Thermal,mechanical, and structural investigation of the effect of electron beam‐irradiation in Bayfol nuclear track detector

Samples from sheets of the polymeric material Bayfol have been exposed to electron beam in the dose range 10–100 kGy. The resultant effect of electron beam irradiation on the thermal properties of Bayfol has been investigated using thermogravimetric analysis. The onset temperature of decomposition T₀ and activation energy of thermal decomposition E_a were calculated, results indicating that the Bayfol polymer decomposes in one main weight loss stage. Also, the electron irradiation in the dose range 40–100 kGy led to a more compact structure of Bayfol polymer, which resulted in an improvement in its thermal stability with an increase in activation energy of thermal decomposition. The variation of transition temperatures with electron dose has been determined using differential thermal analysis. The results indicate that the electron irradiation in the dose range 40–100 kGy causes crosslinking that destroys the crystalline structure depressing the melting temperature and this is most suitable for applications requiring the molding of this polymer at lower temperatures. In addition, the mechanical and structural properties of Bayfol samples were measured and the results revealed that the tensile strength, elongation at break, yield strength, and intrinsic viscosity were affected by the electron doses. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Novel electron beam‐modified surface‐coated silica fillers: Physical and chemical characteristics

A novel process of surface modification of silica fillers has been performed by coating with an acrylate monomer, trimethylol propane triacrylate (TMPTA) and with a silane coupling agent, triethoxy vinyl silane (TEVS), followed by electron beam irradiation of these coated fillers. The surface‐modified fillers have been characterized by Fourier‐Transform Infrared Analysis (FTIR), Electron Spectroscopy for Chemical Analysis (ESCA), Contact angle measurements by dynamic wicking method, Scanning Electron Microscopy (SEM), Energy dispersive X‐ray spectroscopy (EDX), Transmission Electron Microscopy (TEM), Fractal studies, Thermogravimetric analysis (TGA), and X‐ray diffraction (XRD) studies. Presence of the acrylate and the silane coupling agent on the modified fillers is confirmed from the above studies. The contact angle measurements suggest a significant improvement in hydrophobicity of the treated fillers, which is supported by water flotation test. After irradiation and acrylate treatment an increase in filler aggregation is observed, which is not as significant in the case of silanized silica filler. However, XRD studies demonstrate that the entire modification process does not alter the bulk properties of the fillers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2255–2268, 2002     

Effect of electron beam irradiation on mechanical properties of high density polyethylene and its blends with sericite‐tridymite‐cristobalite

Some oxygen containing groups (mainly the CO group) are formed on the molecular chain of high density polyethylene (HDPE) during electron beam irradiation in air. The affinity between HDPE and sericite‐tridymite‐cristobalite (STC), the dispersion of STC in the HDPE matrix, and the mechanical properties of the HDPE/STC blend are improved quite a lot by the introduction of polar groups. Compared with HDPE, the tensile and impact strength of electron beam irradiated HDPE (30 kGy)/STC (60/40) are increased to 29.0 MPa and 518 J/m, respectively, from 24.5 MPa and 215 J/m; the tensile and impact strength of irradiated HDPE (30 kGy)/STC (50/50) are 31.1 MPa and 424 J/m, respectively. The Ceast impact test showed that the increase of impact strength was mainly due to the strong interfacial adhesion between irradiated HDPE and STC, thus preventing the spreading of cracks over wide areas. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 243–249, 2000     

Structure of P(VDF‐TrFE) (80/20) copolymers under electron irradiation and recrystallization

The structural changes of irradiated and recrystallized copolymers of vinylidene fluoride and trifluoroethylene [P(VDF‐TrFE)] (80/20) copolymers have been investigated through IR spectra, X‐ray, and DSC. It is found that recrystallization has a reverse effect on irradiated P(VDF‐TrFE) copolymers, by which the irradiated samples are turned back to original nonirradiated state partially. During recrystallization, trans‐gauche sequences are replaced by all‐trans conformation gradually and the irradiated P(VDF‐TrFE) (80/20) copolymers change from nonpolar phase to polar one. The average crystallite size of polar phase is larger than that in irradiated samples, and the difference between recrystallized and irradiated samples reduces gradually with irradiation dosage. The C?C and conjugated C?C bonds are also found in the recrystallized‐irradiated P(VDF‐TrFE) (80/20) due to rearrangement of broken bonds. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4258–4263, 2006     

Synthesis of starch‐based plastic films by electron beam irradiation

Starch‐based plastic films were prepared by the electron beam irradiation of starch and poly(vinyl alcohol) (PVA) in a physical gel state at room temperature. The influence of starch/PVA composition, irradiation dose, and plasticizer (glycerol) on the properties of the plastic films was investigated. The gel fraction of the starch/PVA films increased with both the radiation dose and PVA content in the plastic film and decreased with increasing glycerol concentration. The starch/PVA compatibility was determined by measurement of the thermal properties of the starch/PVA blends with various compositions with differential scanning calorimetry. The swelling of the starch/PVA films increased with increasing PVA content and decreasing irradiation dose. Mechanical studies were carried out, and the tensile strength of the films decreased at high starch ratios in the starch‐based mixture. This was due to the decrease in the degree of crosslinking of starch. Furthermore, when PVA, a biodegradable and flexible‐chain polymer, was incorporated into the starch‐based films, the properties of the films, such as the flexibility (elongation at break), were obviously improved. The tensile strength of the films decreased with increasing glycerol concentration, but elongation at break increased up to a maximum value at a 20% glycerol concentration, and then, it leveled off and decreased slightly. Biodegradation of the starch/PVA plastic films was indicated by weight loss (%) after burial in soil and morphological shape, which was detected by scanning electron microscopy. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 504–513, 2007     

Structure and morphology of isotactic polypropylene functionalized by electron beam irradiation

The structure and morphology of isotactic polypropylene (iPP), functionalized by electron beam irradiation at room temperature in air, are investigated by elementary analysis, FT‐infrared (FTIR) spectroscopy, electron spectroscopy for chemical analysis (ESCA), polariscope, and static contact angle. Elementary analysis reveals that the element oxygen has been introduced onto iPP chains after electron beam irradiation. In addition, as shown from FTIR spectra, oxygen‐containing groups, such as carbonyl, carboxyl, and ether groups, are introduced onto iPP molecular chains. The dependence of oxygenation extent (as measured by O_1S/C_1S value of ESCA spectra) on electron beam dose is obtained. Under polariscope, it can be observed that the dominant alpha phase appears to become more enhanced, and there is no crystalline phase transition. The static contact angle of iPP decreases with increasing dose. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 75–82, 2000     

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     

Effect of controlled electron beam irradiation on the rheological properties of nanosilica‐filled LDPE‐EVA based thermoplastic elastomer

The effect of controlled electron beam irradiation on the rheological properties of a model LDPE‐EVA thermoplastic elastomer (TPE) system filled with silica nanoparticles is explored in this article. The pristine silica particles were mixed with LDPE‐EVA system in molten condition by varying the sequence of addition and amount of nanosilica. In one composition, Si69 was used to improve the state of dispersion of nanosilica. The rheological behavior of irradiated TPE systems is influenced remarkably by irradiation dose, loadings of silica, variation of sequence, and addition of Si69. All filled TPE systems register an increase in elastic response with increasing frequency and with increase in irradiation dose. Upon irradiation, melt viscosity increases when compared with the unirradiated samples because of the crosslinking effect and improvements in interfacial bonding. The viscoelastic response varies markedly with the temperature. The radiation sensitizing effect of silica is reflected from the rheological data. The dynamic and steady shear rheological properties do not follow a simple correlation. Finally, the rheological behavior is correlated with the morphology of the irradiated systems processed at various shear rates. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Influence of untreated and novel electron‐beam‐modified surface‐coated silica filler on the thermorheological properties of ethylene–octene copolymer

We developed surface‐modified silica fillers by coating these with an acrylate monomer, trimethylolpropane triacrylate, or a silane coupling agent, triethoxyvinyl silane, followed by electron‐beam irradiation at room temperature. These were incorporated in an ethylene–octene copolymer rubber. Thermorheological studies of the unvulcanized ethylene–octene copolymer and its untreated and modified silica‐filled composites were done with a shear dynamic oscillating rheometer. Modification of the silica filler, especially via the silanization process followed by electron beam treatment, significantly reduced filler–filler networking as revealed from the log–log plots of storage modulus and complex shear viscosity, and its real component. The rheological complexity of the compositions was analyzed from a double logarithmic plot of the storage modulus and loss modulus. The results obtained from the master curves constructed on the basis of the time–temperature superposition principle and the activation energy calculated from the Arrhenius equation for the flow of above these compounds further supported these findings. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2453–2459, 2003     

Influence of laser irradiation on the optical and the mechanical properties of Makrofol‐DE polycarbonate

The effect of IR laser irradiation on the optical and the mechanical properties of Makrofol‐DE 1‐1 CC polycarbonate films were investigated. Three hundred microns‐thick films of Makrofol‐DE 1‐1 CC polycarbonate were irradiated with 0.00–10.40 J/cm² of Ga‐As laser pulses, 904 nm, 5 W, and 200‐ns pulse duration. Fourier transform infrared spectroscopy measurements showed that (C?O) groups degrade under laser irradiation at the studied fluence range. The aliphatic and aromatic (C? H) groups exhibited the same behavior, which can be attributed to nature of laser interaction with matter. The Makrofol samples exhibited degradation under the effect of laser irradiation up to 0.94 J/cm², where crosslinking mechanism started and continued until 7.07 J/cm². The refractive index had a minimum value at 0.94 J/cm² and maximum value at 7.07 J/cm² due to the degradation and crosslinking formation inside the sample, respectively. The decrease in elastic modulus, E, of Makrofol irradiated with 0.47–0.94 and 7.07–10.40 J/cm² indicates that the sample becomes more flexible, which results from the decrease in interatomic force constants. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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

Solutions of carboxymethyl sago pulp (CMSP) of various degree of substitution were irradiated with electron beam of various radiation doses. The gelation dose (D_g) and p_o/q_o ratio (p_o is degradation density, q_o 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 p_o/q_o 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     

Effects of γ‐aminopropyltriethoxylsilane on morphological characteristics of hybrid nylon‐66‐based membranes before electron beam irradiation

Nylon‐66 is a typical semicrystalline polymer that can be crosslinked using crosslinking agents and electron beam irradiation. Hybrid nylon‐66‐based membranes are more porous but denser compared to the pure nylon‐66 membrane. Besides that, hybrid nylon‐66 membranes exhibit higher water uptake and severe swelling in water. Si/nylon‐66 membranes were prepared by adding γ‐aminopropyltriethoxylsilane (APTEOS). Crosslinked silica in nylon‐66 membranes is confirmed with high gel content and Fourier transform infrared peaks, but XRD results showed that there is a low crystalline degree in these membranes. The thermal stability of hybrid nylon‐66 membranes is also less affected by APTEOS. The crosslinking agent only improves storage modulus in hybrid nylon‐66 membranes. After irradiation, it is learned that APTEOS improves separation performance of nylon‐66 membranes. However, excessive APTEOS causes the ratio of effective thickness over porosity (Δx/A_k) reduces significantly resulting a lower permeability membrane. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effects of natural antioxidants on the lipid profile of electron beam‐irradiated beef burgers

The purpose of this study was to assess the efficacy of rosemary and oregano extracts in avoiding oxidative changes in beef burgers, and to evaluate the fatty acid profile of these products after electron beam exposition. Extracts, individually or in combination, were added to beef burgers and compared to synthetic antioxidants commonly used in food (butylated hydroxytoluene, butylated hydroxyanisole). The ground beef were submitted to electron beam irradiation at doses of 0, 3.5 and 7 kGy, and stored for 90 days. At regular time intervals, lipid oxidation and fatty acid composition were evaluated through measurement of thiobarbituric acid‐reactive substances (TBARS) and gas chromatography, respectively. The results indicate that, although the irradiation process triggers an increase in the lipid oxidation ratio expressed by TBARS values, great changes in the fatty acid profiles were not observed; instead, they continued to present characteristics very similar to that of non‐irradiated beef. Thus, as irradiation doses of up to 7 kGy for frozen meat can make foods safe from foodborne pathogens, natural antioxidants derived from spices are able to reduce and avoid lipid changes that may cause a deterioration of the sensory quality of these foods, and these natural extracts offer a good choice for replacing synthetic additives.     

Metallocene ethylene‐co‐(5,7‐dimethylocta‐1, 6‐diene) copolymers crosslinked using electron beam irradiation: a tunable alternative

Ethylene‐co‐(5,7‐dimethylocta‐1,6‐diene) copolymers with various 5,7‐dimethylocta‐1,6‐diene contents incorporate double bonds in the lateral chains that facilitate the development of crosslinkings in the resulting polymeric material after electron beam irradiation. As an effect of such irradiation, crystallization is delayed but crystallinity remains practically constant after melting and further cooling of irradiated specimens. Crystallinity, crystallite thickness and gel content are key parameters in the mechanical performance of these copolymers. Consequently, the controlled incorporation of non‐conjugated dienes into the polyethylene structure appears as an alternative strategy for tuning the mechanical response in crosslinked polyolefins. Moreover, the resulting materials exhibit good thermal stability. Copyright © 2011 Society of Chemical Industry     

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     

Biodegradation of low‐density polyethylene/thermoplastic starch foams before and after electron beam irradiation

Foamy low‐density polyethylene/plasticized starch (LDPE/PLST) blends at different compositions were produced in the presence of azodicarbonamide (ACA) compound as foaming agent. The LDPE/PLST blends before and after electron beam irradiation were investigated in terms of mechanical properties, bulk density, and structure morphology. Moreover, the biodegradability of these materials was evaluated by the soil burial test for 2 months, in which the buried sheets were also examined by scanning electron microscopy (SEM). The results showed that the increase of PLST content from 24 to 30% was accompanied by a decrease in the yield and break stresses of 10 and 20% for the unirradiated blends without the foaming agent, respectively. Further decrease in these mechanical parameters was observed after the foaming process. The bulk density, void fraction, cell size measurements as well as the examination by SEM illustrate clearly the cell growth of the foam structure. The soil burial test and SEM micrographs indicate the growth of microorganisms overall the blend sheets and that the blend was completely damaged after two months of burying. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Optical parameters and absorption studies of UV‐irradiated azo dye‐doped PMMA films

PMMA and PMMA films doped with different contents of azo dye have been made by using the casting technique. The absorption spectral analysis showed that the doped films have two absorption bands attributed to the π‐π* and n‐π* transition of chromophore groups. These bands disappear upon UV‐irradiation, suggesting that the studied system undergoes a photo degradation process. The absorption coefficient and optical energy gap (E_g) have been obtained from the absorption edge in the 200–900 nm range. It was found that E_g decreases with increasing doping levels, whereas it increases with increasing irradiation time. The width of the tail of localized states in the band gap (ΔE) was evaluated using the Urbach edge method. Some optical parameters were determined from the reflection and transmission spectra in the spectral range of 200–2500 nm. The dependence of the refractive index on irradiation time and doping level have been discussed. It was found that the photo‐induced refractive index changes are very large. These changes suggest the applicability of the studied system in optical devices. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of the electron beam irradiation on the properties of epoxidized natural rubber (ENR 50) compatibilized linear low‐density polyethylene/soya powder blends

Linear low‐density polyethylene/soya powder blends were prepared by using an internal mixer at 150°C. The soya powder content ranged from 5 to 40 wt %. Epoxidized natural rubber with 50 mol % epoxidation (ENR 50) was added as a compatibilizer. The blends were irradiated by electron beam (EB) at a constant dose of 30 kGy. The changes in gel fraction, tensile properties, morphological and thermal properties of the samples were investigated. The gel content increased after EB irradiation. However, the increment of gel content was hindered by increasing soya powder content. The tensile strength and Young's modulus of the blends were increased by EB whereas the elongation at break decreased. The tensile fracture surface also support the reduction of elongation at break by EB irradiation. Further analysis on the irradiated blends using Fourier transform infrared spectra indicated an increase of oxygenated product after undergoing EB irradiation. The differential scanning calorimetry result indicated that the melting temperature of the blends decreased after EB irradiation whereas the crystallinity increased. EB irradiation also enhanced the thermal stability of the blends as indicated by thermogravimetric analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Structure and mechanical properties of isotactic polypropylene and iPP/talc blends functionalized by electron beam irradiation

The structure and mechanical properties of isotactic polypropylene (iPP) functionalized by electron beam irradiation are investigated by differential scanning calorimetry, wide‐angle X‐ray diffraction, thermogravimetry, thermomechanical analysis, melt index and mechanical measurements. The experimental results show that the degree of crystallinity, the thermal degradation temperature and the dimensional stability increase with dose in the range 0–5 kGy. At 5 kGy, the initial and final degradation temperatures of the irradiated iPP are raised by 66 °C and 124 °C, respectively. The melt index increases with increasing dose. The mechanical measurements show that the stiffness of iPP is greatly enhanced by electron beam irradiation. A small dose of irradiation (0.75 kGy) can increase the Young's modulus to 1284 MPa compared with 1112 MPa for unirradiated iPP. Adding 10 % by weight of irradiated iPP powder into iPP/talc (70/20 % by weight) blends, changes the processing parameters significantly and makes the Young's modulus rise substantially. At a dose of 40 kGy the Young's modulus of iPP/talc blend jumps to 3611 MPa against the original 2201 MPa. © 2000 Society of Chemical Industry