Preparation and characterization of proton exchange membranes from polystyrene grafted poly（vinylidene fluoride） powder

Proton exchange membranes(PEMs) were prepared in three steps:graRing of polystyrene onto PVDF powder using pre-irradiation graft polymerization technique, processing the grafted PVDF powder into membranes of around 50-μm thickness, and sulfonating them with cholorosulfonic acid to form poly(vinylidene fluoride)-g-poly(styrene sulfonic acid) membranes. Kinetics of the graft polymerization was studied. The existing of polystyrene side-chains in the grafted PVDF powders, and PSSA groups in PEMs, were proved by FT-IR. Properties of the PEMs, i.e. the ion exchange capacity, water uptake, proton conductivity, thermal property and oxidative stability,were characterized. Dependence of properties on the degree of grafting was investigated, too.     

Hydrocarbon proton-conductive membranes prepared by radiation-grafting of styrenesulfonate onto aromatic polyamide films

Novel method for preparing aromatic hydrocarbon proton-conductive membranes without sulfonation and membrane casting process is achieved by radiation-grafting of sodium styrenesulfonate to an aromatic polyamide, poly(m-xylylene adipamide) (Nylon-MXD6) films and subsequent ion-exchange. The styrenesulfonate was easily grafted into the Nylon-MXD6 films from an oxygen-free dimethyl sulfoxide (DMSO) solution at 60 °C. As a result, the resulted styrenesulfonic acid-grafted Nylon-MXD6 films, namely proton-conductive membrane, with high ion-exchange capacity up to 1.63 mmol/g, can be obtained. The membrane was transparent and highly hydrophilic. The proton conductivity, water uptake and methanol permeability of the proton-conductive membranes were investigated with respect to their use in fuel cells. The high proton conductivity reached 0.083 S/cm, comparable to Nafion. Furthermore, the methanol permeability was significantly lower than that of the Nafion membrane. Therefore, the Nylon-MXD6-based proton-conductive membrane is a more promising material for the direct methanol fuel cells (DMFCs).     

A study on the distribution of polystyrene sulfonic acid grafts over the cross-section of a PFA film

In this study, the distribution behaviors of polystyrene sulfonic acid (PSSA) grafts over the cross-section of grafted PFA membranes (PFA-g-PSSA) were investigated by using SEM-EDX analysis. Membranes with various degrees of grafting (DOG) and thicknesses were prepared by a simultaneous radiation grafting of styrene and a subsequent sulfonation with chlorosulfonic acid. A SEM-EDX instrument was utilized to directly observe that the distribution behaviors of the PSSA grafts over the cross-section of grafted PFA membranes and the results showed that the distribution behaviors were largely affected by the grafting conditions such as the degree of grafting, monomer concentration, and film thickness.     

Proton exchange membranes prepared by radiation-induced graft copolymerization from binary monomer mixtures onto poly(tetrafluoroethylene-co-hexafluoropropylene) film

Sulfonic acid proton exchange membranes based on a poly(tetrafluoroethylene-co-hexafluoropropylene) film were synthesized through the single-step graft copolymerization of sodium styrenesulfonate and acrylic acid monomers from binary monomer aqueous solutions using the electron beam pre-irradiation method in air. The effects of the various polymerization parameters (absorbed dose, reaction time, and monomer ratio) on the degree of grafting were studied.A correlation between the degree of grafting and some of the physical-chemical properties (water uptake and ion-exchange capacity) of the synthesized copolymers was established. The distribution of the sulfonic acid groups was investigated across the thickness of several membranes in order to gain a better understanding of the graft copolymerization process from binary monomer aqueous solutions onto the fluorinated film and to synthesize membranes with optimal physical-chemical properties.     

Radiolytic preparation of ETFE and PFA based anion exchange membranes for alkaline fuel cell

In this study, a versatile monomer, vinylbenzyl chloride (VBC) was radiolytically grafted onto a partially fluorinated ETFE and perfluorinated polymer PFA films. The VBC grafted films were treated with trimethylamine to prepare the alkaline anion exchange membranes (AAEMs). No significant differences in the ion exchange capacities and water uptakes were observed between the ETFE and PFA based AAEMs with similar degree of grafting (DOG). However, the distribution patterns of the graft chains over the cross-section of the ETFE and PFA based AAEMs were found to be quite different; the even distribution was observed from the ETFE based AAEMs while the uneven distribution was observed from the PFA based AAEMs. It was also found that the PFA based AAEMs have the higher ionic conductivity and chemical stability, compared to the ETFE based AAEMs.     

Anisotropic proton-conducting membranes prepared from swift heavy ion-beam irradiated ETFE films

Poly(ethylene-co-tetrafluoroethylene) (ETFE) films were irradiated by swift heavy ion-beams of ¹²⁹Xe²³⁺ with fluences of 0, 3 × 10⁶, 3 × 10⁷, 3 × 10⁸ and 3 × 10⁹ ions/cm², followed by γ-ray pre-irradiation for radiation grafting of styrene onto the ETFE films and sulfonation of the grafted ETFE films to prepare highly anisotropic proton-conducting membranes. The fluence of Xe ions and the addition of water in the grafting solvent were examined to determine their effect on the proton conductivity of the resultant membranes. It was found that the polymer electrolyte membrane prepared by grafting the styrene monomer in a mixture of 67% isopropanol and 33% water to the ETFE film with an ion-beam irradiation fluence of 3.0 × 10⁶ ions/cm² was a highly anisotropic proton-conducting material, as the proton conductivity was three or more times higher in the thickness direction than in the surface direction of the membrane.     

DVB用量对SDB结构和Pt-SDB催化性能影响研究

以苯乙烯(St)为单体,共聚单体二乙烯基苯(DVB)为交联剂,通过悬浮聚合法制备了不同交联结构的大粒径(2~5mm)多孔聚苯乙烯-二乙烯基苯(SDB)小球,并用浸渍还原法制备了Pt-SDB疏水催化剂。采用傅里叶红外光谱(FT-IR)、热重(TG)、N2吸附-解吸、微机控制电子万能试验机、静态水接触角(CA)、场发射扫描电镜(FSEM)和氢-水催化交换实验等手段分析了DVB用量对SDB的分子结构、热稳定性、孔结构、抗压强度、疏水性、Pt的分散度及催化活性的影响。结果表明:随着DVB用量的增大,热稳定性、抗压强度以及疏水性明显提高,Pt的分散度显著增大,比表面积和孔容逐渐增大,平均孔径则逐渐减小。当DVB与St的摩尔比(n(DVB)∶n(St))=1∶1时,SDB疏水催化剂载体性能优异,孔结构、Pt的分散度及疏水性最佳,制得的Pt-SDB催化剂柱效率达95.6%(65℃)、96.1%(80℃)。     

过氟化聚合物的苯乙烯接枝研究--辐照条件与反应条件的影响

Fuel cell is in focus as a very low exhaust new dynamo system. Especially polymer electrolyte fuel cells (PEFC) using proton exchange membranes (PEM) have attracted much attention for the electrical vehicle and other mobile applications such as cellar phone and personal computer. Conventional perfluoro-sulfonic acid membranes such as Nation() (DuPont de Nemours LTD.) have been the popular PEM used in PFEC. However, there are still several problems such as insufficient gas barrier properties, low thermal resistance, and their high costs.In this study, hawse have studied the partially fluorinated PEM for PEFC by radiation grafting onto per-fluorinated polymers such as PFA, FEP and ETFE with reactive styrene monomers using pre-irradiation grafting method in gas and in liquid phase, respectively, and successive sulfonation. Characteristic properties of the grafted and sulfonated materials have been discussed and optimized fabricating conditions were determined.Characteristic properties of the obtained materials have been measured by differential scanning calorimetry,thermogravimetric analysis and FT-IR spectroscopy, etc.In the case of irradiation in air, glass transition temperatures (Tg) of the grafted materials depend on the yields of styrene grafting onto the materials. That is higher yields of grafting give lower thermal stability. On the other hand, when the peroxy radicals were converted trapped radicals by exposure in air after irradiation under oxygen-free atmosphere, Tg of the grafted materials hardly depends on the grafting yields.Moreover, the yields of grafting in gas phase were higher than that of liquid phase. However, the sample form of grafting in gas phase has been greatly changed, whereas the sample form of grafting in liquid phase has kept its original feature.Therefore, it is suggested that the fabricating conditions for PEFC membranes were preferred to irradiation under oxygen-free atmosphere and grafting in liquid phase.Ion exchange capacities of the sulfonated-materials could be 3.0meq/g. Other properties of the obtained membranes such as chemical structure were also discussed.     

Preparation of a new micro-porous poly(methyl methacrylate)-grafted polyethylene separator for high performance Li secondary battery

In this study, micro-porous poly(methyl methacrylate)-grafted polyethylene separators (PE-g-PMMA) were prepared by a radiation-induced graft polymerization of methyl methacrylate onto a conventional PE separator followed by a phase inversion. After the phase inversion, the micro-pores were generated in the grafted PMMA layer. The prepared micro-porous PE-g-PMMA separators showed an improved electrolyte uptake and ionic conductivity due to their improved affinity with a liquid electrolyte and the presence of pores in the grafted PMMA layer. The PE-g-PMMA separators exhibited a lower thermal shrinkage compared to the original PE separator. The PE-g-PMMA separators showed a better oxidation stability up to 5.0 V when compared to the original PE separator (4.5 V).     

Radiation synthesis and characteristics of PTFE-g-PSSA ion exchange membrane applied in vanadium redox battery

Radiation-induced grafting of styrene onto polytetrafluoroethylene （PTFE） membranes was studied by a simultaneous irradiation technique. Grafting was carded out using γ-radiation from a ^60Co source at room temperature. Effects of absorbed dose, atmosphere, dose rate, and the concentration of initial monomer on the degree of grafting （DOG） were investigated and the most appropriate grafting condition was obtained. Subsequently, sulphonation of the grafted PTFE membrane （PTFE-g-PS） was carded out and a series of ion exchange membranes （PTFE-g-PSSA） was prepared. Further characterizations of FTIR, TGA, and SEM testified that grafting and sulphonation of the membranes were successfully processed; moreover, grafting of styrene not only occurred in the surface of PTFE membrane, but also in the micropores of the membrane. Ion exchange capacity （IEC） and conductivity were found increase with the grafting yield. The results suggest that at a low dose, such as 17 kGy, the ion exchange membrane （IEM） which will be suitable for vanadium redox battery （VRB） use can be obtained.     

Preparation of composite polymer electrolytes by electron beam-induced grafting: Proton- and lithium ion-conducting membranes

Two classes of composite polymer electrolyte membranes, one conducting lithium ions (Li⁺) and the other conducting protons (H⁺) were prepared using simultaneous electron beam-induced grafting. Porous poly(vinylidene fluoride) (PVDF) films were impregnated with styrene and subjected to electron beam (EB) irradiation to obtain polystyrene (PS) filled PVDF precursor films that were subsequently treated with either chlorosulfonic acid/1,1,2,2-tetrachloroethane mixture to obtain H⁺-conducting composite membranes or LiPH₆/EC/DEC liquid electrolyte to obtain Li⁺-conducting composite membranes. The properties of the obtained membranes were evaluated using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and AC impedance measurements. The obtained membranes were found to achieve grafting content up to 46% with superior Li⁺-conductivity of 1.91 × 10⁻³ S/cm and H⁺-conductivity of 5.95 × 10⁻² S/cm. The results of this work show that simultaneous radiation-induced grafting with EB is a promising method to prepare high quality ion-conducting membranes for possible use in fuel cells and lithium batteries.     

Study of radiation-induced grafting of acrylic acid-sodium styrene sulfonate onto poly （tetrafluoroethylene-cohexafluoropropylene） film

Poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) films were immersed in aqueous solution of acrylic acid (AA) and sodium styrene sulfonate (SSS), then irradiated by ^60Co γ-rays at 25℃. The effects o| reaction time, absorbed dose, dose-rate, inhibitor and monomer concentration on the grafting yield were studied. Grafting yields of both AA and SSS onto FEP, respectively, increase with irradiation dose, but some saturation will appear at high dose and monomer concentration. The grafting yield increases with reaction time and then levels off. The grafting of SSS onto FEP is more difficult than the grafting of AA. The analysis of grafted membranes using DSC and FT-IR have been done.     

聚-L-乳酸辐射接枝N-乙烯基吡咯烷酮的研究

以甲醇为溶剂,采用辐射接枝法制备了聚-L-乳酸（Poly-L—lacticacid,PLLA）/N-乙烯基吡咯烷酮（N-vinyl pyrrolidone,NVP）接枝共聚物（Poly（L—lactide）-g—poly（N—vinyl pyrrolidone）,PLLA—g—PVP）。研究了不同吸收剂量对接枝率的影响,并用傅立叶变换红外光谱（Fourier transform infrared spectrometer,FT—IR）、核磁共振氢谱（Nuclear magnetic resonance,^1HNMR）、差示扫描量热法（Differential scanning calorimeter,DSC）对接枝共聚物进行了表征。结果表明,共聚物接枝率随吸收剂量的增加而增加,吸收剂量为5 kGy时,接枝率可达14．9％;NVP链段C=O吸收峰出现在1660—1671cm^-1,随吸收剂量的增加移向高波数;在^HNMR中PLLA链段甲基和次甲基峰面积比大于3：1,说明接枝反应可能发生在PLLA次甲基碳上;PLLA的结晶焓随吸收剂量的增加而增加;接枝共聚物的结晶焓随吸收剂量的增加而降低。     

Properties of poly(ethylene terephthalate) track membranes with a polymer layer obtained by plasma polymerization of pyrrole vapors

The structure and the charge transport properties of poly(ethylene terephthalate) track membrane modified by pyrrole plasma were studied. It was found that polymer deposition on the surface of a track membrane via plasma polymerization of pyrrole results in the creation of composite nanomembranes that, in the case of the formation of a semipermeable layer, possess asymmetric conductivity in electrolyte solutions - a rectification effect similar to that of a p-n junction in semiconductors. It is caused by presence in the membranes of two layers with different functional groups and also by the pore geometry. Such membranes can be used to create chemical and biochemical sensors.     

Study on chemical structures of poly (tetrafluoroethylene-co-perfluoroalkylvinylether) by soft-EB irradiation in solid and molten state

Poly (tetrafluoroethylene-co-perfluoroalkylvinylether) (PFA) was irradiated by soft electron beam (soft-EB) under nitrogen gas atmosphere in solid-state and its molten state, respectively. The changes of thermal property and chemical structures of irradiated PFA in solid-state and molten state were studied by differential scanning calorimetric analysis (DSC) and solid-state ¹⁹F magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. By DSC analysis, the melting temperature shifted to lower temperatures, and crystallinity decreased with increasing soft-EB dose. By solid-state ¹⁹F MAS NMR spectroscopy, the new signals was observed and the detected new signals in irradiated PFA at 315 °C and at 30 °C were due to the tertiary carbon group with branching site (Y-type crosslinking site), perfluoro-propylene site and chain end methylene groups, respectively.Moreover, the molar ratio of perfluoroalkylvinylether (FAVE) structure to -CF₂- units decreased with increasing dose.     

Determining the degree of grafting for poly（vinylidene fluoride） graft-copolymers using fluorine elemental analysis

Acrylic acid (AAc) and styrene (St) were grafted onto poly(vinylidene fluoride) (PVDF) powder or membrane samples by pre-irradiation graft copolymerization.The grafted chains were proved by FT-IR spectroscopy analysis.The degree of grafting (DG) of the grafted PVDF was determined by fluorine elemental analysis (FEA) method,and was compared with the DGs determined by weighing method,acid-base back titration method and quantitative FT-IR method.The results show that the FEA method is accurate,convenient and universal,especially for the grafted polymer powders.     

Vitamin C hinders radiation cross-linking in aqueous poly(vinyl alcohol) solutions

Poly(vinyl alcohol) (PVA) is a promising semi-crystalline material for biomedical applications. It is soluble in water and can be formed into hydrogels by freezing and thawing or crystallizing from an aqueous theta solution such as that of polyethylene glycol (PEG). Radiation cross-linking caused by sterilization or high dose irradiation of concentrated PVA solutions could compromise some properties of these hydrogels. Therefore, we hypothesized that radiation cross-linking of PVA solutions and PVA-PEG theta gels could be prevented by using the antioxidant vitamin C as an anticross-linking agent. Our hypothesis tested positive. Vitamin C concentrations of 0.75 and 4.5 mol/mol of PVA repeating unit could prevent cross-linking in 17.5 wt/v% PVA solutions made with PVA molecular weight of 115,000 g/mol irradiated to 25 and 100 kGy, respectively. Vitamin C also prevented cross-linking in 25 kGy irradiated PVA-PEG theta gels containing up to 5 wt% PEG and decreased the viscosity of those up to 39 wt%.     

Enhancement of the electrical performance of poly(vinyl) alcohol by doping with chlorophyll and gamma irradiation

The electrical properties of poly(vinyl) alcohol (PVA) have been improved pronouncedly by doping with chlorophyll (Chl) and gamma irradiation. PVA/Chl films have been prepared and irradiated with γ-rays at dose levels of 10, 20, 30, 50, 70, 100, 150, 200 and 250 kGy. The crystalline and chemical structures of the samples have been studied using XRD and FTIR techniques. Also, the direct current electrical conductivity and the dielectric constant and loss have been determined for the proposed samples before and after gamma exposure. It is clearly shown that the electrical conductivity of PVA films was increased two orders of magnitude due to chlorophyll doping and about fifteen times due to gamma irradiation. Considering the dielectric constant and loss, their values were shown to increase significantly due to PVA doping with chlorophyll. The obtained results can be attributed to the existence of the conducting Mg atom, as well as, the conjugated double bonds in the chlorophyll. Moreover, the gamma irradiation of PVA/Chl, over 50 kGy, improves also this electrical performance. Therefore, the study suggests the possibility of the utilization of the gamma irradiated PVA/Chl films in different electronic applications.     

Formation of amorphous carbon on the surface of poly(ethylene terephthalate) by helium plasma based ion implantation

The surface modification of poly(ethylene terephthalate) (PET) by helium plasma based ion implantation (He PBII) was studied. The effect of the main process parameters (acceleration voltage, fluence and fluence rate) on the alterations of the surface chemical composition and structure were investigated by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy.According to SRIM calculations, at ion energies above 2 keV the stopping power of PET for He⁺ ions is dominated by the electronic component and the contribution of the nuclear component is relatively small. Degradation of the ester group and carbonisation were observed by XPS due to elimination of O-rich fragments. The total C-content of the modified layer increased with the increase of fluence rate and acceleration voltage of particles, enabling the purposeful alteration of the surface composition. A strong broadening was detected in the Raman spectrum between 1000 and 1700 cm⁻¹, testifying to the intense formation of amorphous carbon. The area ratio of the D (∼1410 cm⁻¹) to G (∼1570 cm⁻¹) band increased with the increase of particle fluence and the increase of acceleration voltage, offering the possibility of tailoring the chemical structure of the amorphous carbon layer created by the He PBII treatment.