Properties of Isotactic Polypropylene Irradiated in Various Atmospheres

In this paper, changes in structure and physical properties of stabilized isotactic polypropylene (iPP) were created by gamma irradiation, up to a dose of 700 kGy, in different media: air, deionized distilled (DD) water and acetylene. Two main effects occur when polyolefins, such as iPP, are subjected to ionizing radiation: crosslinking and scission of macromolecules. The domination of one or the other of these competitive processes is determined by both the structural peculiarities of the polymers and the experimental irradiation conditions. Gel and infrared (IR) spectroscopy measurements were used to determine the changes in the degree of network formation and oxidative degradation, respectively. Sol gel analysis was studied in detail using the Charlesby-Pinner (C-P) equation. The radiation-induced changes in the structure and evolution of oxygen-containing species were also studied through dielectric loss (tan delta) analysis in a wide temperature and/or frequency range. Evolution of low temperature dielectric relaxations with gamma irradiation was investigated. The results showed that degradation was the major reaction in the initial step of irradiation, no matter what the atmosphere was. The C-P equation seemed applicable when stabilized iPP was irradiated within a certain dose range in various atmospheres. The iPP irradiated in acetylene/air had the lowest/highest values for oxidation level, dielectric losses, D(g) and G(s)/G(x) values. The calculated D(g) values are 1.5 and 5 times larger for the irradiation in DD water and air than for the acetylene. Furthermore, our data confirm that oxidation strongly affects the gel point but has a much lower effect on the G(s)/G(x) ratio. In the case of dielectric relaxation measurements, the connection between the oxidative degradation and dielectric properties is well established and is in good agreement with IR spectroscopy measurements. The amount of carbonyl, hydroperoxide and other polar groups is much higher for the irradiation in air than in other media, leading to higher dielectric losses. Disappearance of low temperature (delta and gamma) relaxations with gamma radiation confirmed great sensitivity of iPP structure to radiation-induced changes. Complete vanishing of the gamma relaxation in iPP samples irradiated in air is connected with a large radiation-induced oxidative degradation in this medium. Similar crosslinking, oxidation and dielectric behaviour was observed for the samples irradiated in water and acetylene, indicating DD water as a good crosslinking medium

Structure and characteristics of the hot pressed hydroxyapatite/poly-L-lactide composite

Hydroxyapatite/poly-L-lactide (HAp/PLL) composite biomaterial can be obtained by different processing methods. Three-dimensional blocks of HAp/PLLA composite biomaterial with mechanical characteristics close to the natural bone tissue can be obtained by hot pressing procedure. Effects of synthesis and compacting on the structure and characteristics of the HAp/PLLA composite biomaterial were studied in this work. Using wade angle X-ray structural analyses (WAXS), differentially scanning calorimetry (DSC), thermogravimetric analysis (TGA) and infrared (IR) spectroscopy, the changes occurring in the material during synthesis and hot pressing were monitored. Surface microstructure was analyzed by scanning electronic microscopy (SEM) coupled with electron-dispersion analysis (EDX). The results obtained indicate a possible decrease in the degree of crystallinity with hot pressing time increase. A block of HAp/PLLA composite biomaterial with 1.6 times lower crystallinity of the polymer phase was obtained by hot pressing in a given time interval with a maximum of 60 minutes. Results of TG analysis show that PLLA stability decreases with increasing hot pressing time, and vice versa. IR study proved that neither destructive changes in constituents nor formation of new phases occurred during hot pressing

Swelling, Mechanical and Antimicrobial Studies of Ag/P(HEMA/IA)/PVP Semi-IPN Hybrid Hydrogels

A simple and fast approach to the design and production of new hybrid polymeric biomaterials with silver particles is presented in this work. Silver/semi-interpenetrating network hybrid hydrogels (Ag/semi-IPNHHs) were prepared through an optimized solution crosslinking copolymerization of 2-hydroxyethyl methacrylate (HEMA) and itaconic acid (IA), in the presence of PVP, a silver salt and a reducing green agent (Ag/P(HEMA/IA)/PVP). PVP was chosen due to its protective, reduction, and nucleation properties in the production of metal particles. The structure of the Ag/semi-IPNHH was characterized by Fourier transform infrared spectroscopy (FTIR). The presence of silver and PVP in the network was confirmed by FTIR spectra. The results obtained by dynamic mechanical analysis (DMA) showed good mechanical properties for all samples. The swelling studies of Ag/P(HEMA/IA)/PVP were conducted in the temperature range of 25-55 degrees C, in the buffer of pH 7.40. The Ag/semi-IPNHH showed temperature-sensitive swelling properties, with the lower critical solution temperature (LCST) values in the physiologically interesting interval. The antimicrobial activity of the samples was tested using E. coli, S. aureus and C. albicans pathogens. It was concluded that the antimicrobial potential depends on the hydrogels composition and the type of microbes12th Annual YUCOMAT Conference, Sep 06-10, 2010, Herceg Novi, Montenegr

Dielectric study of post-irradiation effects in gamma-irradiated polyethylenes

The post-irradiation dielectric behaviour of different polyethylenes (PEs) has been studied by means of dielectric loss (tan 5) analysis over the wide temperature (25-325 K) and frequency (1 kHz-1 MHz) ranges. For this reason, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) samples were previously gamma irradiated in air to absorbed dose of 300 kGy. The irradiated samples were divided into two groups, and for the first one annealing treatment which can substantially reduce the concentration of free radicals were employed. For the second group, e.g. samples stored in air at room temperature after irradiation, post-irradiation evolution in free radical concentration, dielectric relaxation spectra and carbonyl content was investigated as a function of storage time, up to 90 days. Dielectric relaxation behaviour is related to differences in the initial structures of PEs (such as branching, crystallinity, etc.) and to the radiation-induced effects: carbonyl groups that were introduced by irradiation and/or delayed (post-irradiation) oxidation were regarded as tracer groups. Electron spin resonance (ESR), differential scanning calorimetry (DSC), infrared (IR) spectroscopy and gel measurements were used to determine the changes in free radical concentration, crystal fraction, oxidation and degree of network formation, respectively. (C) 2010 Elsevier Ltd. All rights reserved

Dielectric studies of molecular beta-relaxation in low density polyethylene: the influence of drawing and ionizing radiation

The dielectric relaxation behavior of low density polyethylene, uniaxially oriented to different draw ratios (3, 7 and 10) and irradiated to different absorbed doses (100, 200, 300, 500 and 700 kGy) of gamma radiation was investigated. Molecular relaxation was studied through dielectric loss (tan delta) analysis, in the temperature range from 25 to 335 K, at several different frequencies ranging from 10(3) to 10(6) Hz. The beta-relaxation was resolved from the gamma by curve fitting and its parameters were determined. Its intensity, position and activation energy were found to be strongly dependent upon the changes in microstructure of the amorphous domain induced by orientation and irradiation. Since the dielectric relaxation processes are very sensitive to prior structure of the samples, we also used differential scanning calorimetry, IR spectroscopy and gel measurements to determine the changes in crystal fraction, oxidative degradation and degree of network formation, respectively. Conclusions derived according to these methods were compared with changes in intensity, position and activation energy of the molecular beta-relaxation detected by dielectric relaxation measurements. (C) 2002 Published by Elsevier Science Ltd

Gel production, oxidative degradation and dielectric properties of isotactic polypropylene irradiated under various atmospheres

In this work, changes in structure and physical properties of stabilized isotactic polypropylene (iPP) were created by gamma irradiation, up to a dose of 700 kGy, in different media: air, deionised distilled (DD) water and acetylene. Gel and infrared (IR) spectroscopy measurements were used to determine the changes in the degree of network formation and oxidative degradation, respectively. Sol-gel analysis was studied in detail using the Charlesby-Pinner (C-P) equation. The radiation-induced changes in the structure and evolution of oxygen-containing species were also studied through dielectric loss (tan delta) analysis in a wide temperature and/or frequency range. Evolution of low temperature dielectric relaxations with gamma irradiation was investigated. In the case of dielectric relaxation measurements, the polar groups that were introduced by irradiation in non-polar iPP were considered as tracer groups. Conclusions derived according to different methods were compared. (c) 2009 Elsevier Ltd. All rights reserved

The influence of molecular orientation on the crosslinking/oxidative behaviour of iPP exposed to gamma radiation

This paper presents a study of the influence of structural peculiarities, uniaxial orientation and fibrillar structure on the radiation-induced changes in iPP. For the purposes of this study, iPP was oriented via solid-state stretching at elevated temperature to various draw ratios and, later on, gamma irradiated in air. In order to investigate orientation- and/or radiation-induced structural changes, optical microscopy (OM), scanning electron microscopy (SEM), wide angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), infrared spectroscopy (IR) and gel measurements were employed. To quantify the degree of molecular orientation, Hermans orientation function (f(c)), was used. IR spectroscopy and gel measurements were used to determine the changes in the oxidative degradation and degree of network formation, respectively. Sol-gel analysis was studied in detail using the Charlesby-Pinner (C-P) equation. The radiation-induced changes in the structure and evolution of oxygen-containing species were also studied through dielectric loss (tan delta) analysis in a wide frequency range; the polar groups that were introduced by irradiation in apolar iPP were considered as tracer groups. Conclusions derived according to different methods were compared. Presented results reveal two different radiation-induced dynamics; gamma irradiation of initial and fully developed fibrillar iPP structures leads to significantly different crosslinking and/or oxidation response. (C) 2009 Elsevier Ltd. All rights reserved

Post-irradiation effects in polyethylenes irradiated under various atmospheres

If a large amount of polymer free radicals remain trapped after irradiation of polymers, the post-irradiation effects may result in a significant alteration of physical properties during long-term shelf storage and use. In the case of polyethylenes (PEs) some failures are attributed to the post-irradiation oxidative degradation initiated by the reaction of residual free radicals (mainly trapped in crystal phase) with oxygen. Oxidation products such as carbonyl groups act as deep traps and introduce changes in carrier mobility and significant deterioration in the PEs electrical insulating properties. The post-irradiation behaviour of three different PEs, low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and high density polyethylene (HDPE) was studied; previously, the post-irradiation behaviour of the PEs was investigated after the irradiation in air (Suljovrujic, 2010). In this paper, in order to investigate the influence of different irradiation media on the post-irradiation behaviour, the samples were irradiated in air and nitrogen gas, to an absorbed dose of 300 kGy. The annealing treatment of irradiated PEs, which can substantially reduce the concentration of free radicals, is used in this study, too. Dielectric relaxation behaviour is related to the difference in the initial structure of PEs (such as branching, crystallinity etc.), to the changes induced by irradiation in different media and to the post-irradiation changes induced by storage of the samples in air. Electron spin resonance (ESR), differential scanning calorimetry (DSC), infra-red (IR) spectroscopy and gel measurements were used to determine the changes in the free radical concentration, crystal fraction, oxidation and degree of network formation, respectively. (C) 2013 Elsevier Ltd. All rights reserved

Complete relaxation map of polypropylene: radiation-induced modification as dielectric probe

The molecular relaxation behaviour of isotactic polypropylene (iPP) exposed to gamma radiation in air to various absorbed doses (up to 700 kGy) has been investigated by dielectric loss (tan delta) analysis; the polar (mainly carbonyl and hydroperoxide) groups that were introduced by radiation-induced oxidation were considered as tracer groups. All relaxation zones (alpha, beta, gamma and delta in the order of decreasing temperature), between 25 K and melting temperature, were studied in the frequency range from 1 kHz to 1 MHz. The changes observed in the dielectric relaxation spectra were related to the modifications in the structural and morphological parameters attributed to exposure of the iPP samples to radiation. Wide-angle X-ray diffraction was used to investigate radiation-induced changes in the crystalline structure and degree of crystallinity, since the alpha relaxation is connected with this phase. Infrared spectroscopy and gel measurements were used to determine the changes in the oxidative degradation and the degree of network formation, respectively. Conclusions derived using different methods were compared. This study reveals high dielectric and/or relaxation sensitivity of iPP to gamma radiation. Disappearance of the low-temperature dielectric (gamma and delta) relaxations together with large changes in intensity, position and activation energy of the dielectric alpha relaxation are observed with gamma irradiation and are mainly connected with oxidative degradation in iPP structure

A dielectric study of molecular relaxations in irradiated high density polyethylene

The molecular relaxation behaviour of high density polyethylene (HDPE), exposed to gamma radiation in air to various absorbed doses (up to 700 kGy), has been investigated by dielectric loss (tan delta) analysis. All relaxation zones (gamma, beta and alpha, in order of increasing temperature), between 25 K and the melt temperature, were studied in the frequency range from 1 kHz to 1 MHz. The changes observed in the dielectric relaxation spectra were related to the modifications in the structural and morphological parameters attributed to exposure of the samples to radiation. Radiation-induced changes in the crystal fraction, oxidative degradation and degree of network formation, observed by wide angle X-ray scattering (WAXS), differential scanning calorimetry (DSC), infrared spectroscopy (IR) and gel measurements, were well connected with the changes in intensity, position and activation energy of alpha and gamma relaxations. Complete disappearance of the already weak beta relaxation with irradiation is attributed to the more restricted chain segment mobility in the net Structure, but the contribution due to radiation-induced increase in crystallinity should also be taken into account. (C) 2009 Elsevier Ltd. All rights reserved