Production of fine powder from silk by radiation

Silk fine powder was prepared directly from silk fibers irradiated with an accelerated electron beam (EB). Irradiated silk fibers were well pulverized only by physical crushing using a ball mill without any chemical pretreatment. Silk fibroin fibers were irradiated at ambient temperature in the dose range of 250–1 000 kGy. Although unirradiated silk fibers were not pulverized at all, irradiated fibers were easily pulverized and showed a high conversion efficiency from fiber to powder at high irradiation doses. The presence of oxygen in the irradiation atmosphere enhanced pulverization of the silk fibers. The electron microscopic observation showed that the minimum particle size of silk powder obtained from fibers irradiated at 1 000 kGy in oxygen was less than 10 μm. It was found that fibroin powder obtained in this work dissolved remarkably in water, thought unirradiated fibroin fibers were insoluble even in hot water. The soluble fraction was about 60% of fibroin powder for 1 000 kGy irradiation in oxygen.     

Evaluation of electron beam-induced crosslinking of poly(ε-caprolactone)—Effect of elevated temperatures

The effect of elevated temperatures (40, 80, and 170 °C) on the electron beam (EB)-induced crosslinking and degradation of poly(ε-caprolactone) (PCL) in nitrogen atmosphere without adding crosslinking agents has been investigated. The increased mass average molecular mass of EB modified masticated PCL (mPCL) samples were measured by size exclusion chromatography. The sol–gel investigation showed that mPCL tended to dominating crosslinking at a temperature of 170 °C. At this temperature, the maximum gel content of 56% was observed for an EB treatment with a dose of 100 kGy. In addition, the ratio of chain scission density to density of crosslinked units amounted to 0.25. The dynamic rheological test demonstrated that EB treatment at 170 °C led to the most remarkable elasticity enhancement behavior with enhanced viscosity, modulus, and decreased loss factor (tan δ). The occurrence of branching structure was evidently detected by van Gurp–Palmen plot in combination with the Cole–Cole plot for dose values ≤50 kGy. Less δ and a broadened relaxation process can be observed due to the introduction of some branched structures into mPCL. The results of enhanced molar mass and gel content analysis were confirmed by the dynamic rheological measurements. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47866.     

多乙烯基单体对溴化丁基胶电子束交联的敏化效应

观察到溴化丁基胶(BIIR)在加速器产生的电子束辐照下可发生交联反应,测得其凝胶化剂量为12 kGy。在剂量较低时辐照产物的凝胶含量与交联密度均随剂量增加而提高,但在80 kGy后则随剂量增加而呈下降趋势。试验了5种多乙烯基单体以敏化BIIR的交联反应,从而避免高剂量下的降解现象。结果表明TMPT(三甲基丙烯酸三羟甲基丙烷酯)是有效的敏化剂,配有TMPT的BIIR交联产物其拉伸强度随TMPT用量增大而明显提高。     

Electron Beam Irradiation to Recrosslink Devulcanized Sulfur Cured Rubber Blended Polypropylene

This study aims to investigate the effect electron beam (EB) irradiation on the polypropylene/devulcanized sulfur cured rubber (PP‐DVC) compound. The PP‐DVC compounds were compounded using twin‐screw extruder and then compression molded into required shapes before irradiation begins. The gel content of all irradiated PP‐DVC compounds gradually increased with higher irradiation dose indicated that the presence of DVC plays an important role in crosslinking enhancement. The mechanical properties of PP‐DVC compounds were observed marginally higher at low irradiation dosages (≤50 kGy). However, higher irradiation dosages up to 200 kGy cause adverse effect to the PP‐DVC compounds. In addition, the application of low irradiation dosage could enhance the dispersion of DVC particles at 20 phr composition in PP matrix. This also found that the scanning electron microscopy (SEM) observation where the DVC particles dispersed better in PP matrix compared to that of nonirradiated samples. Further increment in irradiation dosages up to 200 kGy reduced the crystallinity caused by chain scissoring process could rupture the crystalline structure in PP matrix. It was also found that the wavenumber of the C? H and CH₂ groups for irradiated samples reduced at high irradiation dosages due to the formation of carbonyl group. POLYM. ENG. SCI., 59:1017–1027, 2019. © 2019 Society of Plastics Engineers     

含乙烯基有机硅树脂的电子束固化行为研究

以八甲基环四硅氧烷、四甲基四乙烯基环四硅氧烷为单体,六甲基二硅氧烷为封端剂,碱胶为催化剂,合成了含乙烯基有机硅树脂;并研究了电子束辐射剂量对其固化行为的影响和固化涂层的热性能。红外谱图及凝胶率测试结果表明,有机硅树脂中的碳碳双键吸收峰强度随辐射剂量的增加而减弱,辐射诱导交联网络结构的形成导致固化涂层的凝胶率随剂量的增加而显著增加;辐射剂量为30 kGy时,凝胶率为46.2%;辐射剂量增加至60 kGy时为70.1%和100 kGy时为85.9%。差示扫描量热分析和热质分析结果表明,固化涂层具有优良的耐低温性和热稳定性。     

Molecular structure and physical properties of E‐beam crosslinked low‐density polyethylene for wire and cable insulation applications

Crosslinking of homemade low‐density polyethylene (LDPE) was performed by electron‐beam (EB) irradiation. The gel content of the EB‐exposed LDPE was determined by the solvent‐extraction method. The degree of crosslinking was also evaluated by a hot set measuring test. The results obtained from both the gel–sol and the hot set methods showed that the degree of crosslinking was dependent on the deposited energy in LDPE samples. Increasing the absorbed dose increased the degree of network formation. The LDPE with higher molecular weight yielded higher efficiency of crosslinking at the same irradiation dose. The effect of irradiation dose on the molecular weight between crosslinks (M_c), glass‐transition temperature, and free volume were calculated. Mechanical test results showed that the tensile strength of the samples increased with increase in the irradiation dose up to 150 kGy and then slightly decreased with further increasing the deposited energy. The elongation at break decreased with increasing the absorbed dose. The results obtained from differential scanning calorimetry exhibited a small reduction in the melting point and the degree of crystallinity of the EB‐exposed LDPE samples compared to those of the untreated samples. The effect of crosslinking on the electrical properties of the irradiated samples was insignificant. The dielectric constant of the treated samples remained nearly constant within the irradiation dose range, although the dissipation factor increased slightly with increasing the absorbed dose. The results obtained from characterizing the EB‐induced crosslinking of homemade polyethylene, including LH0030 and LH0075, showed the higher molecular weight polyethylene (LH0030) as a preferred option for wire and cable insulation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1959–1969, 2002     

电子束辐照聚乳酸-聚乙二醇共聚物的结构及热性能研究

本文首先通过直接熔融缩聚法制备了聚乳酸-聚乙二醇共聚物(PLEG),并采用FTIR和1 H NMR对其结构进行表征。然后在辐射剂量0～100kGy范围下,利用衰减全反射红外(ATR-FTIR)、差示扫描量热(DSC)和热失重分析(TGA)研究了电子束辐照对PLEG结构及热性能的影响。结果表明:加入3%的三聚氰酸三烯丙酯(敏化剂TAC)后,由于交联结构的形成,PLEG的凝胶率、玻璃化转变温度(Tg)和热稳定性均随辐射剂量的增加而有所提高,且其热转变行为也发生变化。     

Thermal and physicomechanical properties of gamma‐irradiated EPDM/waste newsprint microfibers composites treated using acrylic styrene emulsion as a coupling agent

This investigation deals mainly with thermal stability and crosslinking density of EPDM/newsprint microfibers composites. The recycled newsprint microfibers were treated using a different ratio of acrylic styrene emulsion (5, 10, and 15 wt% fiber) as a bonding agent to reinforce EPDM rubber matrix. The effect of microfibers content, namely, 5 up to 50 phr (part per hundred part of rubber) and the effect of ionizing radiation on EPDM/newsprint microfibers composites properties were investigated. The microfibers structure and EPDM/microfibers composite were investigated using X‐ray diffraction and FTIR analysis; the results indicate that bonding has occurred between the treated newsprint microfibers and EPDM polymer matrix. EPDM/untreated newsprint microfibers composites have achieved higher crosslinking density than EPDM matrix up to 50 phr microfibers content and up to 100 kGy then decreased with increasing gamma irradiation dose. Meanwhile treatment of the microfibers using 10 wt% acrylic styrene leads to improve crosslinking density at any microfibers content. Thermogravimetric analysis (TGA) was carried out for the microfibers and their composites. TGA indicated that the thermal stability of microfiber was enhanced using acrylic styrene. Whereas there is a slight improvement in thermal stability and activation energy of the composites due to adding treated microfibers using 10 phr microfiber content treated using10 wt% acrylic styrene emulsion and irradiated with 60 kGy gamma radiation dose. J. VINYL ADDIT. TECHNOL., 25:E91–E106, 2019. © 2018 Society of Plastics Engineers     

Radiation grafting/crosslinking of silk using electron‐beam irradiation

The radiation grafting of silk with methacrylamide (MAA) was studied using an electron‐beam (EB) irradiation technique. Two irradiation processes, preirradiation and coirradiation, were compared, and some factors affecting the degree of grafting were investigated. The radiation crosslinking of silk with dimethyloldihydroxyethylene urea (DMDHEU) was preliminarily studied. The physical and mechanical properties such as whiteness, breaking strength, and resilience of the radiation‐grafted/crosslinked silk fabrics were examined. The radiation grafting of silk with MAA increases the silk weight, while the radiation crosslinking of silk with DMDHEU imparts improved crease resistance to silk. X‐ray photoelectron spectroscopy (XPS) and electron spin resonance (ESR) analysis indicate the formation of peroxy and free‐radical species on the EB‐irradiated silk. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2028–2034, 2004     

Synthesis of flexible polymeric shielding materials for soft gamma rays: Physicomechanical and attenuation characteristics of radiation crosslinked polydimethylsiloxane/Bi2O3 composites

Flexible lead‐free high energy radiation shielding material was developed through internal compounding. Polymer‐filler interaction, crosslinking density, specific gravity, physicomechanical characteristics, percentage attenuation, and thermal stability of the crosslinked composites were estimated. It was found that even at very high filler loading composites can be crosslinked; however, the crosslinking density was composition dependent and was highest in 10–50 wt% loading range at 100 kGy and 200 kGy. The Nielsen model was applied to understand the micromechanics of the system. Attenuation of gamma radiation from Am241 was not affected by the crosslinking density. Thermal stability of the composites was found to be significantly affected with bismuth oxide loading. POLYM. COMPOS., 37:756–762, 2016. © 2014 Society of Plastics Engineers     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol) copolymer and poly(L‐lactic acid) by electron beam irradiation

This article investigated the effects of electron beam (EB) irradiation on poly(D ,L ‐lactic acid)‐b‐poly(ethylene glycol) copolymer (PLEG) and poly(L ‐lactic acid) (PLLA). The dominant effect of EB irradiation on both PLEG and PLLA was chain scission. With increasing dose, recombination reactions or partial crosslinking of PLEG can occur in addition to chain scission, but there was no obvious crosslinking for PLLA at doses below 200 kGy. The chain scission degree of irradiated PLEG and PLLA was calculated to be 0.213 and 0.403, respectively. The linear relationships were also established between the decrease in molecular weight with increasing dose. Elongation at break of the irradiated PLEG and PLLA decreased significantly, whereas the tensile strength and glass transition temperature of PLLA decreased much more significantly compared with PLEG. The presence of poly(ethylene glycol) (PEG) chain segment in PLEG was the key factor in its greater stability to EB irradiation compared with PLLA. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synergy modification of the microstructure and the property of PBO fiber by γ‐ray radiation

The effects of γ‐ray radiation on PBO fibers and its composite materials have been investigated, the results showed that the microstructure and the performance of radiated PBO fibers have been improved with 30–120 kGy radiation dose, crosslinking reactions came from PBO polymer molecule chains and micro‐fibrils. As a result, the molecular weight the thermal stability were increased, the tendency of micro‐fibrils to split‐off also decreased, the hook force of radiated PBO fibers increased by 14.0% without tensile strength loss, and the nano‐compression modulus and the flexure strength of radiated PBO fiber composites also increased by 21.0% and 22.7%, respectively. The work indicated that γ‐ray radiation could synchronously strengthen the microstructure and improve the properties of PBO fibers. POLYM. ENG. SCI., 58:272–279, 2018. © 2017 Society of Plastics Engineers     

Degradation of poly(D,L‐lactic acid)‐b‐poly(ethylene glycol)‐b‐poly(D,L‐lactic acid) copolymer by electron beam radiation

This article investigates the effects of electron beam (EB) radiation on poly(D ,L ‐lactic acid)‐b‐poly (ethylene glycol) copolymer (PLA‐b‐PEG‐b‐PLA). The copolymer films were EB irradiated at doses from 0 to 100 kGy. The degradation of these films was studied by measuring the changes in their molecular weight, mechanical and thermal properties. The dominant effect of EB radiation on PLA‐b‐PEG‐b‐PLA is chain‐scission. With increasing irradiation dose, recombination reactions or partial crosslinking may occur in addition to chain scission. The degree of chain scission G_s and crosslinking G_x of sample are calculated to be 0.213 and 0.043, respectively. A linear relationship is also established between the decreases in molecular weight with increasing irradiation dose. Elongation at break of the irradiated sample decreases significantly, whereas its tensile strength decreases slightly. The glass transition temperature (T_g) is basically invariant as a function of irradiation dose. Thermogravimetric analysis shows that its thermal stability decreases with increasing dose. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of antimicrobial silver nanoparticles on silk fibers via γ‐radiation

Antimicrobial silver nanoparticles (NPs) were successfully synthesized on the surface of silk fibers via γ‐ray irradiation. The products were characterized with scanning electron microscope (SEM), energy dispersion spectrum, and X‐ray diffraction. The results revealed that the silver particles with a diameter of less than 20 nm were immobilized and well dispersed on the surface of silk fibers. The antimicrobial capability against the gram positive bacterium Staphylococcus aureus and the washing stability of the silk fibers produced with different conditions were tested and found to be excellent. The silk fibers treated with 1 mM solution and 10 kGy γ‐radiation showed 96% antimicrobial activity and still kept above 85% antibacterial activity after 10 washing cycles. Moreover, a mechanism for the formation of silver NPs on silk fibers under γ‐radiation was generally discussed. The resulting silk fibers coated with silver NPs can be useful as functional fabrics in a range of applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Accelerated electron effects on EVA based compound

The major effects induced by accelerated electron irradiation on EVA based polymeric compound were evaluated for various doses up to 240 kGy. Some main characteristics (gel fraction, density, elongation at break, and tensile strength) were investigated. Oxygen uptake and thermal analysis methods (TG, DTG, and DTA) were applied for determination of oxidation resistance of radiation processed EVA samples. It was established that a 30 kGy exposure dose promotes maximum crosslinking. At this dose the density and tensile strength reach maximum values, which are maintained for higher doses up to 240 kGy. On the other hand, the thermooxidative stability exhibits a sharp decrease as the absorbed dose rises from 0 to 30 kGy and has a constant value for the absorbed dose range 30–240 kGy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 613–617, 2005     

Modified ethylene-propylene-diene elastomer (EPDM)-contained silicone rubber/ethylene-propylene-diene elastomer (EPDM) blends: Effect of composition and electron beam crosslinking on mechanical,heat shrinkability,electrical, and morphological properties

In this investigation, a gamma radiation-induced methacrylic acid (MAA)-grafted ethylene-propylene-diene elastomer (EPDM) was used as a third component (g-EPDM) in silicone rubber (SiR)/ethylene-propylene-diene elastomer (EPDM) blends. These blends were electron beam (EB) crosslinked. The effect of blend composition, the presence of g-EPDM, and EB crosslinking on the mechanical, heat shrinkability, electrical, and morphological properties of SiR/EPDM blends have been studied. To investigate the effect of grafted EPDM (g-EPDM), 10 wt % of g-EPDM was added to immiscible SiR/EPDM blends. Both silicone and EPDM are blended in different proportions (70:30 and 30:70) with and without g-EPDM followed by compression molding. To improve the properties and investigate the crosslinkability of binary and ternary blends further, the SiR/EPDM blends were irradiated by electron beam at different doses (50, 100, and 150 kGy). The gel content was found to increase with EPDM content, the presence of g-EPDM, and radiation dose. The addition of g-EPDM led to improvement of tensile properties (tensile strength, Young's modulus, percentage elongation, and toughness), electrical properties, and shrinkability of blends. EB crosslinking further enhanced the above properties. Surface morphology (SEM) revealed that the presence of g-EPDM and the incorporation of EB crosslinking improved the above properties of blends. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47787.     

Crosslinked Sulfonated Polysulfone-Based Polymer Electrolyte Membranes Induced by Gamma Ray Irradiation

Sulfonated aromatic polymers generally show high swelling at high proton conductivity. This disadvantage makes many of them unfit for proton exchange membrane applications. Crosslinking of the polymer is one way to overcome this problem. In this study, radiation-induced crosslinking was performed on a sulfonated polysulfone membrane, with doses ranging from 2.5 to 25.0 kGy (dose rate: 45 Gy/min) using gamma rays from a ⁶⁰Co source. The pristine sulfonated polysulfones was obtained by mild sulfonation of bisphenol-A-polysulfone with trimethylsilyl chlorosulfonate as sulfonating agent. The proton conductivity of the membranes was characterized by means of electrical impedance spectroscopy techniques. Ion-exchange capacity, degree of sulfonation, water content and chemical stability membrane properties were characterized before and after irradiation. The results show that the mechanical, chemical and thermal stability of the membrane improve after irradiation. The degree of sulfonation and the proton conductivity exhibit a tendency to decrease with increasing irradiation total dose.     

Irradiation dose control for polymer‐matrix composites fabricated by in situ curing with low‐energy electron beam

The electron beam (EB) with emitting energies lower than 150 keV is applicable in in situ curing of polymer‐matrix composites; however, being poor in penetration ability, it leads to significant attenuation of irradiation dose along the prepreg thickness. In this study, polymer‐matrix composites were fabricated by low‐energy EB irradiation curing, and the effect of dose control of double‐sided irradiation was systematically investigated. Experimental results showed that laminates fabricated by single‐sided irradiated prepregs were low in interlaminar shear strength (ILSS) owing to incomplete curing after being post cured at 180 °C for 30 min. A double‐sided irradiation method which included irradiation of equal dose and different doses on both sides of the prepreg was proposed to overcome this difficulty. Analysis showed that under a total dose of 70 and 100 kGy, the ILSS results were high owing to the low curing degree of two adhesive surfaces; under a total dose of 130 and 160 kGy, laminates fabricated with different EB irradiation doses on both sides exhibited enhanced ILSS compared to those with equal dose on both sides, owing to physical adhesion and chemical crosslinking between layers. The ILSS results exhibited the largest increase of 18.9 and 60.5%, respectively, by tuning the dose differences between both sides of the prepregs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44944.     

Effect of crosslinking monomers on the performance of electron beam-induced biodegradable Bionolle–rubber blends

To find out the better crosslinking monomer for vulcanization of natural rubber under electron beam (EB) radiation, the dry rubber was masticated with different polyfunctional monomers like TMPTA, NVP, and ethylene glycol diacrylate of different numbers of CH₂ CH₂ O group, such as 1G, 3G, 7G, and 10 G. The masticated films were irradiated with different doses under EB at 10 kGy/pass. The highest tensile strength (25 MPa) of the rubber was observed in the presence of TMPTA (3phr) at 150 kGy dose. The gel content of the rubber increased with an increase of dose. Bionolle was mixed with the masticated rubber containing 3 phr TMPTA at different proportions; films of these blends along with Bionolle were irradiated under EB with different doses. The concentration of rubber in Bionolle and radiation dose were optimized. The elastomer with 5% masticated showed the highest tensile strength (62 MPa). The gel content of the blends was found to increase with an increase of radiation dose as well as rubber concentration in Bionolle. The elastomers or blends were found to possess good thermal properties. The elastomers exhibited a much lower loss of tensile strength due to the thermal aging compared with pure Bionolle. The elastomers sustained their original shape for 300 min at 180°C, whereas Bionolle sustained its shape for only 3 min at 120°C under the same load (50 g). Among all the elastomers, 5% rubber containing elastomer was found to be better in all respects. It was observed from scanning electron microscopy and differential scanning calorimetry studies that 5% rubber is well mixed with Bionolle. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 799–807, 2001     

Physicochemical properties of irradiated and loaded LDPE films with polyfunctional monomers

Polyfunctional monomers (PFMs), namely, trimethylol propane trimethacrylate (TMPTMA), trimethylol propane triacrylate, ethylene glycol dimethacrylate, and diethylene glycol diacrylate were blended with low‐density polyethylene (LDPE) and exposed to different doses of EB irradiation. Fourier transform infrared and ultraviolet and UV–vis spectroscopy of the unirradiated, irradiated, unloaded, and PFMs‐loaded LDPE films were studied under various irradiation doses up to 300 kGy. The degree of crosslinking and oxidative degradation, as measured by the spectroscopic parameters, were dependent on both the irradiation dose and the type of loaded PFMs. For all of the loaded monomers, the extent of crosslinking increased at different rates as a function of irradiation dose. TMPTMA monomer was the most efficient in enhancing the crosslinking of LDPE films compared to the other loaded monomers. However, the unloaded LDPE film showed the least extent of crosslinking. In addition, the EB‐radiation‐induced changes, such as trans‐vinylene formation, a decrease in vinyl and vinylidene unsaturation; and carbonyl double‐bond formation and change in crystallinity were correlated. The importance of these results on the prediction of the role of polyfunctional monomers in the production of crosslinked polymers is discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2025–2035, 2003