Atkins, com o sachê de adsorção; T2 - mangas cv. Tommy Atkins, sem o sachê de adsorção; T3- mangas cv. Haden com o sachê de adsorção, e T4 - mangas cv Haden sem o sachê de adsorção. As análises de firmeza de polpa, sólidos solúveis (SS), acidez titulável (AT), pH, ácido ascórbico e concentração de etileno foram realizadas na instalação do experimento (dia 0), e aos 7; 14; 21; 28 e 35 dias; e aos 35 dias foi realizado um teste de preferência. Ao final do experimento, observou-se que, em ambas as cultivares, a menor concentração de etileno nas embalagens, a maior firmeza de polpa, a maior contenção no avanço e na diminuição do SS e AT, respectivamente, bem como a melhor manutenção do conteúdo de ácido ascórbico foram detectadas nos frutos acondicionados em embalagens contendo o sachê de adsorção de etileno. Não foram detectadas variações significativas nos valores de pH. No teste de preferência, houve variação significativa, onde os frutos acondicionados sob ação do adsorvedor de etileno foram preferidos por parte dos julgadores.