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.

Combination of nickel and titanium complexes containing nitrogen ligands as catalyst for polyethylene reactor blending

Ethylene was polymerized using a combination of Ni(diimine)Cl-2 (1) (diimine = 1,4-bis(2,6-di-isopropylphenyl)-acenaphthenediimine) and {Tp(Ms)*} TiCl3 (2) (Tp(Ms)* = hydridobis(3-mesitylpyrazol-1-yl)(5-mesityl-pyrazol-1-yl)) compounds in the presence of methyl-aluminoxane (MAO) at 30 degrees C. The productivity reaches a maximum at X-Ni = 0.75 (1400 kg of PE/mol[M] . h), and the produced polyethylene (PE) showed maximal melt flow index (0.13 g/10 min) and minimal intrinsic viscosity (2.24 dL/g) compared to polyethylenes obtained with different values of nickel loading fractions (X-Ni). Productivity intrinsic viscosity data, as well as melt flow index measurements markedly depend upon the content of the late transition metal, thus suggesting a synergic effect between nickel and titanium catalysts.

Role of polyethylene-graft-glycidyl methacrylate compatibilizer on the biodegradation of poly(epsilon-calprolactone)/cellulose acetate blends

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Gelatinous polyethylene in the treatment of the anophthalmic cavity

PURPOSE: Gelatinous polyethylene (GP) has been used as an orbital implant to evaluate volume maintenance and tissue reaction in the anophthalmic socket in a rabbit model. METHODS: Twenty-eight Norfolk white rabbits underwent unilateral evisceration with placement of 2ml GP (GP group - 16 animals) or 2ml 0.9% sodium chloride solution (Control group - 12 animals). Animal behavior, postoperative tissue response and socket conditions were evaluated. The animals were sacrificed at 7, 15, 30 and 60 days after the surgery and the bulbs were enucleated; volume maintenance and histopathological evaluation were done in the enucleated bulbs. The results were submitted to statistical analysis. RESULTS: All animals showed normal behavior. The orbital volume maintenance was better in the GP group. Histopathology in the GP animals showed mild tissue inflammation throughout the evaluation period and a thin pseudocapsule formation surrounding the orbital implant material. CONCLUSION: The clinical findings, good orbital volume maintenance and mild inflammatory tissue response make GP a good choice to replace the lack of volume in anophthalmic socket reconstruction.

Dielectric and viscoelastic properties of cross-linked polyethylene aged under multi stressing conditions

Different measurements were performed in cross-linked polyethylene (XLPE) employed as insulating material in coaxial cables that were field-aged and laboratory-aged under multi-stressing conditions at room temperature. Samples were peeled from the XLPE cable insulation in three different positions: just below the external semiconductor layer (outer layer), in the middle (middle layer) and just above the internal semiconductor layer of the cable (inner layer). The imaginary part of the electric susceptibility showed three peaks that obey the Dissado-Hill model. For laboratory-aged XLPE samples peeled from the inner and from the middle positions the peak at very low frequency region increased while in samples from the outer position a quasi-DC conduction process was observed. In medium frequency range a broadening of the peak was observed for all samples. Viscoelastic properties determined through dynamic mechanical analysis suggested that the aging generates processes that promoted changes of the crystallinity and the cross-linking degrees of the polymer. Fourier transform infrared spectroscopy (FTIR) measurements revealed an increase of oxidation products (esters), evidence of polar residues of the bow-tie tree and the presence of cross-linking by-products (acetophenone). Optical and scanning electronic microscope (SEM) measurements in aged samples revealed the existence of voids and bow-tie trees that were formed during aging in the middle region of the cable.

Porous polyethylene for tissue engineering applications in diabetic rats treated with calcitonin: Histomorphometric analysis

Purpose: The purpose of this work was to study the bone tissue reaction after porous polyethylene (Polipore) implantation into surgical defects in the parietal bones of rats with streptozotocin-induced diabetes, treated with salmon calcitonin. Materials and Methods: Porous polyethylene implants were placed in bone defects created in 36 adult female rats. The rats were divided into 3 equal groups: diabetic treated with calcitonin (DCa), diabetic (D), and control (C). The animals of the DCa group received applications of salmon calcitonin on alternating days immediately after the surgery until sacrifice. The rats were sacrificed after 15, 30, 60, and 90 days, and the defects were examined histologically and statistically through histomorphometric analysis. Results: Histomorphometric analysis showed that there was no statistically significant difference in the mean quantity of inflammatory cells among all study groups after 15 and 90 days. At 30 days, a statistically significant difference was observed between the D and C groups and the D and DCa groups. At 60 days, there was no statistically significant difference between the D and DCa groups. Discussion: Porous polyethylene can be considered an option for implant material when there are investigations that prove its biocompatibility and stability in the host tissues. Salmon calcitonin positively aided the bone repair and attenuated the inflammatory response until 30 days after the surgery. Conclusion: Porous polyethylene was tolerated by the host tissues in all groups, and moderate chronic inflammatory reaction was observed up to the 90-day period. Salmon calcitonin attenuated the inflammatory response up until 30 days.

Production of four cultivars of iceberg lettuce, under protected cultivation, with and without black polyethylene ground cover

The aim of the work was to evaluate the performance of four cultivars of iceberg lettuce, in a greenhouse, with and without ground cover. The experimental design adopted was that of subdivided parcels, where parcels were provided with and without ground cover consisting of black polyethylene and the subparcels consisted of the cultivars. There were three repetitions per treatment and six central plants of each parcel were evaluated. Drip irrigation was utilized. The cultivars studied were: 'Laurel', 'AF-389', 'Mayara' and 'Tainá'. The seeds were planted in Styrofoam trays with 288 cells containing the substrate Plantmax Hortaliças® A. The trays were kept in a greenhouse until transplanting, 25 days after seeding. The parameters examined were: fresh weight of the aerial part per plant, longitudinal (DL) and transverse (DT) diameters of the head, height of the plant and mean number of leaves per plant. Only among the cultivars there were significant differences in transverse and longitudinal diameters of the head and height of the plant. No significant interactions were detected between ground cover and cultivars. With regard to longitudinal and transverse diameters, 'AF-839' (DL = 27.11 cm; DT = 24.53 cm) showed smaller diameters than those of 'Laurel' (DL = 31.13 cm; DT = 30.55 cm), but did not differ from the other cultivars. In regard to height of the plants, 'Laurel' (20.66 cm) had the greatest value and 'AF-839' (16.02 cm) the lowest. The cultivars did not differ with respect to mean number of leaves and fresh weight of the aerial part of the plant. It is concluded that there were no significant differences in the cultivation of the iceberg lettuce with and without ground cover. The cultivar 'Laurel' stood out with respect to longitudinal and transverse diameters and height of the plant, only differing from the 'AF-839' with regard to the diameters.

Polyethylene gel in the subcutaneous tissue of rats: Histopathologic and systemic evaluation

Purpose: To evaluate the histological and systemic response to subcutaneous injection of polyethylene gel in rats. Methods: Twenty-one white male rats were divided into 3 groups (G): G1 and G2 received subcutaneous polyethylene gel injection in the dorsal midline and were sacrificed at 30 and 60 postoperative days, respectively. G3 was not exposed to the polyethylene gel and was sacrificed after 60 days. Blood levels of lactate dehydrogenase (LDH), creatine kinase (CK), and alkaline phosphatase (ALP) were evaluated. The heart, kidney, liver, adrenal gland, injection site, and adjacent tissues were histologically examined. The results were submitted to statistical analysis. Results: There was no clinical evidence of extrusion, reduction of the injected volume, or abnormalities in the adjacent tissues. Blood levels of CK and LDH were normal and similar in all groups. ALP levels were significantly lower in G2 than in G1 and G3. The systemic organs were normal on histological examination in the 3 groups evaluated. Microscopically, the polyethylene gel was surrounded by a thin pseudocapsule formation and minimal inflammatory cell response, which decreased from G1 to G2. Conclusion: The subcutaneous injection of polyethylene gel in rats elicited minimal local inflammatory response and no systemic side effects. Copyright © 2008 Informa Healthcare USA, Inc.

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.

Solid-state hydrolysis of postconsumer polyethylene terephthalate after plasma treatment

Plasma treatments were applied on the surface of postconsumer polyethylene terephthalate (PET) bottles to increase their wettability and hasten the subsequent hydrolysis process. Sixty-four treatments were tested by varying plasma composition (oxygen and air), power (25-130 W), pressure (50-200 mTorr), and time (1 and 5 min). The best treatment was the one applied in air plasma at 130 W and 50 mTorr for 5 min, as it provided the lowest contact angle, 9.4°. Samples of PET before and after the optimized plasma condition were subjected to hydrolysis at 205°C. Although the treatment changed only a thin surface layer, its influence was evident up to relatively high conversion rates, as the treated samples presented more than 40% higher conversion rates than the untreated ones after 2 h of reaction. Infrared spectroscopy showed that the terephthalic acid obtained from 99% of depolymerization was similar to the commercial product used in PET synthesis. © 2012 Wiley Periodicals, Inc.

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

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

Evaluation of Meteorological Elements and Lettuce (lactuca Sativa, L.) Yield Related to Geographic Orientation of Polyethylene Greenhouses

O experimento foi realizado na área experimental do Departamento de Engenharia Rural da Faculdade de Ciências Agronômicas – Unesp/Botucatu, Estado de São Paulo, em duas estufas dispostas em diferentes orientações geográficas, Leste/Oeste e Norte/Sul. A alface (Lactuva sativa L.) cv. Elisa foi cultivada em ambas estufas, sendo semeada em 05/05/99, transplantada em 29/05/99 e colhida em 31/06/99. Utilizou-se tensiômetros para monitorar o potencial de água no solo para realizar o manejo do sistema de irrigação por gotejamento. Microevaporímetros eqüidistantes de 3 m e colocados em 3 alturas, 0.50, 1.00 e 1.50 m, termohigrógrafos e tanques Classe “A” foram instalados nas duas estufas. Através de análise geoestatística, não se observou dependência espacial nem variabilidade espacial da evaporação nas duas estufas. Entretanto, a altura dos evaporímetros apresentou diferenças significativas: a evaporação à altura de 1.50 foi menor que nas outras duas.As médias de temperatura, umidade relativa e déficit de pressão de vapor do arnão diferiram estatisticamente entre as estufas e o ambiente externo. Os valores médios de evaporação de água no tanque Classe A instalado fora das estufas diferiram estatisticamente quando comparados com os instalados no interior das estufas, porém, entre as orientações não se constatou diferença significativa. Pôde-se verificar que não houve diferença significativa das características agronômicas da alface em ambas orientações estudadas. No entanto, houve diferença significativa para essas características entre os canteiros no interior das mesmas, havendo variância espacial para os dados de matéria fresca apenas na estufa N/S.

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.