聚乙烯阴离子交换膜掺混聚偏氟乙烯改性表征

聚偏氟乙烯（PVDF）因含氟乙烯基单体,拥有良好的化学稳定性、热学稳定性和机械性能,与其他高分子膜材料相比更容易提高离子交换膜的性能。本实验采用热压法制备PVDF聚乙烯阴离子交换膜,探讨了PVDF含量对膜性能的影响,如膜电阻、离子交换容量、耐破度、含水率和选择透过性。利用红外光谱仪及扫描电子显微镜表征手段对PVDF膜表面性质和结构进行了分析。结果表明,当PVDF含量增加时,膜面电阻、耐破度升高。离子交换容量、含水率,反离子选择透过性降低。虽然PVDF的添加导致含水率、交换容量等膜性能的下降,但耐破度的升高表明膜稳定性和机械性能得到了提升,这赋予PVDF聚乙烯膜一定的使用价值。     

低温等离子体接枝改性聚乙烯PVDF阴离子交换膜

为了进一步提升掺混了聚偏氟乙烯(PVDF)的聚乙烯阴离子交换膜的综合性能,采用低温等离子体接枝改性的方式,将聚苯乙烯磺酸钠(PSS)接枝到膜上,并考察接枝单体浓度及等离子体辉光放电处理时间对离子交换容量和选择透过性能的影响。利用扫描电子显微镜和红外光谱仪对制备出复合膜的膜面形态及结构组成进行了表征和分析。结果表明,使用低温等离子体放电的方式能够成功地将PSS接枝到膜上,制备出PSS-聚乙烯PVDF阴离子交换膜。实验表明,通过合理的控制接枝过程参数,复合膜的离子交换容量以及选择透过性能得到了有效的提升,PSS浓度为1.5 g/L且放电时间为4 min时接枝效果最好,此时膜的性能达到最优。     

PVDF阳离子交换合金膜聚苯胺浸润法改性

利用掺杂态聚苯胺(PANI)所具备的导电性,以及它可提供交换能力的性质,采用浸润法对以聚合热压法制备的PVDF阳离子交换合金膜进行改性。采用FT-IR和SEM对改性产品进行了表征,并分析了改性产品的性能。结果表明,通过浸润法在PVDF阳离子交换合金膜表面成功引入了聚苯胺颗粒;改性后的PVDF阳离子交换合金膜的交换容量、含水率以及电导率相比改性前均有明显提高。     

二氧化硅改性Nation117阳离子交换膜的性能研究

Nation阳离子交换膜以其优秀的机械和离子选择性能得到广泛应用,而在强酸性条件下,虽然比其他类型阳离子交换膜仍有着明显的优势,但其性能却已明显降低.针对这一问题,采用了正硅酸乙酯对其进行改性处理,并对改性后膜的性能进行了研究.通过对离子交换容量、离子选择透过性、含水率的测试,发现在交换容量和含水率变化不大的情况下,对氯离子的阻挡效果得到了明显的改善,在最优的改性条件下较原膜提高了53.8％.     

二氧化硅改性Nafion117阳离子交换膜的性能研究

Nafion阳离子交换膜以其优秀的机械和离子选择性能得到广泛应用,而在强酸性条件下,虽然比其他类型阳离子交换膜仍有着明显的优势,但其性能却已明显降低。针对这一问题,采用了正硅酸乙酯对其进行改性处理,并对改性后膜的性能进行了研究。通过对离子交换容量、离子选择透过性、含水率的测试,发现在交换容量和含水率变化不大的情况下,对氯离子的阻挡效果得到了明显的改善,在最优的改性条件下较原膜提高了53.8%。     

丁炔二酸化学接枝改性阴离子交换膜的制备及表征

以丁炔二酸为改性药剂,采用化学接枝法改性商用均相阴离子交换膜。通过电渗析试验,研究不同改性因素对膜选择分离性能的影响,优化改性条件,并在适宜改性条件下,对改性膜进行膜面表征与基本性能测试。结果表明,在丁炔二酸溶液浓度1 g/L,浸泡时间60 min,紫外光照时间30 min,未调节浸泡液pH的条件下,改性膜的离子交换容量、含水率、溶胀度分别为1.00 mmol/g、14.82%、5.46%,均小于原膜;改性膜的亲水性下降,选择透过性系数（P (Cl-/SO24-)）为6.128,是原膜的1.49倍。     

BPO和AIBN作引发剂对阳离子交换膜性能的影响

改进传统制备聚偏氟乙烯(PVDF)均相阳离子交换膜的方法,利用引发剂和浓硫酸磺化直接制备PVDF均相阳离子交换膜。通过溶剂蒸发法制备了含引发剂过氧化苯甲酰(BPO)和/或偶氮二异丁腈(AIBN)的PVDF阳离子交换膜,研究不同引发剂及其含量对膜结构和膜性能的影响。利用FE-SEM和FTIR分析了膜的形貌结构。结果表明:含有BPO的阳离子交换膜中PVDF与苯乙烯形成了半互穿网络结构,而含有AIBN的阳离子交换膜中苯乙烯接枝在线性PVDF链上并形成相分离结构。PVDF阳离子交换膜的结构和性能受膜制备时AIBN和BPO的添加量影响。当AIBN占PVDF5%(质量分数)、BPO占PVDF2%(质量分数)时,离子交换膜的膜电阻达最低值4.2Ω×cm~2,离子交换容量最高为1.59 meq/g;当AIBN占PVDF 3%(质量分数)、BPO占PVDF2%(质量分数)时,离子交换膜的迁移数为95.15%。最后通过循环伏安法和计时电位法进一步验证了引发剂对膜电阻和迁移数影响的实验结论。     

负载离子液体的阳离子交换膜在烯烃/烷烃分离中的应用

制备了负载胆碱赖氨酸盐离子液体（[Ch][Lys]）的阳离子交换膜,测定并表征其膜的性能,研究其在电渗析下分离1-己烯/n-己烷的能力。结果表明,膜含水率和离子交换容量随离子交换树脂质量分数和离子液体含量的增加而增大;膜的面电阻随树脂质量分数增大而减小,随离子液体含量的增大而增大;膜中添加离子液体明显提高了其分离1-己烯/n-己烷的能力,当阳离子交换树脂含量为70%、离子液体添加量为15%时,所制的阳离子交换膜对1-己烯分离的选择性最高,其值可达9.5。     

有机无机杂化PVA/SiO_2阳离子交换膜的制备及电化学性能表征

在酸性条件下制备了有机-无机杂化PVA/SiO_2阳离子交换膜,在无机链端引入了磺酸基团。利用扫描电子显微镜(SEM)、傅里叶红外光谱(FTIR)、物理化学(氧化稳定性,IEC和吸水率)和电化学性能测试方法(膜电阻,迁移数和选择透过性)对制备的膜及商品苯乙烯膜进行了广泛表征。结果表明,与苯乙烯膜相比,制备的PVA/SiO_2阳离子交换膜具有良好的选择透过性和低电阻中。6%-PVA/SiO_2的离子交换膜的综合性能最好,可能应用于"双膜三室"钴回收系统。     

有机无机杂化PVA/SiO_2阳离子交换膜的制备及电化学性能表征

在酸性条件下制备了有机-无机杂化PVA/SiO_2阳离子交换膜,在无机链端引入了磺酸基团。利用扫描电子显微镜(SEM)、傅里叶红外光谱(FTIR)、物理化学(氧化稳定性,IEC和吸水率)和电化学性能测试方法(膜电阻,迁移数和选择透过性)对制备的膜及商品苯乙烯膜进行了广泛表征。结果表明,与苯乙烯膜相比,制备的PVA/SiO_2阳离子交换膜具有良好的选择透过性和低电阻中。6%-PVA/SiO_2的离子交换膜的综合性能最好,可能应用于"双膜三室"钴回收系统。     

Preparation and characterization of ABS/HIPS heterogeneous anion exchange membrane filled with activated carbon

Acrylonitrile‐butadiene‐styrene (ABS)/high impact polystyrene (HIPS) blend heterogeneous anion exchange membranes were prepared by phase inversion method using tetrahydrofuran as solvent and anion exchange resin powder as functional group agent. Activated carbon was selected as inorganic filler additive. The additive concentration effect on properties of the prepared membranes was studied. Ultrasonic method was used to help appropriate dispersion of particles in the membrane's matrix. Scanning optical microscopy showed that sonication has a significant influence on distribution of resin particles in the membrane matrix and makes it possible to form more uniform phase. Moreover, images showed a relatively uniform surface for membranes. The increase of activated carbon concentration in casting solution led to a decline in membrane water content. The ion exchange capacity, membrane potential, permselectivity, transport number, ion permeability, ionic flux, and current efficiency of prepared membranes all were increased initially by the increase in additive concentration up to 1% wt and then they showed decrease trend with higher increase in additive concentration from 1 to 4% wt. Conversely, the electrical resistance and energy consumption showed opposite trends. In addition, with more additive loading, the oxidative stability of membranes was slightly decreased and their thermal stability was increased. Membrane with 1% wt additive loading exhibited higher efficiency and electrochemical properties in comparison with other prepared membranes in this research. Furthermore, prepared membranes exhibited suitable electrochemical properties compared to a commercial heterogeneous anion exchange membrane with the same experimental conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Comparative investigations of radiation‐grafted proton‐exchange membranes prepared using single‐step and conventional two‐step radiation‐induced grafting methods

Proton‐exchange membranes containing poly(styrene sulfonic acid) grafts hosted in poly(vinylidene fluoride) (PVDF) films were prepared using two radiation‐induced grafting methods: a single‐step grafting method (SSGM) involving grafting of sodium styrene sulfonate onto electron beam (EB)‐irradiated PVDF films and a conventional two‐step grafting method (CTSGM) in which styrene monomer is grafted onto EB‐irradiated PVDF films and subsequently sulfonated. Differential scanning calorimetry, universal mechanical testing and scanning transmission electron microscopy were used to evaluate the thermal, mechanical and structural changes developed in the membranes during the preparation procedures. Physicochemical properties such as water uptake, hydration number and ionic conductivity were studied as functions of ion‐exchange capacity and the results obtained were correlated with the structural changes accompanying each preparation method. Membranes obtained using the SSGM were found to have superior properties compared to their counterparts prepared using the CTSGM suggesting the former method is more effective than the latter for imparting desired functionality and stability properties to the membranes. Copyright © 2010 Society of Chemical Industry     

Cation exchange membranes by radiation‐induced graft copolymerization of styrene onto PFA copolymer films. II. Characterization of sulfonated graft copolymer membranes

PFA‐g‐polystyrene sulfonic acid membranes were prepared by simultaneous radiation‐induced graft copolymerization of styrene onto poly(tetrafluoroethylene‐co‐perfluorovinyl ether) (PFA) film followed by sulfonation. The membrane physico‐chemical properties such as swelling behavior, ion exchange capacity, hydration number, and ionic conductivity were studied as a function of the degree of grafting. Thermal as well as chemical stability of the membranes was also investigated. The membrane properties were found to be mainly dependent upon the degree of grafting. The water uptake, ion exchange capacity, hydration number, and ionic conductivity of the membranes were increased, whereas the chemical stability decreased as the degree of grafting increased. The membranes showed reasonable physico‐chemical properties compared to Nafion 117 membranes. However, their chemical stability has to be further improved to make them acceptable for practical use in electrochemical applications. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1–11, 2000     

Synthesis and characteristics of radiation‐grafted membranes for fuel cell electrolytes

Proton exchange membranes were prepared by simultaneous radiation grafting of styrene onto polytetrafluoroethylene (PTFE) films at room temperature and subsequent sulfonation by chlorosulfonic acid. A series of grafted films with degree of grafting ranging from 0.947% to 35.4% were obtained. The effect of styrene concentration on the grafting yield was investigated and the maximum value was obtained at a monomer concentration of 70‐vol%. The structure of PTFE‐graft‐polystyrene sulfonic acid membranes was studied by infrared spectroscopy. The membrane properties, such as water uptake, ion exchange capacity, swelling performance and ionic resistance, were studied as functions of the degree of grafting. The thermal and chemical stability of the sulfonic acid membranes was also investigated. The membrane properties were found to depend on the degree of grafting and the amorphous character of the membrane structure, and the better membrane properties were obtained at a degree of grafting in the range 12–21%. Copyright © 2003 Society of Chemical Industry     

燃料电池用纳米改性聚苯并咪唑阴离子交换膜的制备

以环氧氯丙烷和1–甲基咪唑为原料制备新型离子液体(IL),以IL为原料对氧化石墨烯(GO)进行表面修饰制备离子液体功能化氧化石墨烯(IL–GO),以IL–GO为添加剂制备基于含氟聚苯并咪唑(FPBI)复合膜。研究了IL–GO的含量对复合膜的热稳定性、力学强度、离子电导率、离子交换容量(IEC)、吸水率、溶胀度和耐碱性等性能的影响。研究结果表明,复合膜的IEC、离子电导率和拉伸性能都随着IL–GO含量的增加而增大,当IL–GO含量为30%时其拉伸应力和拉伸弹性模量分别达到77.5 MPa和1.95 GPa,在80℃下,其最大离子电导率可达72.3 m S/cm,然而复合膜的热稳定性并没随着IL–GO含量的增加而改变。FPBI/IL–GO复合膜具有良好的稳定性,该系列阴离子交换膜有望在碱性阴离子交换膜燃料电池中得到应用。     

交联聚苯乙烯磺酸钠结构与性能表征

通过溶液自由基聚合法合成了交联的聚苯乙烯磺酸钠(PSS)。并以红外、凝胶渗透色谱(GPC)、元素分析、电导率、表面张力、分散稳定性仪对合成的交联聚苯乙烯磺酸钠的结构和性能进行了表征,表明合成的交联PSS具有w(S)=6.76%的高磺酸根含量、多分散性(Mn/Mw)为1.52的相对分子质量分布集中的结构特征。该聚合物还具有阴离子高分子表面活性剂的特征,25℃时,其临界胶束质量浓度为5 g/L,在该质量浓度时,表面张力为64 mN/m,水溶液的电导率为435μs/cm,并具有优良的分散稳定性能,当PSS质量分数从0变化到1.0%时,TiO2悬浮液2 h内平均粒径的增加值由418.747μm减小到1.499μm,分散稳定指数从29.47降为9.01,其分散能力优于目前广泛使用的萘磺酸盐甲醛缩合物分散剂。     

Hydrophilic interpolymer membranes from crosslinked blends of poly(vinylalcohol), poly(styrene sodium sulfonate) and poly(vinyl methyl ether–alt–maleic anhydride)

Interpolymer ion exchange membranes were prepared from a compatible casting solution that contained poly(styrene sodium sulfonate), poly(vinyl methyl ether–alt–maleic anhydride), and poly(vinyl alcohol). Crosslinking of the films was accomplished through the formation of ester linkages that were stable in aqueous environments. Membrane properties (water content, capacity, concentration potential, equivalent conductivity) were measured over a wide range of membrane compositions. Ultrafiltration was carried out with a feed solution that was 0.01N in KCI and 15 ppm in erythrosin. Rejection and hydraulic permeability data were reported as a function of membrane composition.     

Fundamental studies of homogeneous cation exchange membranes from poly(2,6‐dimethyl‐1,4‐phenylene oxide): Membranes prepared by simultaneous aryl‐sulfonation and aryl‐bromination

Strong acid homogenous cation exchange membranes were obtained by simultaneously introducing sulfonic and bromine groups into poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO). The ion‐exchange capacity (IEC), water content, transport number, diffusion coefficient, contact angle, and tensile strength of the obtained membranes were studied. The results show that the membrane intrinsic properties are largely dependent on the substitution of bromine: the IEC and water content decrease with bromine content, while the area resistance and permselectivity of the membranes increase with this trend. Therefore, by properly balancing them, a series of homogenous cation exchange membranes having good electrical properties and physical stability can be obtained to comply with different industrial electromembrane processes, such as diffusion dialysis, electrodialysis, electrodeionization, etc. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2238–2243, 2006     

基于PVDF薄膜辐照接枝制备质子交换膜

含氟磺酸型质子交换膜是一类具有高热稳定性、化学稳定性及良好力学性能的离子交换膜,具有极其广阔的应用前景。采用⁶⁰Co辐照接枝技术,在聚偏氟乙烯（PVDF）基膜上产生自由基聚合位点,进而接枝对苯乙烯磺酰氯单体,经过一定条件酸碱处理得到一种新型偏氟磺酸型质子交换膜。并对其进行红外分析,结果显示PVDF膜上成功接枝上了对苯乙烯磺酰氯单体;定量研究了在相同辐照总剂量、不同剂量率条件下,所得质子交换膜的质子传导率、吸水率及离子交换容量与接枝率的关系,结果表明：当剂量率为40 Gy·min^-1时,所得质子交换膜接枝率为52.7%,吸水率为36.85%,80℃时质子传导率达到136 mS·cm^-1,离子交换容量为1.274 mmol·g^-1。