Gelation Dose Research Articles

Identification of the effect of ionizing radiation on epichlorohydrin-based homo-, co-, and ter-polymers

In this study, the effects of ionizing radiation on a series of epichlorohydrin (ECH)-based polymers, namely poly(epichlorohydrin) (CO) homopolymer, poly(epichlorohydrin-co-ethylene oxide) (ECO) copolymer, and poly(epichlorohydrin-co-ethylene oxide-co-allyl glycidyl ether) (GECO) terpolymer, were examined. Polymers are irradiated at room temperature with accelerated electrons in the 0–150 kGy absorbed dose range. The effect of irradiation on the chain structure polymers was examined with sol-gel and rheological analyses. While ECH-based homo- and co-polymers showed crosslinking up to a specific dose, it was found that chain scission above a critical dose value was more dominant. On the other hand, in the ECH terpolymer, crosslinking tendency in the 0–80 kGy dose range was found to be dominant over chain scission. It was found that radiation stability varies depending on the initial molecular mass of the copolymer. Using the Charlesby–Pinner and Charlesby–Rosiak equations for each polymer, the chain scission and crosslink yield ratio (p0/q0), gelation dose (Dg), and virtual gelation dose (Dv) were determined and the effect of ionizing radiation on these polymers, which has increased in use in recent years, was examined. In this study, the effect of ionizing radiation on the long-chain branching value of ECH-based polymers was also examined using a rubber process analyzer (RPA) and large amplitude oscillatory shear testing (LAOS), and a mechanism for the exchange of branching has been proposed.

Modeling and Correcting Cure‐Through in Continuous Stereolithographic 3D Printing

AbstractContinuous stereolithography offers significant speed improvements over traditional layer‐by‐layer approaches but is more susceptible to cure‐through, undesired curing along the axis of exposure. Typically, cure‐through is mitigated at the cost of print speed by reducing penetration depth in the photopolymer resin via the addition of nonreactive light absorbers. Here, a mathematical approach is presented to model the dose profile in a part produced using continuous stereolithography. From this model, a correction method is developed to modify the projected images and produce a chosen dose profile, thereby reducing cure‐through while maintaining print speed. The method is verified experimentally on a continuous stereolithographic 3D printer, and the practicality of various dose profiles is investigated. In optimizing the critical dose parameter, the measured gelation dose Dgel is found to be insufficient for accurate reproduction of features, and an optimal value of Dc = 5Dgel is chosen for the test resin. Using optimized parameters with a high‐absorbance height resin (ha = 2000 µm), feature height errors are reduced by over 85% in a test model while maintaining a high print speed (s = 750 mm h−1).

Reducing the hydrocarbon gas diffusion and increasing the pressure-impact strength of fuel transfer pipelines for use in the automotive industry using radiation crosslinked polyamide 12

The main aim of this study was to reduce the rate of daily hydrocarbons (HC) released into the atmosphere from polyamide-based automotive fuel transfer system pipes due to diffusion using radiation processing technology. The second aim of this study was to improve the pressure level and impact strength of these pipelines. In order to manage these aims, layer by layer extruded pipelines constructed from different types of thermoplastic materials (i.e. PA6, EVOH and radiation crosslinkable 5% 1,3,5-triallyl-1,3,5-triazin-2,4,6(1H,3H,5H)-trion (TAIC) containing PA12 (Creamid-12)) were irradiated using γ-rays (up to 100 kGy) at room temperature to carry out a radiation-induced crosslinking process. The mechanical properties of the samples were evaluated using tensile and cold impact tests. Sol-gel analysis of the irradiated samples was performed to determine the gel content, gelation dose and chain scission/crosslinking ratio. The Charlesby–Pinner and Charlesby–Rosiak equations were used for our calculations. The change in the HC diffusion of the crosslinked pipes was measured using a sealed housing for evaporative determination (SHED) device. An improvement in the pressure resistance was observed for the samples under an increasing fluid pressure using a blasting test device. The SHED results showed that the gas permeability value is reduced ~1.9 fold in the 65 kGy irradiated fuel transfer pipelines. The blasting test results indicate that the average pressure resistivity of the 65 kGy irradiated and 76.5% cross-linked pipe samples was ~19% greater than that observed for the unirradiated samples. The results of this study show that the radiation cross-linking process is an excellent strategy to reduce the daily hydrocarbon emissions from new generation fuel transfer pipelines.

Effect of Ionizing Radiation on the Chemical Structure and the Physical Properties of Polycaprolactones of Different Molecular Weight.

Polymers used in the biomedical sector can be exposed to ionizing radiation (X-ray, gamma) in vivo as implants or ex vivo for sterilization purposes (gamma, electron beam). This ionizing radiation can, at certain levels, cause degradation of the polymer. Polycaprolactones (PCL) of different molecular weights were irradiated with electron beam and the changes in their chemical structure and physical properties with the dose were evaluated. Electron beam irradiation produced crosslinking and chain scission in the PCL chain without significant predominance of one mechanism over the other. Minimum dose for gelation decreased with the increase in PCL molecular weight whereas crosslinking efficiency was almost independent of PCL molecular weight. Carboxylic groups, hydroxyl groups and new saturated hydrocarbon species were detected by proton nuclear magnetic resonance (NMR). These species were consistent with a mechanism where chain scission could take place at any bond in the PCL chain with preference in the –COO–CH2– bond. Crosslinking decreased significantly the crystallization temperature of PCL. Tensile properties decreased continuously with the increase in dose. Irradiation with gamma rays produced a faster decay in mechanical properties than electron beam.

Chitosan-containing hydrogel wound dressings prepared by radiation technique

The aim of the study was to develop an antimicrobial hydrogel wound dressing by means of radiation-initiated crosslinking of hydrophilic polymers, i.e. by well-established technology comprising gel manufacturing and its sterilization in one process. The approach included admixture of chitosan of relatively low molecular weight dissolved in lactic acid (LA) into the initial regular components of the conventional hydrogel dressing based on poly(N-vinyl pyrrolidone) (PVP) and agar. Molecular weight of chitosan was regulated by radiation-initiated degradation in the range of 39–132kgmol−1. Optimum total concentration of LA in the resultant hydrogel dressing was evaluated as 0.05moldm−3, that is ca. 0.5%. Presence of LA in the system influenced essential radiation and technological parameters of hydrogel manufacturing. The setting temperature of the pre-hydrogel mixture, resulting from agar ability to congeal, was reduced with LA concentration, yet remained significantly above the room temperature. 0.5% of chitosan was effectively dissolved in aqueous solution of lactic acid due to its pH (lower than 5.5). Radiation parameters of PVP crosslinking in the presence of LA, as determined with generalized Charlesby–Pinner equation, were reflected in slight reduction of the maximum gel fraction and increase in gelation dose and in the factor comparing yields of scission to crosslinking. Nevertheless, essentially physical characteristics of the hydrogel was not affected, except for somewhat increased water uptake capacity, what in turn improves functionality of the dressing as extensive exudate for the wound can be efficiently absorbed. Preliminary microbiological studies showed antimicrobial character of the chitosan-containing hydrogel towards Gram-positive bacterial strain.

2-(2-methoxyethoxy)ethyl methacrylate hydrogels with gradient of cross-link density

Abstract Electron beam irradiation of 2-(2-methoxyethoxy)ethyl methacrylate and ethylene glycol dimethacrylate mixtures leads to the formation of cross-linked structures that exhibit a gradient of cross-link density, as demonstrated by gel fraction, swelling and Differential Scanning Calorimetry analysis. The reason for observed phase separation is formation of the high molecular weight clusters and its precipitation before gelation dose. This effect can be controlled/influenced by absorbed dose and cross-linker concentration.

Preparation of carboxymethyl sago pulp hydrogel from sago waste by electron beam irradiation and swelling behavior in water and various pH media

AbstractSolutions of carboxymethyl sago pulp (CMSP) of various degree of substitution were irradiated with electron beam of various radiation doses. The gelation dose (Dg) and po/qo ratio (po is degradation density, qo is crosslinking density) is dependent on CMSP concentration and degree of substitution. In the range of concentrations of 10% to 80% (w/v) CMSP with degree of substitutions of 0.4, 0.6, and 0.8, the po/qo ratio decreases with increasing %CMSP showing that crosslinking processes are dominating and increasing the gel network of the CMSP hydrogel. The fourier transform infrared spectra of CMSP hydrogels of degree of substitutions of 0.4, 0.6, and 0.8 with percentage of gel fractions 25, 35, and ≥ 40 show differences in the intensity of the absorption bands at 1020–1100, 1326, and 1422 cm−1 with different degree of substitutions and percentage of gel fraction (%GF) that correspond to different extents of chain scission and crosslinking. The swelling behavior in water shows that CMSP hydrogels could absorb 3500–5300% of water by 1 g of CMSP hydrogel. The ability to absorb water increases with the decrease of degree of substitution and %GF of the CMSP hydrogels. It is also observed that the optimum pH for swelling CMSP hydrogel is at pH 7. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013

Radiation Yield and Radicals Produced in Irradiated Poly (Butylene Succinate)

Normal 0 false false false EN-US X-NONE X-NONE MicrosoftInternetExplorer4 The main chemical effects of ionizing irradiation on polymers are crosslinking and chain scission. Both processes occur simultaneously and their yields determine the final results of processing. The radiation yield of crosslinking could be determined by several methods depending on the characteristics of the material and properties of the gel. Radiation parameters of gelation, such as gelation dose and ratio of scission yield to crosslinking yield, as well as their values were estimated. In this study, those parameters depend on the amount of Trimethallyl isocyanurate (TMAIC) in Poly(butylene succinate) (PBS), molecular weight of PBS, and irradiation condition. In the absence of TMAIC, higher molecular weight of PBS required less energy to start gelation process compare to lower molecular weight of PBS. While in the presence of TMAIC all of the PBS samples require similar energy to start gelation process. The existence of macroradicals were observed by Electron Spin Resonance measurements. The result showed that the spectra consisted of signals derived from radicals on carbon nearby carbonyl, and signals derived from radicals on carbon reside between two similar carbon on polymer, both of radicals lead to crosslinking.

How do monomeric components of a polymer gel dosimeter respond to ionising radiation: A steady-state radiolysis towards preparation of a 3D polymer gel dosimeter

Ionising radiation-induced reactions of aqueous single monomer solutions and mixtures of poly(ethylene glycol) diacrylate (PEGDA) and N, N′-methylenebisacrylamide (Bis) in a steady-state condition are presented below and above gelation doses in order to highlight reactions in irradiated 3D polymer gel dosimeters, which are assigned for radiotherapy dosimetry. Both monomers are shown to undergo radical polymerisation and cross-linking, which result in the measured increase in molecular weight and radius of gyration of the formed polydisperse polymer coils. The formation of nanogels was also observed for Bis solutions at a low concentration. In the case of PEGDA-Bis mixtures, co-polymerisation is suggested as well. At a sufficiently high radiation dose, the formation of a polymer network was observed for both monomers and their mixture. For this reason a sol–gel analysis for PEGDA and Bis was performed gravimetrically and a proposition of an alternative to this method employing a nuclear magnetic resonance technique is made. The two monomers were used for preparation of 3D polymer gel dosimeters having the acronyms PABIG and PABIG nx. The latter is presented for the first time in this work and is a type of the formerly established PABIG polymer gel dosimeter. The elementary characteristics of the new composition are presented, underlining the ease of its preparation, low dose threshold, and slightly increased sensitivity but lower quasi-linear range of dose response in comparison to PABIG.

Influence of electron beam irradiation on physicochemical properties of poly(trimethylene carbonate)

Electron beam (EB) irradiation of poly(trimethylene carbonate) (PTMC), an amorphous, biodegradable polymer used in the field of biomaterials, results in predominant cross-linking and finally in the formation of gel fraction, thus enabling modification of physicochemical properties of this material without significant changes in its chemical structure. PTMC films ( M w : 167–553 kg mol −1) were irradiated with different doses using an electron accelerator. Irradiation with a standard sterilization dose of 25 kGy caused neither significant changes in the chemical composition of the polymer nor significant deterioration of its mechanical properties. Changes in viscosity-, number-, weight-, and z-average molecular weights of PTMC for doses lower than the gelation dose ( D g ) as well as gel–sol analysis and swelling tests for doses above D g indicate domination of cross-linking over degradation. EB irradiation can be considered as an effective tool for increasing the average molecular weight of PTMC and sterilization of PTMC-based biomaterials.

Gamma radiation on poly(ϵ‐caprolactone) in the presence of vinyltrimethoxysilane

AbstractThe performance and radiation‐induced cross‐linking of polycaprolactone (PCL) in the presence of vinyltrimethoxysilane (VTMS) have been investigated. Radiation‐induced cross‐linking of PCL in the presence of VTMS followed the Charlesby–Pinner equation, and VTMS promoted the radiation‐induced cross‐linking of PCL. As the concentration of VTMS increased, the gelation dose and the ratio of degradation to cross‐linking (p0/q0) decreased and the efficiency of radiation‐induced cross‐linking increased. Differential scanning calorimetry analyses showed differences between the first and second scans. Glass‐transition temperature (Tg) and mechanical properties of the polymers increased. Radiation‐induced cross‐linking of PCL in the presence of VTMS was found to retard hydrolytic degradation greatly. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers

Effects of sensitizer length on radiation crosslinked shape–memory polymers

Shape–memory polymers (SMPs) are smart materials that can be designed to retain a metastable state and upon activation, recover a preprogrammed shape. In this study, poly(methyl acrylate) (PMA) is blended with poly(ethylene glycol) diacrylate (PEGDA) of various molecular weights in various concentrations and subsequently exposed to ionizing radiation. PEGDA sensitizes the radiation crosslinking of PMA, lowering the minimum absorbed dose for gelation and increasing the rubbery modulus, after crosslinking. Minimum dose for gelation, as determined by the Charlesby–Pinner equation, decreases from 25.57 kGy for unblended PMA to 2.06 kGy for PMA blended with 10.00 mole% PEGDA. Moreover, increase in the blend concentration of PEGDA increases the crosslinking density of the resulting networks. Sensitizer length, namely M n of PEGDA, also affects crosslinking and final mechanical properties. Increase in the length of the PEGDA molecule at a constant molar ratio increases the efficacy of the molecule as a radiation sensitizer as determined by the increase in gel fraction and rubbery modulus across doses. However, at a constant weight ratio of PEGDA to PMA, shorter PEGDA chains sensitize more crosslinking because they have more reactive ends per weight fraction. Sensitized samples of PMA with PEGDA were tested for shape–memory properties and showed shape fixity of greater than 99%. Samples had a glass transition temperature near 28 °C and recovered between 97% and 99% of the induced strain when strained to 50%.

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

AbstractBACKGROUND: 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 γ‐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 (Tm) and the heat of fusion (ΔHm) of PBAT exhibited almost no change in the first scan. The second scan, however, showed a decrease in Tm and ΔHm. The glass transition temperature of irradiated PBAT increased with increasing radiation dose. The weight loss of control and irradiated PBAT resulting from thermal degradation was a one‐step process. Moreover, the tensile strength and elongation at break decreased with an increase in radiation dose. However, the Young's modulus and stress at yield were not greatly affected by γ‐radiation.CONCLUSION: PBAT can be crosslinked using γ‐radiation. The crosslinking efficiency is relatively low. The thermal and mechanical properties of PBAT are affected by γ‐radiation. Copyright © 2009 Society of Chemical Industry

Radiation and postirradiation crosslinking and structure of two unsaturated polyester resins

AbstractRadiation and postirradiation crosslinking of two unsaturated polyester (UP) resins were monitored, and substantial differences in the reaction course and extents were observed. DSC thermograms of one of the resins showed double peaks and significantly lower residual reaction heats. Extraction revealed that gelation dose of the resin with double peak was twice the gelation dose of the other resin that had single peak in DSC thermograms. Although other components of the polyesters were identical, NMR spectra of the resin with a single peak revealed isophthalic units while in the polyester of the resin having double DSC peaks orthophthalic units were detected. Orthophthalate reduced the compatibility of polyester and styrene and caused the reaction‐induced phase separation, influencing gel structure that was visible in scanning electron microscope micrographs. Previously, the double peaks in crosslinking thermograms of UP resins were usually attributed to initiator effects, but here no initiator was used, and, in the literature, we found that the double peaks are almost exclusively present in the thermograms of UP resins containing orthophthalates, whereas in resins with isophthalates double peaks almost never appear. Crosslinking extents were significantly higher in the resin‐containing isophthalate and in both cases enhanced by postirradiation reaction that is often neglected. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers

Enhanced radiation crosslinking of carboxymethylated chitosan in the presence of acids or polyfunctional monomers

Carboxymethylated chitosan (CMCt) hydrogels were synthesized by γ-ray radiation-induced crosslinking in the presence of acids or polyfunctional monomers. Compared with that of CMCt hydrogels synthesized without additives, the gel fraction was improved and the gelation dose was decreased obviously after incorporating acids or polyfunctional monomers into CMCt hydrogels. The diffusion behavior of water in the CMCt gels prepared at different conditions was Fickian diffusion, and the swelling of the CMCt gels displayed characteristic pH sensitivity, which was analyzed by fluorescence molecular probes. Preliminary mechanism of radiation-induced crosslinking of CMCt in the presence of acids or polyfunctional monomers was discussed based on the FTIR and sol–gel analysis. Furthermore, it was found that CMCt hydrogels were hydrodegradable with high temperature (>60 °C), and incorporating polyfunctional monomers into the CMCt hydrogels also could improve the thermal stability of the CMCt hydrogels obviously.

Radiation effects on hydroxypropyl methylcellulose phthalate in aqueous system

A water-insoluble cellulose derivative, hydroxypropyl methylcellulose phthalate (HPMCP) hydrogels, was converted to Na type to form hydrogel in paste-like status by radiation crosslinking. Mechanism for radiation crosslinking of cellulose-derivatives in paste-like status was discussed. Crosslinkers, i.e. methyl N, N-bis-acrylamide (MBA) or ethyleneglycol dimethacrylate (EGDMA) has been used to decrease gelation dose (Dg) of synthesis HPMCP hydrogels and improve its mechanical properties. HPMCP-MBA hydrogels were found to be more rigid and HPMCP-EGDMA hydrogels were more flexible. Swelling degree of HPMCP hydrogel in many kinds of salt solutions followed Hofmeister series, which is ubiquitous in polyelectrolyte hydrogel. Specific reswelling was observed in concentrated KF solution, implying a very strong F − binding ability of benzyl group. The comprehensive results obtained in this study will be utilized on the design of HPMCP-based controlled release system.

Radiation-chemical synthesis of crown-containing poly(ethylene oxide) hydrogels. Swelling behavior and crown ether retention

Poly(ethylene oxide) hydrogels containing physically immobilized dicyclohexano-18-crown-6 (DCH18C6) were synthesized by radiation-chemical cross-linking. DCH18C6 concentration in initial polymer solution has insignificant effect on the gelation dose at the weight ratio of crown ether to polymer lower than 0.2. The higher molecular weight of PEO results in lower gelation dose and higher gel fraction. An increase in absorbed dose leads to a noticeable decrease in the swelling ratio corresponding to a denser hydrogel network. At the same time the absorbed dose in the range of 5–100 kGy has no pronounced effect on the DCH18C6 retention.

Shape memory behaviour of radiation-crosslinked PCL/PMVS blends

The performance and radiation crosslinking of polycaprolactone (PCL) and polymethylvinylsiloxane (PMVS) blends has been investigated. Radiation crosslinking of PCL/PMVS blends followed the Charlesby–Pinner equation, and PMVS promoted the radiation crosslinking of the blends. As the concentration of PMVS increased, the gelation dose and the ratio of degradation to crosslinking ( p 0 / q 0 ) decreased and the efficiency of radiation crosslinking increased. The elastic modulus below the melting point of PCL of radiation-crosslinked PCL/PMVS blends decreased with the increase of PMVS, and increased above the melting point. The crosslinked PCL/PMVS blends exhibited excellent shape memory effects, and the ratios of deformation to recovery were more than 95%.

Adsorption of metal ions by carboxymethylchitin and carboxymethylchitosan hydrogels

Radiation cross-linking of CM-chitin and CM-chitosan has been investigated. Such parameters of radiation cross-linking as gelation doses, cross-linking and degradation radiation yields and ratios of scission to cross-linking has been determined for both polymers.The absorption ability of various metal ions into EB-radiation cross-linked carboxymethylchitin and carboxymethylchitosan has been investigated. The highest adsorption of scandium and gold has been obtained for carboxymethylchitin (CMCht) and carboxymethylchitosan (CMChts), respectively. Kinetic studies showed that adsorption of most of the metal ions occur in a relatively short period of time (2h). Detail investigation of adsorption of gold ions has been carried out for both hydrogels. The maximum uptake of Au cations, based on Langmuir equation was determined to be 37.59 for CM-chitosan and 11.86 for CM-chitin. Both hydrogels indicate favorable adsorption of gold cations.

Electron‐beam curing of hydrogenated acrylonitrile–butadiene rubber

AbstractThe electron‐beam‐induced crosslinking of hydrogenated acrylonitrile–butadiene rubber (HNBR) was investigated. HNBR sheets were exposed to electron‐beam irradiation in air at a room temperature of 25 ± 2°C over a dose range of 0–20 Mrad. An attempt was made to correlate the structure of the irradiated rubber with the properties. The ratio of chain scission to crosslinking and the gelation dose were determined by a method proposed elsewhere. The gel content and dynamic storage modulus increased with the radiation dose. Fourier transform infrared studies revealed the formation of double bonds and carbonyl and ether groups. These observations were further supported by a thermogravimetric analysis of the carbonaceous residue of irradiated HNBR. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 648–651, 2005