Improvement of processability of poly(ε‐caprolactone) by radiation techniques

Improvement of processability of Poly(ε‐caprolactone) (PCL) was achieved by introduction of a branch structure using gamma‐irradiation from a ⁶⁰Co source. Irradiated PCL has higher molecular weight by producting a branch structure. Hence, the irradiation at a lower dose, such as 3 Mrad, leads to a higher melt viscosity. The branched structure gave improved properties for dynamic viscoelasticity and elongational viscosity. High elongational viscosity was observed by entanglement due to branch chain formed during irradiation, and the elongational viscosity for 3 Mrad is higher than 1.5 Mrad. Due to a higher elongational viscosity, PCL foam can be produced by a molding process. Foam produced from irradiated PCL pellets at 3 Mrad has honeycomb‐like structure, and the foam showed higher enzymatic degradation compared to film samples. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1815–1820, 1999     

Radiation effects of an electron beam on the microhardness of poly(methyl methacrylate): Poly(chlorotrifluoroethylene) polyblends

Specimens of poly(methyl methacrylate) (PMMA): poly(chlorotrifluoroethylene) (PCTFE) polyblends with different weight percentage ratios were subjected to electron beam irradiation (1–10 Mrad). The effect of irradiation on the strength of the blend specimens was studied by measuring the surface microhardness using a Vicker's microhardness tester attached to a Carl Zeiss NU 2 Universal research microscope. Significant changes were observed in the Vicker's hardness number, H_v. An irradiation dose of 3 Mrad was found to enhance greatly the microhardness level of the specimens. An increase of approximately 78% in microhardness was observed as the radiation dose was increased from 1 to 3 Mrad. Electron irradiation was also found to induce crosslinking and degradation in the material. The degree of crosslinking was found to be maximum at a dose of 3 Mrad. Specimens incorporating 10 wt% PCTFE were found to exhibit the highest level of microhardness at all radiation doses.     

Electron‐beam curing of hydrogenated acrylonitrile–butadiene rubber

The 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     

辐照交联对PE-HD薄膜结构和性能的影响

制备了辐照改性的高密度聚乙烯(PE-HD)薄膜,并对薄膜的结构和性能进行了分析。结果表明,随着辐照剂量的增加,薄膜的拉伸强度、耐撕裂强度得到提高,而薄膜的韧性降低太大。当辐照的剂量由1Mrad提高到6Mrad时,薄膜的纵向拉伸强度由20.5MPa提高到了23.2MPa,横向拉伸强度由18.1MPa提高到了19.5MPa,而纵向撕裂强度由11.8mN提高到了17.2mN,横向撕裂强度由8.3mN提高到了9.3mN,可见适度的辐照剂量可提高薄膜的力学性能,同时当辐照的剂量由1Mrad提高到6Mrad时,薄膜的断裂伸长率变化不大,当辐照剂量达到8Mrad时,薄膜的力学性能提高明显,而随着辐照剂量的进一步提高,薄膜的力学性能下降明显,同时凝胶含量增加,分子间的交联程度提高,从薄膜的熔体流动速率测试结果可以看到这种趋势。     

Radiational hardening of poly(vinylidene fluoride)–poly(methyl methacrylate)–polystyrene ternary blends

Specimens of poly(vinylidene fluoride) (PVDF)–poly(methyl methacrylate) (PMMA)–polystyrene (PS) polyblends with different weight percentage ratios of the three polymers were prepared with the solution cast technique. The effect of γ irradiation on the Vicker's microhardness was studied. Among the three pure polymers, PVDF, PMMA, and PS, the γ irradiation imparted crosslinking in PVDF, thereby causing radiational hardening. In the cases of PMMA and PS, the effect of irradiation exhibited a predominance of both the scissioning and crosslinking processes in different ranges of doses. Moreover, at a dose of 5 Mrad, in both PMMA and PS, maximum radiational crosslinking was observed. The effect of γ irradiation seemed to stabilize beyond 15 Mrad in PVDF and beyond 20 Mrad in PMMA and PS. Microhardness measurements on ternary blends of PVDF, PMMA, and PS revealed that the blend with low contents of PMMA, that is, up to 5 wt %, yielded softening, whereas increasing the content of PMMA beyond 5 wt % produced a hardened material because of radiational crosslinking, and a higher content of PMMA in the blend facilitated this crosslinking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3107–3111, 2004     

聚己内酯的辐射交联及改性研究

实验研究了多官能团单体(PFM)对聚己内酯(PCL)的辐射交联效应及对PCL的力学性能的影响。结果表明,在相同辐照剂量时,多官能团单体的用量越大,官能团数目越多,所生成凝胶含量越多,辐照交联效应越明显。并研究了无机羟基磷酸钙粉末(CPP)作填料时对PCL的增强作用,发现随着CPP用量的增加,共混物的拉伸强度提高,但对PCL的辐射交联没有影响。     

Structural modifications in an irradiated ethylene-vinyl alcohol copolymer

Extraction experiments and calorimetric measurements have been performed, on a commercial ethylene-vinyl alcohol copolymer irradiated in the dose range 0–20 Mrad. The results support the idea that crosslinking predominates over chain scission at small irradiation doses and all together is the main effect in the explored dose range.     

Crosslinking of polycaprolactone in the pre-gelation region

Polycaprolactone (PCL) crosslinked below the gel point either with peroxide or by exposure to ionizing radiation was compared by Theological studies. As a result of peroxide crosslinking, PCL increases in viscosity and shear rate dependence and exhibits increased dynamic moduli that converge at higher frequencies. The analysis of gases evolved from γ-irradiated PCL shows that the yield of hydrogen (G = 0.39) approximates the sum of the yields of carbon monoxide (G = 0.19) and carbon dioxide (G = 0.21). It is inferred that equal amounts of crosslinking and scission result from ionizing irradiation. As a result, PCL is converted by irradiation to a densely branched system. Steady shear viscosities do not depend strongly on dose and overlap at higher shear rates. Similarly, dynamic moduli, especially G″, become less sensitive to dose.     

Electron beam‐induced piezoelectric phase in poly(vinylidene fluoride) nanohybrid: effect at the molecular level

A nanohybrid has been synthesized by incorporating organically modified layered silicate in a poly(vinylidene fluoride) (PVDF) matrix. Molecular‐level phenomena have been explored after exposing PVDF and its nanohybrid to an electron beam of varying doses. The electron beam interacts with polymer chains and thereby generates different free radicals, the number of which is quite high in nanohybrid as compared to pure PVDF. The stability of free radicals has been confirmed through density functional theory energy minimization, predicting stable β‐phase free radicals in the nanohybrid. Quantitative analyses of chain scission, crosslinking and double bond formation are reported and compared after irradiation for both PVDF and its nanohybrid using UV‐visible and Fourier transform infrared spectroscopies, sol–gel analyses and gel permeation chromatography, revealing both chain scission and crosslinking phenomena in irradiated PVDF and its nanohybrid, but at higher dose (>90 Mrad) crosslinking dominates in the nanohybrid due to more free radicals and proximity of radical chains on top of templated system in the nanohybrid as compared to pure PVDF. The enhanced crosslinking alters the nanostructure causing disappearance of the peak at 2θ ≈ 3°. Moreover, the electron beam induces significant piezoelectric β‐phase in the nanohybrid against only α‐phase in pure PVDF at a similar dose and raises the possibility for the use of electron‐irradiated nanohybrid as an electromechanical device. β‐Phase formation is also supported through solid‐state NMR, scanning electron microscopy and differential scanning calorimetry studies. The thermal properties in terms of heat of fusion and degradation temperature have been verified indicating steady decrease of melting point and heat of fusion for pure PVDF while considerably less effect is observed for the nanohybrid. The combined effect of chain scission and crosslinking makes both PVDF and its nanohybrid brittle, but with greater stiffness with respect to unirradiated specimens. © 2014 Society of Chemical Industry     

纤维素辐照改性及其应用

辐照技术利用电离辐射诱发物理化学反应(例如交联、聚合、接枝、降解等)对材料进行加工或改性,与常规加工方法相比,具有节能、无环境污染等特点。将辐照技术应用于纤维素改性过程近年已成为非动力核技术应用领域研究的热点之一。本工作对目前纤维素的辐照技术及其基本反应机理进行了概述,其中包括纤维素膜材料、纤维素水凝胶、纤维素微晶/纳米材料,并对纤维素辐照改性过程的辐照环境,包括溶剂、敏化剂、温度、辐照剂量、环境氛围、结晶度等进行了总结。     

Electron beam irradiation of ethylene‐propylene terpolymer: Evaluation of trimethylol propane trimethacrylate as a crosslink promoter

The effect of electron beam irradiation on ethylene‐propylene terpolymer (EPDM) was investigated. A 50‐part oil‐extended EPDM with high termonomer (ENB) content (iodine number of base polymer) 19, was selected for this study. An increase in irradiation dose from 0 to 200 kGy resulted in increased crosslinking, measured by an increase in gel contents and better swelling resistance. The effect of the multifunctional monomer trimethylol propane trimethacrylate (TMPTMA) as a crosslink promoter was studied using IR spectroscopy. The IR studies revealed enhanced peak absorbances at 1725, 1257, and 1023 cm^?1 as a result of the increased concentration of C = O and C‐O‐C groups and reduced absorbance at 1630 cm^?1 due decreased concentration of C = C groups with TMPTMA level in the irradiated samples. The presence of TMPTMA increased the level of crosslinking at a given irradiation dose, which was manifested by improvement in tensile properties. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 968–975, 2005     

Heat resistance of radiation crosslinked poly(ε-caprolactone)

Polycaprolactone (PCL) was gamma-irradiated at different phases such as solid state at 30 to 55°C, molten state, and supercooled state, under vacuum or air atmosphere, to elucidate its crosslinking behavior. Irradiation in the molten state (80°C) gave higher gel content compared to room temperature. The resulting gel, however, contains many voids due to the gas evolved during irradiation. Conversely, irradiation of PCL in the supercooled state led to the highest gel content among the three irradiation conditions and it was free of voids. Based on these findings, to evaluate heat resistibility of crosslinked PCL prepared by irradiation in supercooled state, the crosslinked PCL was hot pressed at 200°C to form a film. Unirradiated PCL melted at 60°C. The film prepared from 160 kGy irradiated PCL (crosslinked sample) under an applied load of 0.667 MPa, at a temperature of 110°C did not break even after 3 h. At a temperature of 120°C, the film has a tensile strength of 3 MPa. Furthermore, the film extended by hot pressing is transparent and has high heat shrinkability. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 581–588, 1998     

Electron‐beam irradiation of poly(vinyl chloride)/epoxidized natural rubber blends in presence of trimethylolpropane triacrylate

Electron‐beam initiated crosslinking of poly(vinyl chloride)/epoxidized natural rubber blends, which contained trimethylolpropane triacrylate (TMPTA), was carried out over a range of irradiation doses (20–200 kGy) and concentrations of TMPTA (1–5 phr). The gel content increased with the irradiation dose and the TMPTA level, although the increase was marginal at higher doses and higher TMPTA levels. Blends containing 3–4 phr TMPTA achieved optimum crosslinking, which in effect caused the maximum tensile strength (TS) at a dose of 70 kGy. A further addition of TMPTA caused a decline in the TS above 40 kGy that was due to embrittlement, which is a consequence of excessive crosslinking and the breakdown of the network structure. The possible formation of a more open network as a result of the breakdown of the network structure was further confirmed by the modulus results. Dynamic mechanical analysis (tan δ curve) and scanning electron microscopy studies on samples irradiated at 0 and 200 kGy were undertaken in order to gain further evidence on the irradiation‐induced crosslinking. The plasticizing effect of TMPTA prior to irradiation and the formation of microgels upon irradiation were also discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1926–1935, 2001     

Properties of γ-irradiated compostions based on polyvinyl chloride

A Co-60 source was used to irradiate compositions based on PVC, and containing plasticizer additives including DIDP and TOTM, and chlorinated PE (CPE). Polyfunctional acrylic monomers were used as crosslinking agents, and irradiation dosages to about 8Mrad were applied to crosslink the compounds. Analyses included crosslink density estimates from solvent swelling data, and stress/strain evaluations of mechanical responses. It was shown that plasticizers reduce the crosslinking efficiency of irradiation, TOTM being the better inhibitor. The presence of CPE counteracts the trend. Mechanical properties differentiate strongly between the use of difunctional and trifunctional crosslinking agents. The latter produce networks at higher dosages (Eq > 4Mrad) characterized by two apparent yield stresses. This suggests the presence of two (or more) distinct network structures. DSC scans of partially crosslinked samples support the contention. The work indicates the importance of composition-property relationships in multicomponent vinyl systems.     

Evidence of irradiation‐induced crosslinking in miscible blends of poly(vinyl chloride)/epoxidized natural rubber in presence of trimethylolpropane triacrylate

Electron‐beam initiated crosslinking of a poly(vinyl chloride)/epoxidized natural rubber blend (PVC/ENR), which contained trimethylolpropane triacrylate (TMPTA), was carried out over a range of irradiation doses (20–200 kGy) and concentrations of TMPTA (1–5 phr). The gelation dose was determined by a method proposed by Charlesby. It was evident from the gelation dose, resilience, hysteresis, glass‐transition temperature (T_g), IR spectroscopy, and scanning electron microscopy studies that the miscible PVC/ENR blend underwent crosslinking by electron‐beam irradiation. The acceleration of crosslinking by the TMPTA was further confirmed in this study. Agreement of the results with a theory relating the T_g with the distance between crosslinks provided further evidence of irradiation‐induced crosslinking. The possible mechanism of crosslinking induced by the irradiation between PVC and ENR is also proposed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1914–1925, 2001     

Enhanced Interfacial Adhesion of Bioflour‐Filled Poly(propylene) Biocomposites by Electron‐Beam Irradiation

Summary: The effect of electron‐beam (EB) irradiation on interfacial adhesion in bioflour (rice‐husk flour, RHF)‐filled poly(propylene) (PP) biocomposites in which either only the RHF had been EB irradiated or the whole biocomposite had been EB irradiated was examined at different EB‐irradiation doses. The tensile strengths of PP–RHF biocomposites with EB‐irradiated RHF and EB‐irradiated PP and PP–RHF biocomposites were slightly higher than those of the nonirradiated samples. The improved interfacial adhesion of PP–RHF biocomposites with EB radiated RHF and the EB‐irradiated PP–RHF biocomposites compared with the nonirradiated samples was confirmed by the morphological characteristics. In addition, the thermal stability of EB‐treated biocomposites was slightly higher than those of nonirradiated samples at the irradiation doses of 2 and 5 Mrad. However, at the high irradiation dose (30 Mrad), the tensile strengths of the biocomposites were slightly decreased by main‐chain scission (degradation) of PP and RHF. Attenuated total reflectance FT‐IR and X‐ray‐photoelectron‐spectroscopy findings confirmed this result by showing that that EB irradiation changed the functional groups of RHF, PP, and the biocomposites and improved the surface characteristics of the biocomposites. The thermal characteristics of the EB‐irradiated PP and biocomposites were investigated using differential scanning calorimetry. From the results, we concluded that use of low‐dose EB radiation increases the interfacial adhesion between matrix polymer and biofiller.

     

Radiation vulcanization of hydrogenated acrylonitrile butadiene rubber (HNBR)

Raw polymer and compound of hydrogenated acrylonitrile butadiene rubber (HNBR) were subjected to γ-ray irradiation. Crosslinking was found to be the main chemical reaction induced by irradiation; the ratio of chain scission to crosslinking as well as the does at which gelation occurred were determined from gel content measurements to be 0.41 and 3.8 Mrad, respectively. The excellent hot-air and oil-resistant properties should be retained because no formation of double bonds or changing of the nitrile groups were observed with in the optimum dose range. Desired mechanical properties of the vulcanizate may be conveniently obtained by controlling the radiation dose. © 1994 John Wiley & Sons, Inc.     

Shape‐memory behaviors of sensitizing radiation‐crosslinked polycaprolactone with polyfunctional poly(ester acrylate)

The sensitizing effects of polyfunctional poly(ester acrylate) on the radiation crosslinking of polycaprolactone (PCL) were studied. The influences of the use of the polyfunctional material, the number of functional groups, and the radiation dose on the radiation crosslinking, dynamic mechanical properties, and shape‐memory behaviors of PCL, respectively, were investigated. The radiation crosslinking of PCL, under the conditions in which the polyfunctional material was applied, did not follow the classic Charlesby–Pinner equation but instead followed the Chen–Liu–Tang relation. The efficiency of the radiation crosslinking of PCL was distinctly improved with the polyfunctional material. The greater the usage and functional group number were, the greater gel content and the more distinctive the radiation‐crosslinking effects were. This also indicated that the polyfunctional material directly participated in the crosslinking reaction. Dynamic mechanical analysis indicated that enhanced radiation crosslinking better raised the heat deformation temperature of PCL and presented a higher and wider rubbery‐state plateau; it also produced greater strength at temperatures higher than the melting temperature and provided greater force for recovering the deformation than pure PCL. The shape‐memory results revealed that sensitizing crosslinked PCL presented 100% recoverable deformation and a quicker recovery rate. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 634–639, 2005     

辐照交联PVC／EVA共混物的形态结构与性能

以电子束为辐照源，以三羟甲基丙烷三丙烯酸酯（TMPTA）单体为交联敏化剂，对聚氯乙烯与乙烯－醋酸乙烯共聚物（EVA）的共混物进行辐照交联。采用红外吸收光谱、扫描电镜方法分析了添加改性EVA的共混物形态结构。通过凝胶含量、力学性能的测定，得到结论：EVA共聚物与PVC共混可以促进PVC辐照交联，改性EVA促进效果更明显；辐照剂量增大、体系凝胶含量增加，力学性能及热延伸性能提高，但辐射剂量高于5Mrad之后，体系降解程度明显增加。     

Structure and properties of closed‐cell foam prepared from irradiation crosslinked silicone rubber

Silicone rubber foam was prepared through crosslinking with electron beam irradiation and foaming by the decomposing of blowing agent azobisformamide (AC) in hot air. The crosslinking and foaming of silicone rubber was carried out separately, which was different from the conventional method of chemical crosslinking and foaming. After foaming, the silicone rubber foam was irradiated again to stabilize the foam structure and further improve its mechanical properties. The effects of irradiation dose before and after foaming, and the amount of blowing agents on the structure and properties of silicone rubber foam were studied. The experimental results show that with the increase of AC content, the average cell diameter of silicone rubber foam increases a little, the foam density decreases to a minimum value when AC content is 10 phr. With the increase of irradiation dose before foaming from 10 to 17.5 kGy, the cell nucleation density of silicone rubber foam increases, the average cell diameter decreases, and the foam density increases. With the increase of irradiation before foaming, the tensile strength, tensile modulus, and the elongation at break of the silicone rubber foam increase. Through irradiation crosslinking again after foaming, the foam density is decreased and the mechanical properties of silicone foam are further improved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009