Kinetics of sono-photooxidative degradation of poly(alkyl methacrylate)s

The mechano-chemical degradation of poly(methyl methacrylate) (PMMA), poly(ethyl methacrylate) (PEMA) and poly(n-butyl methacrylate) (PBMA) using ultrasound (US), ultraviolet (UV) radiation and a photoinitiator (benzoin) has been investigated. The degradation of the polymers was monitored using the reduction in number average molecular weight (M-n) and polydispersity (PDI). A degradation mechanism that included the decomposition of the initiator, generation of polymer radicals by the hydrogen abstraction of initiator radicals, reversible chain transfer between stable polymer and polymer radicals was proposed. The mechanism assumed mid-point chain scission due to US and random scission due to UV radiation. A series of experiments with different initial M-n of the polymers were performed and the results indicated that, irrespective of the initial PDI, the PDI during the sono-photooxidative degradation evolved to a steady state value of 1.6 +/- 0.05 for all the polymers. This steady state evolution of PDI was successfully predicted by the continuous distribution kinetics model. The rate coefficients of polymer scission due to US and UV exhibited a linear increase and decrease with the size of the alkyl group of the poly(alkyl methacrylate)s, respectively. (C) 2010 Elsevier B.V. All rights reserved.

Thermal expansion of irradiated nylon-6 from 10 K to 340 K

Thermal expansion of irradiated nylon-6 has been studied in the temperature range 10 to 340 K using a three-terminal capacitance bridge technique. Irradiation is carried out using cobalt-60 gamma-rays up to 500 Mrad dosage. Radiation enhances chain scission over crosslinking. alpha increases from 0 to 250 Mrad between 10 to 340 K and not much variation is observed between 250 to 500 Mrad for samples from 10 to 250 K.

Continuous distribution kinetics for the thermal degradation of LDPE in solution

Polymer degradation in solution has several advantages over melt pyrolysis, The degradation of low-density polyethylene (LDPE) occurs at much lower temperatures in solution (280-360degreesC) than in conventional melt pyrolysis (400-450degreesC). The thermal degradation kinetics of LDPE in solution was investigated in this work. LDPE was dissolved in liquid paraffin and degraded for 3 h at various temperatures (280-360degreesC). Samples were taken at specific times and analyzed with high-pressure liquid chromatography/gel permeation chromatography for the molecular weight distribution (MWD), The time evolution of the MWD was modeled with continuous distribution kinetics. Data indicated that LDPE followed random-chain-scission degradation. The rapid initial drop in molecular weight, observed up to 45 min, was attributed to the presence of weak links in the polymer. The rate coefficients for the breakage of weak and strong links were determined, and the corresponding average activation energies were calculated to be 88 and 24 kJ/mol, respectively. (C) 2002 John Wiley Sons, Inc.

Thermal degradation studies of para-substituted poly(styrene peroxide)s

The thermal degradation of a series of para-substituted poly(styrene peroxide)s with electron-donating [CH3, C(CH3)(3)] and electron-attracting (Br) substitutents are investigated by thermogravimetric analysis (TGA). The results indicate that the Hammett relationship can describe quantitatively the trends in maximum rate of polymer decomposition (T-max) observed in TGA and thus thermostability of substituted poly(styrene peroxide)s depends only on the electronic nature of substituents and their ability to stabilize macroradicals formed during chain scission. The experimental results are also substantiated by thermochemical calculations. (C) 2002 Elsevier Science Ltd. All rights reserved.

Grafting of m-isopropenyl-alpha, alpha-dimethylbenzyl-isocyanate (m-TMI) onto isotactic polypropylene: Synthesis and characterization

A novel vinyl monomer with an isocyanate functional group, m-isopropenyl-alpha,alpha-dimethylbenzyl-isocyanate (m-TMI), was grafted onto isotactic polypropylene (i-PP) using dicumyl peroxide (DCP) as the initiator. This would open up the possibility of using the grafted polymer with the reactive isocyanate group as compatibilizer for blending carbohydrates such as cellulose with. polypropylene. The grafting was carried out in a Brabender Plasticoder at 180degreesC. The effects of monomer and initiator concentrations on the yield of grafting were investigated by performing statistical analysis. While the grafting yield increased with the concentration of DCP at any given concentration of m-TMI, the variation of the grafting yield with m-TMI concentration, for a given concentration of DCP, went through a maximum, the optimum yield of 7.8% (w/w) being obtained at 10 wt.% concentration of both DCP and m-TMI. The grafting reaction is. accompanied by considerable chain scission of I-PP, resulting in a decrease in the molecular weight of the grafted polymer. While the molecular weight drops sharply even at a low concentration of DCP, there occurs no further significant change in the molecular weight even at much higher concentrations of the initiator.

Thermal degradation kinetics of poly(trimethylol propane triacrylate)/poly(hexane diol diacrylate) interpenetrating polymer network

Interpenetrating polymer networks (IPNs) of trimethylol propane triacrylate (TMPTA) and 1,6-hexane diol diacrylate (HDDA) at different weight ratios were synthesized. Temperature modulated differential scanning calorimetry (TMDSC) was used to determine whether the formation resulted in a copolymer or interpenetrating polymer network (IPN). These polymers are used as binders for microstereolithography (MSL) based ceramic microfabrication. The kinetics of thermal degradation of these polymers are important to optimize the debinding process for fabricating 3D shaped ceramic objects by MSL based rapid prototyping technique. Therefore, thermal and thermo-oxidative degradation of these IPNs have been studied by dynamic and isothermal thermogravimetry (TGA). Non-isothermal model-free kinetic methods have been adopted (isoconversional differential and KAS) to calculate the apparent activation energy (E a) as a function of conversion (α) in N 2 and air. The degradation of these polymers in N 2 atmosphere occurs via two mechanisms. Chain end scission plays a dominant role at lower temperature while the kinetics is governed by random chain scission at higher temperature. Oxidative degradation shows multiple degradation steps having higher activation energy than in N 2. Isothermal degradation was also carried out to predict the reaction model which is found to be decelerating. It was shown that the degradation of PTMPTA follows a contracting sphere reaction model in N 2. However, as the HDDA content increases in the IPNs, the degradation reaction follows Avrami-Erofeev model and diffusion governed mechanisms. The intermediate IPN compositions show both type of mechanism. Based on the above study, debinding strategy for MSL based microfabricated ceramic structure has been proposed. © 2012 Elsevier B.V.

Effect of gamma-radiation on the thermal and mechanical properties of a commercial poly(butylene adipate-co-terephthalate)

BACKGROUND: Poly(butylene adipate-co-terephthalate) (PBAT) has attracted wide interest as a biodegradable polymer. However, its use is restricted in certain applications due to its low melting point.RESULTS: PBAT was treated using gamma-radiation. The radiation features were analyzed using Soxhlet extraction, and the ratio of chain scission and crosslinking and gelation dose were determined using the classical Charlesby-Pinner equation. The results showed that PBAT is a radiation-crosslinkable polymer. The degree of crosslinking increased with increasing radiation dose; the relation between sol fraction and dose followed the Charlesby-Pinner equation. Differential scanning calorimetry analyses showed that the melting temperature (T-m) and the heat of fusion (Delta H-m) of PBAT exhibited almost no change in the first scan. The second scan, however, showed a decrease in T-m and Delta H-m. The glass transition temperature of irradiated PBAT increased with increasing radiation dose.

Effect of peroxide crosslinking on thermal and mechanical properties of poly(epsilon-caprolactone)

Poly(epsilon-caprolactone) (PCL), a saturated polyester, derived from ring-opening polymerization of epsilon-caprolactone, was chemically crosslinked with various amounts of benzoyl peroxide (BPO) by a two-step method by first evenly dispersing the BPO into the PCL matrix and then crosslinking at elevated temperature. The gel fraction increased with an increase in BPO content. The modified Charlesby-Pinner equation was used to calculate the ratio of chain scission and crosslinking. The results showed that both scission and crosslinking occurred, and that crosslinking predominated over scission. The number-average molecular weight between the crosslinks determined by the rubber elasticity theory using the hot set test showed a decrease with increasing BPO content. The melting temperature and crystallinity decreased with an increase in BPO content, and the crystallization temperature increased after crosslinking. Dynamic mechanical analysis results showed a decrease in the glass transition temperature as a result of chemical crosslinking of PCL. This was explained by the observed reduction in crystallinity and the increase in free volume due to restrictions in chain packing.

Nano-reactors for controlling the selectivity of the free radical grafting of maleic anhydride onto polypropylene in the melt

This paper reports on a successful application of the concept of nanoreactors to effectively controlling the selectivity of the free radical grafting of maleic anhydride (MAH) onto polypropylene (PP) in the melt, an industrially relevant process. More specifically, a free radical initiator of type ROOR was first confined into (or encapsulated by) the galleries of an organically modified montmorillonite (o-MMT) whose interdistance was 2.4 nm. Primary free radicals (RO center dot) formed inside the o-MMT galleries had to diffuse out before they could react with the PP backbone. The controlled release of the primary free radicals significantly increased the grafting degree of MAH onto PP and greatly reduced the level of the chain scission of the latter. Those results were better understood by electron spin resonance studies on model systems and by Monte Carlo simulations.

Thermal degradation kinetics of uncapped and end-capped poly(propylene carbonate)

In order to improve its thermal stability, poly(propylene carbonate)(PPC) was end-capped by different active agents. Thermogravimetric data show that the degradation temperature of uncapped PPC was lower than that of end-capped PPC. The kinetic parameters of thermal degradation of uncapped and end-capped PPC were calculated according to Chang's method. The results show that different mechanisms operate during the whole degradation temperature range for uncapped PPC. In the first stage, chain unzipping dominates the degradation. With increasing temperature, competing multi-step reactions occur. In the last stage, random chain scission plays an important role in degradation. For end-capped PPC, random chain scission dominates the whole degradation process.

The kinetics of the thermal decomposition of poly(3-hydroxybutyrate) and maleated poly(3-hydroxybutyrate)

The thermal decomposition mechanism of maleated poly(3-hydroxybutyrate) (PHB) was investigated by FTIR and H-1 NMR. The results of experiments showed that the random chain scission of maleated PHB obeyed the six-membered ring ester decomposition process. The thermal decomposition behavior of PHB and maleated PHB with different graft degree were studied by thermogravimetry (TGA) using various heating-up rates. The thermal stability of maleated PHB was evidently better than that of PHB. With increase in graft degree, the thermal decomposition temperature of maleated PHB gradually increased and then declined. Activation energy E. as a kinetic parameter of thermal decomposition was estimated by the Flynn-Wall-Ozawa and Kissinger methods, respectively. It could be seen that approximately equal values of activation energy were obtained by both methods.

RADIATION VULCANIZATION OF HYDROGENATED ACRYLONITRILE-BUTADIENE RUBBER (HNBR)

Raw polymer and compound of hydrogenated acrylonitrile butadiene rubber (HNBR) were subjected to gamma-ray irradiation. Crosslinking was found to be the main chemical reaction induced by irradiation; the ratio of chain scission to crosslinking as well as

EFFECT OF IRRADIATION ON CRYSTALLINITY AND MECHANICAL-PROPERTIES OF ULTRAHIGH MOLECULAR-WEIGHT POLYETHYLENE

Ultrahigh molecular weight polyethylene (UHMWPE) has been irradiated (0-40 Mrad) with a Co-60 source at room temperature under vacuum. The crystallinity has been investigated by differential scanning calorimetry (DSC) and small-angle X-ray scattering (SAXS). The mechanical properties have been determined at room temperature. A significant increase of heat of fusion can be seen at low irradiation doses, which is attributed to crystallization, caused by chain scission during the process of irradiation. It is also observed that the thickness of the lamellae changes with irradiation dose. The Young's modulus has been improved significantly after irradiation at low doses. (C) 1993 John Wiley & Sons, Inc.

Through-thickness control of polymer bioresorption via electron beam irradiation

Predicable and controlled degradation is not only central to the accurate delivery of bioactive agents and drugs, it also plays a vital role in key aspects of bone tissue engineering. The work addressed in this paper investigates the utilisation of e-beam irradiation in order to achieve a controlled (surface) degradation profile. This study focuses on the modification of commercially and clinically relevant materials, namely poly(L-lactic acid) (PLLA), poly(L-lactide-hydroxyapatite) (PLLA-HA), poly(L-lactide-glycolide) co-polymer (PLG) and poly(L-lactide-DL-lactide) co-polymer (PLDL). Samples were subjected to irradiation treatments using a 0.5 MeV electron beam with delivered surface doses of 150 and 500 kGy. In addition, an acrylic attenuation shield was used for selected samples to control the penetration of the e-beam. E-beam irradiation induced chain scission in all polymers, as characterized by reduced molecular weights and glass transition temperatures (T-g). Irradiation not only produced changes in the physical properties of the polymers but also had associated effects on surface erosion of the materials during hydrolytic degradation. Moreover, the extent to which both mechanical and hydrolytic degradation was observed is synonymous with the estimated penetration of the beam (as controlled by the employment of an attenuation shield). (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.