Post-irradiation time effects on the graft of poly(ethylene-alt-tetrafluoroethylene) (ETFE) films for ion exchange membrane application

Grafting of styrene followed by sulfonation onto poly(ethylene-alt-tetrafluoroethylene) (ETFE) was studied for synthesis of ion exchange membranes. Radiation-induced grafting of styrene onto ETFE films was investigated after simultaneous irradiation (in post-irradiation condition) using a ⁶⁰Co source. The ETFE films were irradiated at 20 kGy dose at room temperature and chemical changes were monitored after contact with styrene for grafting. The post-irradiation time was established at 14 days when the films were remained in styrene/toluene 1:1 v/v. After this period the grafting degree was evaluated in the samples. The grafted films were sulfonated using chlorosulfonic acid and 1, 2-dichloroethane 20:80 (v/v) at room temperature for 5 h. The membranes were analyzed by infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), thermogravimetric measurements (TG) and degree of grafting (DOG). The ion exchange capacity (IEC) of membranes was determined by acid–base titration and the values for ETFE membranes were achieved higher than Nafion^® films. Preliminary single cell performance was made using pure H₂ and O₂ as reactants at a cell temperature of 80 °C and atmospheric gas pressure. The fuel cell performance of ETFE films was satisfactory when compared to state-of-art Nafion^® membranes.     

Radiation-grafting of 4-vinylpyridine and N-isopropylacrylamide onto polypropylene to give novel pH and thermo-sensitive films

Here 4-vinylpyridine (4VP) was grafted onto polypropylene films (PP) by mutual irradiation method to give PP-g-4VP; N-isopropylacrylamide (NIPAAm) was then grafted onto the PP-g-4VP films to give (PP-g-4VP)-g-NIPAAm by pre-irradiation method, using a ⁶⁰Co γ-source. The dependence of grafting percentage on radiation dose, temperature, reaction time, and monomer concentration was studied. (PP-g-4VP)-g-NIPAAm films were characterized by infrared spectroscopy (FTIR-ATR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The critical pH point and lower critical solution temperature (LCST) were determined by swelling and water contact angle measurements. The LCST also was determined by DSC. The binary graft copolymer films are shown to be thermo-pH sensitive.     

γ-Ray-induced grafting of DMAEMA and AAc onto PP by two step method

Binary graft copolymerization of thermosensitive 2-(dimethylamino) ethyl methacrylate (DMAEMA) and pH sensitive acrylic acid (AAc) monomers onto polypropylene (PP) films was carried out by a two step method using a ⁶⁰Co gamma radiation source. The PP film was initially modified by grafting of DMAEMA through a direct method. The DMAEMA-g-PP film obtained was then subjected to radiation grafting of AAc by the pre-irradiation method to give (DMAEMA-g-PP)-g-AAc. The optimal conditions, such as reaction time, reaction temperature, monomer concentration, and dose were studied. The grafted samples were verified by the FTIR-ATR spectroscopy and swelling; thermal properties were analyzed by DSC and TGA.     

Novel comb-type hydrogels of net-[PP-g-AAc]-g-4VP synthesized by gamma radiation,with possible application on Cu2+ immobilization

A novel comb-type grafted hydrogel system of net-[PP-g-AAc]-g-4VP was synthesized by gamma radiation in three steps. In the first step a pH sensitive graft copolymer of AAc onto PP film was obtained by radiation grafting of acrylic acid (AAc) onto polypropylene (PP) films in aqueous solution at radiation doses of 10 kGy with a ⁶⁰Co source. The grafted side chains of poly (acrylic acid) (PAAc) were then cross-linked with gamma radiation at different radiation doses to give net-[PP-g-AAc]. Finally, 4-vinylpyridine (4VP) was grafted into the net-[PP-g-AAc]. The comb-type grafted hydrogel obtained, net-[PP-g-AAc]-g-4VP, has been studied through determination of graft yield and swelling behavior at room temperature. Two critical pH values were found for net-[PP-g-AAc]-g-4VP at 4.5 and 7.2. Initial studies on the immobilization of Cu²⁺ ions from solution into net-[PP-g-AAc]-g-4VP films were performed.The comb-type grafted hydrogel, grafted onto PP was also characterized by differential scanning calorimetry (DSC), scanning electronic microscopy (SEM) and FTIR-ATR.     

Radiation-induced grafting of stimuli-responsive binary monomers: PDMAEMA/PEGMEMA onto PP films

Both poly[2-(dimethylamino) ethyl methacrylate] (PDMAEMA) and poly(ethylene glycol) methyl ether methacrylate (PEGMEMA) were radiation grafted onto polypropylene films (PP) using gamma radiation from a ⁶⁰Co source. PP was pre-irradiated by gamma ray for modification following by grafted PDMAEMA and PEGMEMA by a one step method. Grafting was studied as a function of the pre-irradiation dose between 20 and 180 kGy, dose rate of 10.4 kGy/h, and monomer concentration 50% of PDMAEMA/PEGMEMA (1/1) in different solvents (toluene, acetone, and methanol). FTIR-ATR, TGA, and DSC were carried out in the characterization of the graft copolymer obtained. Stimuli-responsive behavior and critical pH point were studied by swelling in water. pH and thermo-responsive films of PE-g-(DMAEMA/PEGMEMA) presented a lower critical solution temperature (LCST) of 50 °C and critical pH point around 8.7.     

Pre-irradiation induced grafting of styrene into crosslinked and non-crosslinked polytetrafluoroethylene films for polymer electrolyte fuel cell applications. I: Influence of styrene grafting conditions

Crosslinked and non-crosslinked polytetrafluoroethylene (PTFE) films [RX-PTFE and V-PTFE films, respectively], were irradiated in air at room temperature using γ-rays from a ⁶⁰Co source. The irradiated films were grafted with styrene in liquid phase. The grafting of styrene into PTFE films was proved by FT-IR spectroscopy. The influence of the reaction temperature and pre-irradiation doses on the resulted degree of grafting was discussed. The grafting speed and the degree of grafting were determined by the reaction temperature and pre-irradiation doses. The apparent activation energies were calculated as 39.7 kJ/mol for RX-PTFE films and 59.5 kJ/mol for V-PTFE films. The dependence index on absorbed doses at pre-irradiation for RX-PTFE films is 0.66, and for V-PTFE films it is 1.57. The geometric size changes of the grafted films were measured and discussed. Interestingly, the thickness of the grafted films was strongly influenced by the reaction temperature. The tensile strength and the elongation at break of the non-grafted and grafted RX-PTFE and V-PTFE films were measured. The grafted films then are sulfonated by chlorosulfonic acid for polymer electrolyte fuel cell (PEFC) applications and the highest IEC value gained is over 3. The analysis of the sulfonated films are now in progress.     

Radiation grafting of N,N′-dimethylacrylamide and 2-hydroxyethylmethacrylate onto polypropylene films by one step method

The work presented herein reports on polypropylene films grafted with N,N′-dimethylacrylamide and 2-hydroxyethylmethacrylate. The grafted films were obtained by an oxidative pre-irradiation method in one step using a gamma source of ⁶⁰Co. The optimal conditions such as reaction time, monomer concentrations and radiation doses were investigated. Characterization of the grafted polymers was carried out through FTIR-ATR, TGA, DSC, and swelling. Grafts onto polymeric films between 10 and 850% were obtained at doses from 20 to 150 kGy and a dose rate of 8.3 kGy/h.     

Relations entre la structure et les proprietes des membranes de polytetrafluoroethylene greffe—III. Membranes non-ionisables contenant de la poly-n-vinylpyrrolidone

Equilibrium properties (swelling) and transport phenomena (dialysis) of non-ionizable membranes, obtained by radiation grafting of N-vinylpyrrolidone onto thin PTFE films, were studied. Grafting was conducted by the direct method with monomer solutions in benzene. The overall activation energy of grafting determined between 20 and 50° is high (12.5 kcal mol^?1): the reaction is controlled by the monomer diffusion into PTFE film. The length of grafted chains increases with temperature.The molality of the membranes decreases when the temperature of grafting increases; for a given grafting ratio, the swelling is higher for membranes containing a small number of long grafts than for membranes with numerous short branches. The transfer of both ions and water is a function of the free volume in the films, it depends on the grafting ratio and is not influenced by the preparation conditions.     

Radiation grafted poly(vinylidene fluoride)-graft-polystyrene sulfonic acid membranes for fuel cells: Structure-property relationships

<正>Structure-property relationships for poly(vinylidene fluoride)-graft-polystyrene sulfonic acid(PVDF-g-PSSA) fuel cell membranes prepared by a single step method involving radiation-induced grafting of sodium styrene sulfonate(SSS) onto electron beam(EB) irradiated poly(vinylidene fluoride)(PVDF) films were established.The physico-chemical properties of the membranes such as ion exchange capacity,water swelling and proton conductivity were correlated with the degree of grafting(G,%) and the structural changes taking place in the membrane matrix during the preparation procedure. The variation in the crystallinity and the thermal stability of membranes was studied by differential scanning calorimetry (DSC) and thermogravimetric analysis(TGA),respectively.The membranes were found to undergo substantial structural changes in forms of ionic sites increase,hydrophilicity enhancement,hydrophobicity reduction and crystallinity decrease with the variation in G(%) and the preparation method.The structural and thermal properties of the obtained membranes were also compared with their counterparts prepared by a conventional two-steps method i.e.radiation induced grafting of styrene onto EB irradiated PVDF films followed by sulfonation.The PVDF-g-PSSA membranes obtained by a single-step method were found to have superior properties compared to those obtained by the conventional two-steps method.     

Radiation-induced grafting in the polyethylene–styrene system and differential thermal analysis of the grafted samples

The graft polymerization of styrene onto high-density polyethylene films was carried out by γ-irradiation in the vapor phase. Two methods were used for grafting in these experiments: a preirradiation method and a simultaneous irradiation method. The effects of these grafting methods on the reaction mechanism of grafting and on the properties of the grafted samples were investigated. The amounts of styrene homopolymer in the grafted samples is under 2% in the case of the preirradiation method and above 10% in the case of the simultaneous irradiation method. The activation energies were calculated to be 18 kcal/mole for grafting in the preirradiation method and 15 kcal/mole for weight increase of polyethylene films in styrene vapor. The difference in the dimensional expansion between in the direction of stretching and the direction prependicular to it is smaller with preirradiation grafting than with grafting by the simultaneous irradiation method. Differential thermal analysis of the grafted films shows an endothermic peak due thermal decomposition which decreases gradually from 450°C to 415°C with increase in degree of grafting from 30 to 60%. The lowering of this peak temperature appears at a lower degree of grafting when the preirradiation method is used. On the basis of these results, it is concluded that the reaction rate of radiation-induced grafting in the vapor phase depends closely upon the processes of adsorption, dissolution, and diffusion of styrene monomer in polyethylene films; in the case of simultaneous irradiation method, the reaction proceeds comparatively uniformly in the amorphous region, while in the case of the preirradiation method, the reaction proceeds mainly at the boundary of the crystalline and amorphous regions.     

辐射接枝医用水凝胶的研究Ⅰ.硅橡胶辐射接技N-乙烯基吡咯烷酮

采用填加SiO_2增强的甲基乙烯基硅橡胶混炼压片。通过~(60)Co-γ射线引发辐射硫化,利用共辐照方法,将N-乙烯基吡咯烷酮接枝到该硅橡胶上,制备了高纯度医用水凝胶。本文较系统地研究了接枝单体浓度、辐照剂量率、剂量、温度和接枝试片厚度等因素对接枝共聚反应的影响。建立了接枝速率与单体浓度、剂量率之间的动力学关系式:R_g=k[M]~(4/5)D~(1/2)。讨论了反应机制和接枝区域。     

Parameter Study for the Pre‐Irradiation Grafting of Styrene/Divinylbenzene onto Poly(tetrafluoroethylene‐co‐hexafluoropropylene) from Isopropanol Solution

Pre‐irradiation grafting of styrene/divinylbenzene (DVB) onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films from isopropanol (ⁱPrOH) solution was investigated with respect to the effect of irradiation dose, film thickness, cross‐linker concentration, and reaction temperature. A mathematical model was applied to the kinetic curves to extract information on the polymerization rate, the radical‐recombination rate, and the grafting through time. It turned out that the two closely correlated reaction rates for polymerization and radical recombination can be varied over a wide range by changing the irradiation dose, the cross‐linker concentration, and the reaction temperature. On the other hand, the time until the grafting front has progressed to the center of the film is mainly affected by the film thickness and the reaction temperature. The formation of homopolymer in the grafting solution increases steeply with temperature and cross‐linker concentration.     

A novel approach to graft acrylates onto commercial silicones for release film fabrications by two-step emulsion synthesis

In this study, a two-step emulsion polymerization method was specially designed so as to effectively graft acrylate monomers onto commercial silicones and improve the properties of release films. FT-IR, DSC and grafting ratio tests showed that the grafting reaction happened and a high grafting ratio can be achieved when the silicone content was more than 20%. According to SEM-EDX result, the “sea-island” structure on the surface of release films made by acrylate-modified silicone latexes was proven. The silicones formed the continuous “sea” structure and the grafted acrylate polymers formed the segregated “island” structure. The carbon and silicon distributions were not uniform through the cross-section of release films made by acrylate-modified silicone latexes. After acrylate modification, the surface tension of silicone release films increased from 19-21 mN/m (before acrylate modification) to 30 mN/m and the release force increased from 8.1 g/in. to 47 g/in. As a result, the properties of release films have been effectively improved by our novel method for advanced applications.     

Pre‐Irradiation Grafting of Styrene/Divinylbenzene onto Poly(tetrafluoroethylene‐co‐hexafluoropropylene) from Non‐Solvents

Pre‐irradiation grafting of styrene/divinylbenzene (DVB) onto poly(tetrafluoroethylene‐co‐hexafluoropropylene) (FEP) films was studied with respect to the influence of solvent. Particularly favorable grafting conditions with long radical lifetimes and reasonably high polymerization rates were achieved with solvents that are precipitants for the newly formed polystyrene, e.g., low‐molecular‐mass alcohols like ⁱPrOH, AcOH, their mixtures with H₂O, and H₂O/surfactant systems. Using one of these solvents significantly extended the range of accessible graft levels, and a specific degree of grafting was obtained at a much lower monomer concentration and irradiation dose than with grafting in a good solvent such as toluene. As practical consequences, the monomer was used more efficiently, and the radiation damage of the perfluorinated base material was reduced with the result of improved mechanical properties of the grafted films.     

Radiation grafting of pH and thermosensitive N-isopropylacrylamide and acrylic acid onto PTFE films by two-steps process

Polytetrafluoroethylene (PTFE) was grafted (g) with acrylic acid (AAc) by γ-ray pre-irradiation method to get PTFE-g-AAc films, then N-isopropylacrylamide (NIPAAm) was grafted onto PTFE-g-AAc films with γ-ray to get (PTFE-g-AAc)-g-NIPAAm. PTFE films were irradiated in air at a dose rate of 3.0 kGy h^–1 and different radiation dose. The irradiated films were placed in glass ampoules, which contained aqueous solutions with different monomer concentration (AAc), and then they were heated at different temperatures and reaction time. NIPAAm onto PTFE-g-AAc was carried out with the same procedure with monomer concentration of 1 mol L⁻¹. The thermosensitivity of the samples was defined and calculated as the ratio of the grafted samples swelling at 28 and 35 °C, and pH sensitivity defined as the ratio of the grafted samples swelling at pH 2 and 8.     

Radiation-induced grafting of styrene into poly(vinylidene fluoride) film by simultaneous method with two different solvents

Radiation-induced grafting of styrene into poly(vinylidene fluoride) (PVDF) films with 0.125 mm thickness at doses of 1 and 2.5 kGy in the presence of a styrene/N,N-dimethylformamide (DMF) solution (1:1, v/v) and at doses of 20, 40 and 80 kGy in presence of a styrene/toluene solution (1:1, v/v) at dose rate of 5 kGy h^?1 was carried out by the simultaneous method under nitrogen atmosphere and room temperature, using gamma rays from a Co-60. The films were characterized before and after modification by calculated grafting yield (GY %), infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TG/DTG). GY results shows that grafting increases with dose, and the grafting of styrene was confirm by FT-IR due to the new characteristic peaks and by the TG and DSC attributed to changes in thermal behavior of the grafted material. Results showed that the system allows the controlled grafting of styrene into PVDF using gamma rays at doses as low as 1 kGy in DMF.     

Styrene grafted ethylene chlorotrifluoroethylene (ECTFE‐g‐PSSA) protonic membranes: Preparation,characterization, and transport mechanism

The main goal of the present work is the development of partially fluorinated, low‐cost proton exchange membranes. The styrene grafted onto commercial ethylene chlorotrifluoroethylene (ECTFE) membranes using solution grafting technique, and after that the membranes were sulfonated. Diluting styrene on ECTFE with a solvent mixture of methanol plus methylene chloride (1:1) was highly effective in promoting the grafting reaction as indicated by the increase in the degree of grafting (DG) to 21.3% compared to other solvents. The DG in ECTFE membranes increased with an increase in the monomer concentration up to 60% and then declined. Fourier transform infrared spectroscopic analysis confirmed grafting and sulfonation onto ECTFE films. The maximum value of proton conductivity for ECTFE‐g‐PSSA film with DG = 21.3% was observed to be 141 mS cm⁻¹, which is also higher than those of Nafion 212 membrane. Furthermore, the activation energy of ECTFE‐g‐PSSA membranes was obtained ranging from 8.27 to 9.726 kJ mol⁻¹. So both proton transport mechanisms (hopping and vehicle) have been commonly accepted. The mobility of the charge carriers calculated from proton conductivity data has robust dependence on the grafting yield and temperature. Moreover, the tensile strength and elongation at break ratio decreases with the increase in DG. The water and methanol uptakes increase up to 0.97% and 30%, respectively, for the highest DG value. Finally, the ECTFE‐g‐PSSA has lower cost and higher conductivity they could be better used instead of Nafion in direct methanol fuel cells.     

Structure of styrene–butadiene–styrene block copolymers by diffusion analysis

In this study, solvent sorption was used to investigate the morphology of a styrene–butadiene–styrene (SBS) triblock copolymer. The sorption process was found to deviate from the normal Fickian character, usually found in conventional elastomer–solvent systems, because of the presence of an interfacial region for both polybutadiene and polystyrene. This interphase absorbed solvent at a temperature below its glass transition and contributed to the resulting non-Fickian time-dependent diffusion process. The equilibrium diffusion coefficient was estimated to be 3.2 × 10^?7 cm²/sec regardless of the casting surface. Nevertheless, according to the sorption measurements, the casting surface did have an effect on the approach to equilibrium. The results indicated a denser packing of the molecules and hence a decreased diffusion coefficient for Teflon and glass cast films, because of internal stresses left within the films during casting.     

Evaluating aging of coatings and sealants: Mechanisms

Photodegradation mechanisms of a model coating/sealant system based upon styrene-butadiene-styrene triblock copolymer have been investigated. The model system was exposed to ultraviolet-visible radiation using an integrating sphere-based exposure chamber at 30 °C and <1% relative humidity. Chemical degradation was monitored by transmission Fourier transform infrared (FTIR) spectroscopy and changes in mechanical properties via dynamic mechanical thermal analysis (DMTA). It was found that cross-linking was the dominant degradation process, causing substantial increases in storage modulus and glass transition temperature of the butadiene units with increasing exposure. The styrene units were relatively stable as indicated by the lack of significant changes in the FTIR bands or in the glass transition temperature associated with the styrene units. The present study clearly has shown that chemorheological investigations provide useful tools to characterize the mechanisms of environmental attack of polymers. The ability to investigate both chemical and mechanical-rheological properties provides the opportunity to make modifications to the material and, hence, improve its chemical and mechanical-rheological properties.     

Preparation and photolysis of poly-4′-acetylacrylophenone and its copolymers with styrene and methyl methacrylate

Poly-4′-acetylacrylophenone (P4AcAP) and its copolymers with styrene (4AcAP/S) and methyl methacrylate (4AcAP/MMA) were prepared. Ultraviolet (UV) spectra of these polymers show an absorption band at 29,500 cm^?1 (? = 270) of n-π* character. The low temperature emission spectra of films of copolymers studied exhibit a less resolved vibrational structure and are bathochromically shifted with respect to those of polyacrylophenone and its styrene and methyl methacrylate copolymers. The emission decay is slightly nonexponential and has a lifetime of about 0.02 sec. Quantum yields of main chain scission in solution with 366-nm radiation are of the same order as those of the unsubstituted polyacrylophenone. Substitution by a strong electron-accepting group, in comparison with polyacrylophenone, influences the value of the quantum yield only a little but prolongs the lifetime of the lowest triplet state. This is also evident in an increase in the Stern–Volmer constant in passing from polyacrylophenone–naphthalene in benzene (68 mole^?1) to P4AcAP–naphthalene in dioxane (380 mole^?1). With biphenyl as a triplet quencher, the Stern–Volmer constants are low because of back transfer: