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.     

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.     

Radiolytic preparation of poly(styrene sulfonic acid) - grafted poly(tetrafluoroethylene-co-perfluorovinyl vinyl ether) membranes with highly cross-linked networks

In this study, various amounts of a divinylbenzene (DVB) cross-linking agent (5∼30%) were introduced during a simultaneous irradiation grafting of styrene onto a PFA film of a 25 μm thickness in order to prepare a series of poly(styrene sulfonic acid)-grafted poly(tetrafluoroethylene-co-perfluorovinyl vinyl ether) (PFA) membranes with various degrees of cross-linking and grafting (29∼74%). The effects of the DVB cross-linking agent on the properties of the prepared membranes, such as water uptake, proton conductivity, methanol permeability, and chemical stability, were also investigated in this study. The results indicated that the ion exchange capacity (IEC) slightly decreased with increasing DVB content, whereas the water uptake, proton conductivity, and methanol permeability of the membrane greatly decreased. The chemical stability of the prepared membranes was found to be significantly improved with increasing DVB content. The results indicated that the cross-linked network membranes are promising for application in a direct methanol fuel cell.     

γ共辐射接枝丙烯酸改善聚醚砜粉体亲水性的研究

利用γ射线共照射技术在聚醚砜（Polyethersulfone,PES）粉体上按枝了丙烯酸。研究了丙烯酸单体体积分数、接枝溶液pH值、吸收剂量、阻聚剂（Cu^2＋）浓度等对接枝率的影响规律。通过与称重法相结合,得到了利用红外光谱对接枝率进行定量分析的工作曲线。研究结果表明,当吸收剂量为25kGy、单体体积分数为30％、阻聚剂用量为0．004mol／L时,可以获得最高的接枝率。接枝溶液中盐酸的添加有利于提高接枝率。提高接枝率有助于改善PES的亲水性。     

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.     

聚丙烯辐射接枝硅烷的制备及表征

采用γ射线固相辐射接枝方法,在聚丙烯粉末表面接枝乙烯基三甲氧基硅烷制备PP—g—Si。研究了不同吸收剂量对聚丙烯接枝率的影响,发现加入第二单体苯乙烯可以提高其接枝率到4．2％。吸收剂量的提高可显著提高硅烷在聚丙烯上的接枝量,使得接枝聚丙烯水解后物理交联凝胶含量增加。由于γ射线辐射会引起聚丙烯分子链断裂,经固相辐射接枝聚丙烯的熔体流动速率会变大。利用DSC研究了产物PP—g—Si的熔点随辐射吸收剂量的变化,同时以XRD研究了PP-g—Si的结晶形态。     

Development of function-graded proton exchange membrane for PEFC using heavy ion beam irradiation

The graded energy deposition of heavy ion beam irradiation to polymeric materials was utilized to synthesize a novel proton exchange membrane (PEM) with the graded density of sulfonic acid groups toward the thickness direction. Stacked Poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) films were irradiated by Xe⁵⁴⁺ ion beam with the energy of 6 MeV/u under a vacuum condition. The induced trapped radicals by the irradiation were measured by electron spin resonance (ESR) spectroscopy. Irradiated films were grafted with styrene monomer and then sulfonated. X-ray photo-electron spectroscopy (XPS) spectra showed that the densities of sulfonic acid groups were controlled for injection “Surface” and transmit “Back” sides of the fabricated PEM. The membrane electrode assembly (MEA) fabricated by the function-graded PEM showed improved fuel cell performance in terms of voltage stability. It was expected that the function-graded PEM could control the graded concentration of sulfonic acid groups in PEM.     

聚四氟乙烯膜辐射接枝反应条件的研究

采用了共辐射接枝技术，在室温下将苯乙烯接枝到聚四氟乙烯薄膜上，合成了辐射接枝膜。研究了溶剂种类、单体浓度、辐射剂量以及剂量率等因素对接枝反应的影响。结果表明，单体浓度和辐射剂量率是反应的主要影响因素，两者对接枝反应速率的影响指数分别为1．2和0．4。     

One step graft copolymerization of acrylic acid and sodium styrene sulfonate onto high－density polyethylene film by preirradiation method

High-density polyethylene(HDPE)films were irradiated by ^60Co gamma ray with a dose of 100kGy in air and then immersed in aqueous solution of acrylic acid(AA) and sodium styrene sulfonate(SSS) at different temperature.The effects of grafting conditions such as temperature,reaction time ,Mohr‘s salt concentration,and total concentration of monomer on grafting yield were studied.Both grafting yield of AA and SSS onto HDPE respectively increases with total concentration of monomer on grafting yield were studied.Both grafting yield of AA and SSS onto HDPE respectively increases with total concentration of monomers.The highest grafting yield was observed at 3mol/L monomers where the grafted PE swelled to the largest extent in the monomers mixture.The grafting yield increases with reaction time and then levels off.At higher temperature,the grafting yield decreases with Mohr‘s salt concentration,but increases at low temperature when Mohr‘s salt concentration is 0.083%.Which can be interpreted that in the presence of Fe^2 diperoxides and hydroperoxides may decompose at low temperature to form radical which can initiate the grafting.The physical and chemical properties of grafting films were also investigated.     

辐射法制备聚丙烯酸-改性壳聚糖体系的两性凝胶

以O-马来酸酐化N-邻苯二甲酰化壳聚糖(MPCS)为中间产物,通过γ射线引发,在均相溶液体系制备含有改性壳聚糖.聚丙烯酸的两性凝胶.用红外光谱证实了接枝反应的发生.同时还系统地研究了接枝反应的影响因素,结果表明,接枝率依赖于单体浓度和所用的剂量.通过研究了接枝产物在不同pH值缓冲溶液中溶胀度的变化,结果发现,接枝产物在酸性条件(Ph<7)下溶胀较小,在碱性条件(pH>7)下溶胀度较大.而且还测试了接枝产物在DMF溶剂中的溶胀情况.     

电子束引发双功能基阳离子交换膜的制备研究

在所有的离子交换膜中,最引人注目的当数20世纪70年代已商品化的Nation系列膜。具有磺酸功能基的Nation膜电阻低,但用在氯碱工业时电流效率低。1974年Seko发明了全氟羧酸阳离子交换膜,使电流效率有实质性提高,并推动了复合膜的发展。复合膜具有磺酸膜的低电阻性能和羧酸膜的高电流效率。本工作采用辐射接枝法制备含羧酸基团和磺酸基团的双功能基阳离子交换膜,目的主要是以低成本且简单可行的辐射接枝法代替共聚法,制备稳定性好、低电阻、高电流效率的阳离子交换膜。     

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.     

马来酸酐紫外辐照接枝高密度聚乙烯的制备及表征

采用紫外辐照技术制备了高密度聚乙烯-马来酸酐接枝物（HDPE—g—MAH）,并用红外光谱对接枝物进行了表征。研究了紫外光辐照时间、单体及引发剂浓度、第二单体苯乙烯（St）等因素对接枝率及凝胶含量的影响。结果显示,辐照时间为30s时,接枝效果最佳。马来酸酐（Maleic anhydride,MAH）用量的增加使接枝率不断上升,而接枝效率则在MAH含量为5．2％时达到最大值,之后开始下降。光引发剂二苯甲酮（Benzophenone,BP）的用量对接枝率及凝胶含量有重要影响,其用量为0．5％时接枝效果较好;St的加入使接枝物的凝胶含量显著降低。     

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.     

粉体PVDF辐射接枝苯乙烯

以聚偏氟乙烯（PVDF）粉体为基材,采用预辐射接枝方法,在PVDF粉体上接枝聚合苯乙烯单体。并通过红外光谱、元素分析、差示扫描量热分析、热重分析对接枝后粉体进行了表征。红外光谱证明苯乙烯被成功接枝到PVDF粉体上,DSC图谱反映出结晶度随接枝率的增大而减小,接枝苯乙烯后粉体的热重图与接枝前的粉体比较也有明显的变化,进一步佐证了苯乙烯的成功接枝。     

超高分子量聚乙烯纤维预辐照接枝丙烯酸甲酯

采用预辐照接枝的方法研究了丙烯酸甲酯（MA）单体在超高分子量聚乙烯（UHMWPE）纤维表面的接枝聚合反应。考察了吸收剂量、单体浓度、接枝聚合反应温度对接枝率的影响。结果表明：UHMWPE纤维接枝MA的接枝率较高,最高可达约151％,接枝率随吸收剂量、单体浓度、反应温度升’高而增加。用红外光谱法分析了接枝前后纤维官能团的变化,通过扫描电镜观察了接枝前后纤维表面的形貌。     

Radiation grafting of methyl methacrylate onto polyethylene separators for lithium secondary batteries

Micro-porous polyethylene separator was modified by radiation grafting of methyl methacrylate in order to improve its affinity with a liquid electrolyte. The degree of grafting (DOG) increased with the monomer concentration and grafting time. The morphological change of the modified separator was investigated by scanning electron microscopy. The degree of crystallinity upon grafting was reduced due to the formation of an amorphous PMMA layer. The electrolyte uptake and the ionic conductivity of the separator increased with an increase in the DOG. The ionic conductivity reached 2.0 mS/cm for the grafted polyethylene separator with 127 wt% DOG.     

γ辐射接枝甲基丙烯酸改善聚醚砜膜亲水性的研究

利用 γ 射线共辐照技术在聚醚砜(PES)膜上接枝了甲基丙烯酸。通过改变甲基丙烯酸单体浓度,获得了具有不同接枝率的改性 PES 膜。研究结果表明,在单体浓度<10%的范围内,接枝率与单体浓度成线性关系,提高接枝率有助于改善聚醚砜膜的亲水性。