Modification Of Polyethylene Research Articles

Modification and Degradation of Polyethylene under the Action of Oxygen Plasma

The results of measurements of the rates of formation of gaseous products and the composition of functional groups in the surface layer of polyethylene upon treatment in a low-temperature dc oxygen discharge plasma are presented. Based on these data, the mechanisms of polyethylene modification and oxidative degradation are discussed.

Surface Modification of Low-Density Polyethylene by Inductively Coupled Argon Plasma

The surface chemistry and nanotopography of low-density polyethylene (LDPE) were modified by downstream, inductively coupled, radio frequency (rf) Ar plasma without inducing surface damage. The extent of surface modification was controlled by the applied ion energy fluence, determined from the plasma ion density measured with a Langmuir probe. The treated LDPE surfaces were characterized by atomic force microscope (AFM) imaging, contact angle measurements, and X-ray photoelectron spectroscopy (XPS). Analysis of AFM surface images confirmed that topography changes occurred at the nanoscale and that surface damage was insignificant. Contact angle measurements demonstrated an enhancement of the surface hydrophilicity with the increase of the plasma power. XPS results showed surface chemistry changes involving the development of different carbon-oxygen functionalities that increased the surface hydrophilicity. Physical and chemical surface modification was achieved under conditions conducive to high-density inductively coupled rf plasma.

Surface modification of polyethylene and polypropylene in atmospheric pressure glow discharge

An atmospheric pressure glow discharge (APGD) was used for surface modification of polyethylene (PE) and polypropylene (PP). The discharge was generated between two planar metal electrodes, with the top electrode covered by a glass and the bottom electrode covered by the treated polymer sample. The discharge burned in pure nitrogen or in nitrogen–hydrogen or nitrogen–ammonia mixtures. The surface properties of both treated and untreated polymers were characterized by scanning electron microscopy, atomic force microscopy, surface free energy measurements and x-ray photoelectron spectroscopy. The influence of treatment time and power input to the discharge on the surface properties of the polymers was studied. The ageing of the treated samples was investigated as well. The surface of polymers treated in an APGD was homogeneous and it had less roughness in comparison with polymer surfaces treated in a filamentary discharge. The surface free energy of treated PE obtained under optimum conditions was 54 mJ m−2 and the corresponding contact angle of water was 40°; the surface free energy of treated PP obtained under optimum conditions was 53 mJ m−2 and the contact angle of water 42°. The maximum decrease in the surface free energy during the ageing was about 10%.

Chemical and Thermal Stability of Surface‐Modified Porous Polyethylene Membranes

In this paper, we describe the surface modification of porous polyethylene by the adsorption of polyelectrolyte mutilayers on plasma‐activated polyethylene surfaces. We use the migration rates of deionized water as an effective alternative to contact angle measurements in order to probe the interfacial energy of the modified surface. The newly acquired surface properties that result from the surface modification are monitored with respect to several key chemical and environmental variables. These variables were chosen so that they will reflect some of the common handling procedures in a laboratory or health care environments, such as exposure to solvents of different pH and polarities, and fluctuations of ambient temperature over an extended period, i.e., “shelf‐life” duration. The stability of these surface properties of the modified membranes is a fundamental requirement for their potential use in a variety of applications involving lateral flow and binding media for bio‐assays. In this paper, we show that a membrane modified by a polyelectrolyte monolayer is more stable than a membrane that has undergone plasma activation alone, while a membrane modified by a polyelectrolyte bilayer exhibits retention of the enhanced surface hydrophilic properties under various conditions and over a long period of time.

Determination of the Residence Time Distribution in Twin Screw Extruders via Free Radical Modification of PE

Abstract The main objective of the present work was to introduce an inline method for measuring the residence time distribution (RTD) of twin screw extruders on the basis of information obtained from the melt free radical modification of polyethylene in a modular intermeshing co-rotating twin screw extruder. The trend of increasing rate of the extruder total torque resulted from replacing the neat polyethylene feed by a mixture of polyethylene and reactants which are chemically capable of creating chainbranching and/or crosslinking reactions was considered as the main information source for evaluating the RTD of the extruder. The RTD results were compared with those obtained from the tracer pulse input method, and good agreement was found. It was also demonstrated that, the present in-line RTD measuring technique has reliability of following the effect of feeding rate, screw speed and reactant concentration on the RTD of the twin screw extruders. It was found that, increasing the feeding rate results in decreasing the minimum residence time, and results in a narrower RTD. At constant feeding rate increasing the screw speed decreased the minimum residence time and broadened the RTD. The results also showed that, reactant concentration and variation of the viscosity along the screw have not appreciable effect on the twin screw extruders RTD.

Modyfikacja polietylenu malej gestosci allilomocznikiem

Modification of low-density polyethylene (PE-LD) with allylurea (AM) by reactive extrusion in the presence of dicumyl peroxide (DCP) as radical initiator of the expected grafting reaction has been described. Modification has been done in order to increase PE-LD susceptibility to degradation in the environment. FT-IR investigations showed the probability of the intermolecular AM condensation during processing at the conditions applied (Figs. 2, 3). The changes found should not impede the process of AM grafting. The slip of extruder screw, caused by AM, has been limited by addition of silica (K) to the composition. Composition properties have been studied in wide range of concentrations of silica (up to 8 wt. %), allylurea (up to 8 wt. %) and peroxide (up to 0.6 wt. %). The material showing good breaking strength was obtained when silica content in the composition (equal to AM content) was 3 wt. %. Gel number of various compositions was also determined. The samples obtained at small amounts of DCP, up to 0.2 wt. %, showed required low crosslinking degree (Table 1). FT-IR analysis suggests the partial grafting of allylurea onto PE chains (Table 2).

Modification of lignin–polyethylene blends with high lignin content using ethylene–vinylacetate copolymer as modifier

AbstractBlending of polyethylene with lignin in concentrations > 20 wt % yielded blends with relatively low mechanical properties. A new method, based on modification of polyethylene with ethylene–vinylacetate (EVA) copolymer, was developed for the preparation of polyethylene blends containing about 30 wt % lignin with acceptable strength properties. The addition of 10 wt % EVA caused an increase of tensile strength about twice and elongation at break about 13 times compared to those of the corresponding nonmodified samples. The optimization of lignin–polyethylene–EVA blend composition was based on a regression equation, which was obtained as output from an experimental design. The prepared composite material with 33.6 wt % lignin showed acceptable processing and mechanical properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1855–1860, 2004

Surface modification of polyethylene powder by nitrogen and ammonia low pressure plasma in a fluidized bed reactor

A combination of a fluidized bed and a low pressure plasma has been employed for the surface modification of low density polyethylene (LDPE) powders. Optical Emission Spectroscopy and Laser Doppler Anemometry has been used for the characterization of the reactor. XPS and contact angle measurements were carried out to reveal surface modification of nitrogen and ammonia plasma treatment of LDPE powders. Both nitrogen and ammonia plasma treatment show an increase of the hydrophilic character of the surface treated LDPE powders. XPS analysis shows the incorporation of new functional moieties including C–N, C–O groups on the surface of treated powders. In this configuration nitrogen plasma treatment leads to a better incorporation of nitrogen containing functional groups when compared to ammonia plasma.

Surface modification of polyethylene by plasma pretreatment and UV‐induced graft polymerization for improvement of antithrombogenicity

AbstractThe purpose of this study was to enhance blood compatibility of polyethylene (PE) films. Glycidyl methacrylate (GMA) was grafted onto the surface of PE by Ar plasma pretreatment and UV‐induced graft polymerization without photo‐initiator, then heparin was immobilized onto the poly (glycidyl methacrylate) segments. The surface compositions and microstructure of GMA graft polymerized PE films were studied by X‐ray photoelectron spectroscopy (XPS) and Attenuated Total Reflectance Fourier Transfer Infrared (ATR‐FTIR) spectroscopy. It was confirmed that heparin was successfully immobilized onto the surface of PE films by XPS analysis. The antithrombogenicity of the samples was determined by the activated partial thromboplastin time (APTT), prothrombin time (PT), thrombin time (TT), and plasma recalcification time (PRT) tests and platelet adhesion experiment. Results indicated that the antithrombogenicity of modified PE was improved remarkably. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2014–2018, 2004

Plasma surface modification of polystyrene and polyethylene

Polystyrene (PS) and polyethylene (PE) samples were treated with argon and oxygen plasmas. Microwave electron cyclotron resonance (ECR) was used to generate the argon and oxygen plasmas and these plasmas were used to modify the surface of the polymers. The samples were processed at different microwave powers and treatment time and the surface modification of the polymer was evaluated by measuring the water contact angle of the samples before and after the modification. Decrease in the contact angle was observed with the increase in the microwave power for both polystyrene and polyethylene. Plasma parameters were assessed using Langmuir probe measurements. Fourier transform infrared spectroscopy showed the evidence for the induction of oxygen-based functional groups in both polyethylene and polystyrene when treated with the oxygen plasma. Argon treatment of the polymers showed improvement in the wettability which is attributed to the process called as CASING, on the other hand the oxygen plasma treatment of the polymers showed surface functionalization. Correlation between the plasma parameters and the surface modification of the polymer is also discussed.

Photo-immobilization of a phospholipid polymer for surface modification

A photo-reactive polymer having a phospholipid polar group was prepared, and the polymer was photo-immobilized on polymeric surfaces, where its interactions with biocomponents were investigated. By using a photo-immobilization method, the polymer was used for surface modification of polyethylene and polypropylene, polymers whose surfaces were not treated in our previous development of the phosphorylcholine-derived polymer. The photo-reactive polymer was synthesized by a coupling reaction involving copolymer consisting of 2-methacryloyloxyethyl phosphorylcholine and methacrylic acid with 4-azidoaniline. When the polymer was unpattern immobilized on the surface, X-ray photo-electron spectroscopic analysis and static contact angle measurements were performed. It was shown that the surface was covered with phospholipid polar groups. Micropattern immobilization was carried out using a micropatterned photo-mask. Measurements using atomic force microscopy showed that the swelled micropatterned polymer was five times as thick as the dried one. Protein adsorption and platelet adhesion were reduced on the polymer-immobilized regions. Mammalian cells did not adhere, and formed aggregates on the immobilized regions. In conclusion, the photo-reactive phospholipid polymer was covalently immobilized on the conventional polymer surfaces and it tended to reduce interactions with proteins and cells.

Effect of surface modification of high-density polyethylene by direct current and radio frequency glow discharge on wetting and adhesion characteristics

The present investigation aims to optimize the process parameters of Direct Current (DC) and Radio Frequency (RF) glow discharge treatment through air in terms of discharge power and time of exposure for the surface modification of high-density polyethylene (HDPE) sheet, for attaining best adhesive joint of the polymer to mild steel. In order to estimate the extent of surface modification, the surface energies of the polymer surfaces exposed to glow discharge have been determined by measuring contact angles using two standard test liquids of known surface energies. It is observed that at a given power level of DC glow discharge, surface energy and its polar component increase with increasing exposure time, attaining a maximum and then decreasing. In the case of RF glow discharge, surface energy and its polar component increase with increasing exposure time and then saturate. Surface modification by DC glow discharge increases the surface energy of HDPE relatively more at a lower power compared to that observed for RF glow discharge. The dispersion component of surface energy remains almost unaffected. The surfaces have also been studied by electron spectroscopy for chemical analysis (ESCA) and energy-dispersive spectra (EDS). A significant oxygen peak is observed for surface-modified polymer as detected by ESCA and EDS. Lap shear tensile test of an adhesive (Araldite AY 105) joint of HDPE with mild steel has been carried out in optimizing the parameters of DC and RF glow discharge for maximum joint strength. When HDPE is exposed to DC glow discharge, improvement of adhesive joint strength of HDPE to mild steel is found to be by a factor more than 7. On the other hand, when HDPE is exposed to RF glow discharge, results in improvement of adhesive joint strength of HDPE to mild steel by a factor nearer to 7 are found. Thus, DC glow discharge is more capable for increasing wetting and adhesion characteristics of the polymer.

Synthesis and tensile properties of a novel composite of Chlorella and polyethylene

AbstractA novel composite of the green microalga Chlorella sp. with polyethylene (PE) was synthesized through chemical modification of PE with maleic anhydride (MA), with respect to the biological fixation of CO2 with Chlorella sp. The interaction of Chlorella grains with a PE matrix is strikingly enhanced by the chemical modification of PE with MA. The tensile strength of a Chlorella–MA‐modified PE composite (Ch–MPE) with a Chlorella content of 40 wt % is more than 2 times greater than that of a composite derived from unmodified PE. The marked increase in tensile strength is attributed to the formation of chemical bonds between Chlorella grains and the PE matrix, from IR and SEM studies. Because of the satisfactory thermal plasticity of Ch–MPE, it can be easily shaped into plate and dishlike moldings by a heat‐pressurizing method. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 812–816, 2004

Use of the affinity chromatography principle in creating new thromboresistant materials

The principle of affinity chromatography was used for preparation of thromboresistant bilayer coatings. The outer biospecific layer containing ε-aminocaproic acid residues (from 2.2 up to 5.5 nmol/cm 2) was synthesized using a copolymer of maleic anhydride with N-vinylpyrrolidone and l-lysine dihydrochloride or N-ε- tert-BOC- l-lysine. This surface can selectively adsorb plasminogen (fibrinolytic zymogen) from blood. The biospecific layer (from 2.0 up to 3.6 μg/cm 2) was applied for covering chitosan (native or modified) or albumin interlayer. Such bilayer coatings (BCs) were stable and represented the insoluble polyelectrolyte complexes. BCs were proposed for bilayer modification of synthetic vascular grafts, polyethylene, and other materials contacting with blood. This technique allowed us to significantly reduce thrombogenic properties of polyethylene surfaces.

Plasma surface modification of polyethylene

Oxidative (oxygen and air) RF-plasma treatment of HDPE was found as an effective tool for improving wettability, as well as for increasing its surface micro-hardness. The latter plasmas generate wide range of reactive species in the system, which undergo consecutive chemical reactions, creating thus several oxygen based functionalities at the interface (carbonyl, carboxyl, ether, peroxide etc.) as were detected by ATR FTIR and XPS analysis. An increased negative surface charge of plasma treated polyethylene (PE) confirms the presence of functional ionogenic groups containing oxygen. Simultaneously, the vigorous increase of the surface roughness was found as a result of the successful plasma etching.

Modification of polyethylene–octene elastomer by silica through a sol–gel process

AbstractIn this study, tetraethoxysilane (TEOS) and a metallocene polyethylene–octene elastomer (POE) were chosen as the ceramic precursor and the continuous phase, respectively, for the preparation of new hybrids by an in situ sol–gel process. To obtain a better hybrid, a maleic anhydride‐grafted polyethylene–octene elastomer (POE‐g‐MAH), used as the continuous phase, was also investigated. Characterizations of POE‐g‐MAH/SiO2 and POE/SiO2 hybrids were performed by Fourier transform infrared (FTIR) and 29Si solid‐state nuclear magnetic resonance (NMR) spectrometers, a differential scanning calorimeter (DSC), a thermogravimetry analyzer, and an Instron mechanical tester. The results showed that the POE‐g‐MAH/SiO2 hybrid could improve the properties of the POE/SiO2 hybrid because the interfacial force between the polymer matrix and the silica network was changed from hydrogen bonds into covalent SiOC bonds through dehydration of hydroxy groups in POE‐g‐MAH with residual silanol groups in the silica network. The existence of covalent SiOC bonds was proved by FTIR spectra. For the POE/SiO2 and POE‐g‐MAH/SiO2 hybrids, maximum values of the tensile strength and the glass transition temperature were found at 9 wt % SiO2 since a limited content of silica might be linked with the polymer chains through the covalent bond. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 966–972, 2003

Neural differentiation of midbrain cells on various protein-immobilized polyethylene films.

The effect of surface modification of polyethylene (PE) film on differentiation of midbrain (MB) cells obtained from rat embryos was determined by their micromass culture system. When cultured on untreated PE film, cell differentiation was suppressed to approximately two-thirds of that observed in a control culture dish. On the contrary, type I collagen-immobilized PE film increased differentiated foci of the MB cells more than did the untreated PE film. RGDS (Arg-Gly-Asp-Ser) peptide immobilization onto PE film resulted in almost the same differentiation activity as the collagen immobilized PE film. Bovine serum albumin (BSA) immobilization onto PE film enhance the differentiation activity more than did the untreated PE film, but not up to the levels of collagen- and RGDS-immobilized PE. The number of differentiated foci of the MB cells on untreated PE film were increased by the addition of the condition medium prepared from the collagen-immobilized PE film. However, the number of foci was not increased by the addition of other condition media obtained from control dish, untreated, BSA-, and RGDS-immobilized PE. On the other hand, none of these condition media enhanced a differentiation of the neuronal cell line of PC12 cells, suggesting that some factors effectively differentiate midbrain cells, composed of neuronal epithelial and mesenchymal cells, but not the PC12 cells secreted in the condition media prepared from collagen-immobilized PE. In addition, it is probable that neural growth factor was not secreted in these condition media, which could not induce the differentiation of PC12 cells.

A Comparison of PE Surfaces Modified by Plasma Generated Neutral Nitrogen Species and Nitrogen Ions

The surface modification of polyethylene (PE) by neutral nitrogen species (ground and excited state N2 as well as atomic N; modified nitrogen plasma treatment) has been compared to the effect of nitrogen ion bombardment using X-ray Photoelectron Spectroscopy (XPS) and contact angle measurements. XPS results indicate that a greater nitrogen concentration was grafted during the modified nitrogen plasma treatment of PE, an effect that was attributed to surface sputtering during ion beam modification. The distribution of nitrogen-containing functionalities was strongly dependent upon the treatment strategy; the modified nitrogen plasma treatment lead predominantly to imine groups being formed at the PE surface, while amine groups were the dominant species produced during ion beam modification. The presence of electron irradiation during the modified nitrogen plasma treatment of PE did not modify the rate of nitrogen incorporation or change the nature of N-containing functional groups produced but did lead to a systematic decrease in contact angle.

Chemical modification of molten polyethylene by thermal decomposition of peroxyesters

The functionalization of polyethylene was realized by the thermal decomposition of peroxyesters in molten polymer in the absence of any other additive. Ester and acid functions were introduced onto the polymer operating with various peroxyesters. This grafting resulted from the combination of a polymer radical, generated in the abstraction of a hydrogen from polyethylene by an alkoxy radical, with an acyloxy or carbon-centered radical arising from the perester. A complete methodology was set up to identify and to titrate the functions present onto the polyethylene and to determine the extent of crosslinked polymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 699–707, 2003

A study on ultraviolet irradiation modification of high-density polyethylene and its effect in the compatibility of HDPE/PVA fibre composites

Oxygen-containing groups such as C–O, CO and C(O)O were introduced onto the molecular chain of high-density polyethylene (HDPE) by ultraviolet irradiation in air. The content of these groups increases with irradiation time. After irradiation, the molecular weight and melting temperature of HDPE decrease, and the degree of crystallinity and hydrophilicity increase. Adding a small amount of irradiated HDPE to the HDPE/polyvinyl alcohol (PVA) fibre composites can improve their mechanical properties. Compared with that of HDPE/PVA fibre (85/15) composite, the yield and impact strength of HDPE/PVA fibre (75/15) composites made compatible with 10% wt. of HDPE irradiated for 48 h are increased from 32.6 MPa and 480 J/m to 40.5 MPa and 532 J/m, respectively.