季铵化壳聚糖/[Nbmm]OH碱性复合阴离子膜的制备及性能

以季铵化壳聚糖(QCS)为制膜原料,[Nbmm]OH碱性离子液体为掺杂物,通过溶液浇铸法制备了一系列掺杂碱性离子液体([Nbmm]OH)的交联复合膜(QCS/[Nbmm]OH)。采用红外光谱、热重分析及扫描电镜对复合膜的结构、热稳定性和微观形貌进行分析。同时考察离子液体掺杂量对QCS/[Nbmm]OH复合膜的含水率、力学强度及导电性能等指标的影响。结果表明,随着[Nbmm]OH离子液体掺杂量的增加,复合膜的含水率、离子交换量以及电导率均增加,但是拉伸强度和断裂伸长率略有下降。其中,当离子液体掺杂量为15%(质量分数)时,复合膜在70℃的电导率为0.0115S/cm,拉伸强度为19 MPa,离子交换量为1.25 mmol/g,含水率和溶胀度分别为143%和87%。     

新型[BTMG]OH离子液体的合成及其在阴离子交换膜中的应用

以溴代正丁烷、N,N,N′,N′-四甲基胍(TMG)为原料,通过两步法合成新型氢氧型N,N,N′,N′-四甲基-N″-丁基胍离子液体([BTMG]OH).以聚乙烯醇为制膜原料、戊二醛为交联剂、离子液体[BTMG]OH为掺杂物,通过流延法制备了PVA/[BTMG]OH复合膜.实验过程中,通过红外光谱、热重分析对所制备的复合膜的结构、热稳定性进行表征.同时考察了离子液体含量对PVA/[BTMG]OH复合膜的含水率、溶胀性能、离子交换容量、机械性能及电导率的影响.其中,当离子液体质量分数为38.07%时,复合膜具有良好的综合性能,此时膜的含水率和拉伸强度分别为139.6%和19.6MPa;60℃时,该膜的电导率为2.33×10-2 S/cm.另外,该膜经过60℃、400h、KOH(6mol/L)的耐碱性测试,60℃时的电导率为2.25×10-2S/cm,降幅仅为3.3%,且外观形貌无明显变化,表现出优异的耐碱稳定性.     

PVA—PWA—Al2O3无机-有机复合质子交换膜的研究

以聚乙烯醇（PVA）、磷钨酸（PWA）和氧化铝（Al2O3）溶胶为原料，制备得到PVA—PWA—Al2O3无机-有机复合质子交换膜，测定了膜的电导率、含水率、溶胀度和甲醇透过系数等性质．测试结果表明，该复合膜具有较高的导电率和较好的阻醇效果，室温下测得电导率最高达到1．162S／cm，甲醇透过系数在10^-7cm^2／s左右．复合膜中PWA含量增加，膜的电导率、含水率、溶胀度和甲醇透过系数都有所上升；膜中Al2O3含量增加，膜的电导率、含水率、溶胀度提高，但甲醇渗透系数稍有下降．     

PVA-PWA-Al2O3无机-有机复合质子交换膜的研究

以聚乙烯醇(PVA)、磷钨酸(PWA)和氧化铝(Al2O3)溶胶为原料,制备得到PVA-PWA-Al2O3无机-有机复合质子交换膜,测定了膜的电导率、含水率、溶胀度和甲醇透过系数等性质.测试结果表明,该复合膜具有较高的导电率和较好的阻醇效果,室温下测得电导率最高达到1.162 S/cm,甲醇透过系数在10-7cm2/s左右.复合膜中PWA含量增加,膜的电导率、含水率、溶胀度和甲醇透过系数都有所上升;膜中Al2O3含量增加,膜的电导率、含水率、溶胀度提高,但甲醇渗透系数稍有下降.     

磺化聚苯醚-磷酸锆质子交换复合膜的制备与性能研究

采用溶胶-凝胶法将磺化聚苯醚(SPPO)与磷酸锆(ZrP)复合得到质子交换膜,重点考察了ZrP含量对复合膜含水率、溶胀度和质子电导率的影响,采用红外光谱和交流阻抗法表征SPPO-ZrP复合膜的微观结构和质子电导率。结果表明,SPPO-ZrP复合膜含水率和溶胀度都随着ZrP质量分数增加而逐渐减小,当ZrP质量分数为20%时,膜的含水率和溶胀度分别达到18%和2.1%。通过交流阻抗法对质子传导性能的表征结果显示,随ZrP质量分数增加复合膜质子电导率逐渐增大,ZrP质量分数20%的SPPO-ZrP复合膜质子电导率在室温下达到1.6×10-2S/cm。     

磺化聚苯醚-磷酸锆质子交换复合膜的制备与性能研究

开发价格低廉且性能优异的质子交换膜是目前燃料电池研究的热点.采用溶胶-凝胶法将磺化聚苯醚(SPPO)与磷酸锆(ZrP)复合得到质子交换膜,重点考察了ZrP含量对复合膜含水率、溶胀度和质子电导率的影响,采用红外光谱和交流阻抗法表征SPPO-ZrP复合膜的微观结构和质子电导率.结果表明SPPO与ZrP产生相互作用使SPPO结构发生变化.SPPO-ZrP复合膜含水率和溶胀度都随着ZrP质量分数增加而逐渐减小,当ZrP质量分数为20％时,膜的含水率和溶胀度分别达到18％和2.1％.通过交流阻抗法对质子传导性能的表征结果显示,随ZrP质量分数增加复合膜质子电导率逐渐增大,ZrP质量分数20％的SPPO-ZrP复合膜质子电导率在室温下达到1.6×10-2S/cm.     

PVA/ZSM-5分子筛复合膜的制备与性能研究

目的以聚乙烯醇(PVA)为基体材料,添加ZSM-5沸石分子筛和富马酸交联剂制备出一系列的复合膜,研究分子筛含量对复合膜性能的影响。方法用流延法制备复合膜,进行X射线衍射分析和扫描电镜分析,测定复合膜的拉伸性能、耐水溶胀性、透光率与雾度。结果经富马酸交联后PVA薄膜的拉伸强度和耐水溶性得到了明显改善,随着分子筛含量的增多,复合膜的拉伸强度逐渐减小,分子筛的加入对复合膜的溶胀度和透光性都有降低作用。结论从综合测定结果来看,ZSM-5分子筛质量分数为5%时的复合膜具有相对较好的性能。     

聚苯胺/聚乙烯醇复合膜的性能研究

采用聚乙烯醇为基质材料制备了聚苯胺/聚乙烯醇(PANI/PVA)复合膜,讨论了PANI与PVA质量比、膜干燥温度对复合膜性能的影响,并对PVA膜、HCl掺杂PANI膜以及PANI/PVA复合膜的拉伸断裂强度、断裂伸长率、电导率以及热稳定性作了比较。结果表明:PVA膜的拉伸断裂强度、断裂伸长率最强,但是电导率最小;PANI/PVA复合膜电导率最大,其拉伸断裂强度、断裂伸长率比未加PVA的HCl掺杂PANI膜都得到了大大提高。在180℃之前,PVA膜最稳定,HCl掺杂PANI膜稳定性最差;在260℃之后,HCl掺杂PANI膜最稳定,PVA膜稳定性最差。     

丝胶/PVA/玉米淀粉共混凝胶膜的制备及其体外降解调控研究

废弃蚕茧中提取并制得易溶性丝胶蛋白(SS)粉末,玉米淀粉(MS)作填充剂,与PVA经水相共混和反复冻融制备了不同配比SS/PVA/MS复合凝胶膜。经红外检测对其结构进行了确认;分别以去离子水和模拟体液(SBF)为介质,考察了SS/PVA质量比及MS含量对膜材料力学性能、溶胀性和降解性的影响。结果显示SS/PVA质量比为3/7,MS含量为18%时,膜的断裂伸长率为最优,拉伸强度可达到较优水平,而通过对MS含量和SS/PVA质量比的调整,可以达到调节复合膜降解速率的目的。     

聚乙烯醇/合成硅酸镁锂纳米复合膜的制备研究

以聚乙烯醇(PVA)和合成硅酸镁锂为原料,采用溶液插层-流延成膜法制备了不同合成硅酸镁锂含量的PVA/合成硅酸镁锂纳米复合膜,并对PVA/合成硅酸镁锂纳米复合膜进行了表征。研究结果表明:6%(wt,质量分数)合成硅酸镁锂含量制得的PVA/合成硅酸镁锂纳米复合膜,结晶熔融温度达到253.1℃,平衡溶胀比为2.6,拉伸强度最大达到78MPa、断裂伸长率达到100%,耐水性、热性能和力学性能都得到明显改善。     

燃料电池用QCS键和层析硅胶膜的制备及其性能表征

以季铵化壳聚糖(QCS)和层析硅胶为原料,制备了不同硅胶含量的多孔膜。用傅里叶变换红外(FTIR)和扫描电镜(SEM)对多孔膜的结构和形貌进行表征。同时,考察了层析硅胶的用量对多孔膜的含水率(WU)、溶胀度(SR)、机械性能和电导率的影响。结果表明,随着层析硅胶含量的增加,多孔膜的含水率、溶胀度和电导率均升高,但机械性能下降。当层析硅胶的用量为40%时,多孔膜的含水率高达816%,但是膜的溶胀度仅为189%,拉伸强度为5.6MPa,断裂伸长率为4.2%;在测试温度为70℃时,不同层析硅胶含量多孔膜的电导率数值分布在2.4~3.9×10~(-2)S/cm的范围内,且随硅胶含量的增加而增加。     

One-step carbon nanotubes grafting with styrene-co-acrylonitrile by reactive melt blending for electrospinning of conductive reinforced composite membranes

Aim of this research was to electrospin conductive composite membrane of styrene-co-acrylonitrile (SAN) reinforced with carbon nanotubes (CNTs). To improve electrical conductivity of final membrane ionic liquid (IL) was used. For better dispersion of CNTs in SAN matrix one-step reactive melt blending method for grafting of SAN onto CNTs was developed. Influence of SANm-g-CNTs on solutions properties was studied and compared to solutions with ungrafted CNTs and carboxyl group functionazed CNTs (CNT-COOHs). Combination of IL and SANm-g-CNTs increase in to orders of magnitude SAN membrane tensile stress and modulus. Electrical conductivity of obtained membranes achieved the level of semi-conductor materials.     

Guanidine分子在燃料电池用阴离子交换膜中的应用

以壳聚糖(CS)和2,3-环氧丙基三甲基氯化铵(GTA)为原料,制备季铵化壳聚糖(QCS),将其与小分子游离胍(Guanidine)共混,借助戊二醛(GA)的化学交联作用,将季铵化壳聚糖中的氨基以及胍中的氨基交联,形成网状结构,由此制得含有不同含量Guanidine分子的交联QCS-G阴离子交换膜。实验过程中,对该膜的含水率、溶胀度、力学强度、电导率及耐碱稳定性等进行了详细的考察。结果表明,游离胍的引入可有效地提高膜的电导率和耐碱稳定性,同时降低了膜的溶胀度及含水率。其中小分子游离胍质量分数为2.5%的膜(QCS-G2.5%)在70℃时的电导率可达到6.58×10~(-2)S/cm;在10 mol/L NaOH溶液中浸渍72 h后该膜70℃测得的电导率损失仅为3.8%,离子交换量损失仅为3.82%,表明该膜的耐碱性能较好。     

Solid biopolymer electrolytes based on all-cellulose composites prepared by partially dissolving cellulosic fibers in the ionic liquid 1-butyl-3-methylimidazolium chloride

This study investigated the effects of an ionic liquid, 1-butyl-3-methylimidazolium chloride ([Bmim]Cl), as a doping salt, on the properties of resulting solid biopolymer electrolytes (SPEs) based on all-cellulose composites. The conductivity of the resulting SPEs increased with the [Bmim]Cl loading. Both incubation time and chemical loading affected the tensile properties of the SPEs. The SPEs prepared under the optimum processing conditions exhibited a tensile strength and conductivity of 18.2 MPa and 1.28 × 10⁻³ S cm⁻¹, respectively, when tested at room temperature. FTIR and XPS spectra showed that the concentration of [Bmim]Cl in the SPEs was greater at the surface than at the interior. Treatment with [Bmim]Cl resulted in a decrease in the crystallinity and thermal stability of the SPEs as evidenced by XRD and TGA analyses. This study demonstrates that treatment of cellulosic materials with the ionic liquid [Bmim]Cl can create biomass-based SPEs with high conductivity, improved mechanical properties, good thermal stability and easy processability.     

静电纺丝与静电喷雾技术共纺制备PPESK/PVDF复合锂电池隔膜

为了改善传统静电纺丝无纺布纤维膜力学性能较差的缺点,采用静电纺丝和静电喷雾技术相结合的方法,同时进行静电纺PPESK浓溶液和PVDF稀溶液,制备得到PPESK纤维/PVDF珠粒复合锂电池隔膜,并在160℃进行热压后处理。通过扫描电子显微镜、万能拉伸试验机、电化学工作站及充放电测试仪等表征复合锂电池隔膜的微观结构、力学性能、离子电导率和相应的电池充放电性能。结果表明,该复合隔膜具有良好的电解液润湿性,室温下离子电导率达到1.92mS·cm^-1,PVDF珠粒均匀地分布在PPESK纤维中,珠粒经热压产生微熔融有效增强了纤维之间的黏结力,使复合膜的力学强度提高到13.2MPa。此外,使用复合隔膜装配的电池展现出较高的放电比容量和稳定的循环性能。     

Electropolymerization in proton-functionalized anilinium salts/glycol deep eutectic solvents

Novel proton-functionalized solid anilinium salts (anilinium hydrochloride ([HANI]Cl) and anilinium nitrate ([HANI]NO₃)) are synthesized. Simply mixing proton-functionalized anilinium salt with glycol in appropriate ratios can get deep eutectic solvents (DESs) which are liquid at room temperature. DES system is a new type of ionic liquids (ILs) or IL analogs. Tests show that the resulting DES systems have higher conductivity and lower viscosity which are suitable for electropolymerization. The electropolymerization of aniline in novel liquid DES ([HANI]Cl/(CH₂OH)₂ and [HANI]NO₃/(CH₂OH)₂) without exogenous protons is first reported. The cyclic voltammograms (CVs) in neat DES show two pairs of redox peaks. Unlike in acidic aqueous solutions, the electropolymerization of aniline in the DES needs no exogenous protons. UV–Vis and FTIR analysis show that the conductive polyaniline (PANI) is obtained. Moreover, the specific capacitance of PANI from the [HANI]Cl/(CH₂OH)₂ system is ca. 341 F g^?1 and that from the [HANI]NO₃/(CH₂OH)₂ is ca. 492 F g^?1, which are superior to that of the PANI obtained in an acid medium. The SEM characterization indicates that the resulting PANI on ITO is cross-linked nanoporous polymer membrane, which is benefit for the capacitance performance of PANI.     

Soft but Powerful Artificial Muscles Based on 3D Graphene–CNT–Ni Heteronanostructures

Bioinspired soft ionic actuators, which exhibit large strain and high durability under low input voltages, are regarded as prospective candidates for future soft electronics. However, due to the intrinsic drawback of weak blocking force, the feasible applications of soft ionic actuators are limited until now. An electroactive artificial muscle electro‐chemomechanically reinforced with 3D graphene–carbon nanotube–nickel heteronanostructures (G–CNT–Ni) to improve blocking force and bending deformation of the ionic actuators is demonstrated. The G–CNT–Ni heteronanostructure, which provides an electrically conductive 3D network and sufficient contact area with mobile ions in the polymer electrolyte, is embedded as a nanofiller in both ionic polymer and conductive electrodes of the ionic actuators. An ionic exchangeable composite membrane consisting of Nafion, G–CNT–Ni and ionic liquid (IL) shows improved tensile modulus and strength of up to 166% and 98%, respectively, and increased ionic conductivity of 0.254 S m^?1. The ionic actuator exhibits enhanced actuation performances including three times larger bending deformation, 2.37 times higher blocking force, and 4 h durability. The electroactive artificial muscle electro‐chemomechanically reinforced with 3D G–CNT–Ni heteronanostructures offers improvements over current soft ionic actuator technologies and can advance the practical engineering applications.     

Effect of coordinated water of hexahydrate on nickel platings from choline–urea ionic liquid

Impacts of coordinated water of nickel chloride hexahydrate (NiCl₂·6H₂O) on the properties of choline–urea (ChCl–2Urea) ionic liquid (IL), including viscosity and electrical conductivity, and electrodeposition behavior of Ni coatings were investigated. Results reveal that the coordinated water exhibited a profound influence on reducing viscosity, improved electrical conductivity and promoted the formation of a nanocrystalline Ni coating, while the Ni nucleation mechanism was not altered by the presence of coordinated water, proceeding via that from the progressive three-dimensional nucleation to instantaneous nucleation with hemispherical diffusion-controlled growth when the deposition potential shifts to the negative direction. When water content was maintained no more than?~?8 wt%, a compact nanocrystalline Ni coating, with a current efficiency of almost 100%, was prepared from ChCl–2Urea–NiCl₂·6H₂O with an aid of 400 mg/L nicotinic acid (NA) at 318 K. These results indicate hydrated Ni salts can be used to replace anhydrous counterparts in preparation of Ni coating from choline–urea IL, which could reduce the impact on environment and product cost. Such a strategy may be extended to other hydrated metal salts in IL electrolyte electrodeposition for high-quality coating preparation.     

Mechanical and Electrical Properties of Cryo-worked Cu

For manufacturing the magnets of fusion machines pure copper of both high mechanical resistance and electrical conductivity is required. Though high purity copper guarantees high electrical conductivity, its mechanical properties may be not suitable for the applications in tokamaks. In this view, a new procedure developed for obtaining high purity copper with excellent mechanical strength is described in this work. Samples of oxygen free copper (OFC) have been worked by pressing in liquid nitrogen (77 K). It has been verified that the mechanical properties of the worked metal are strongly dependent on the strain rate. Very low strain rates permitted to attain values of tensile yield strength (550 MPa) significantly higher than those obtained by traditional cold-working at room temperature (450 MPa). The electrical conductivity of the cryo-worked Cu decreases with the tensile yield strength even though the hardest samples of tensile yield strength of 550 MPa exhibit still acceptable values of conductivity (about 94 % IACS at room temperature).     

凝固浴组成对PVDF-g-PACMO共聚物膜结构与抗污染性能的影响

采用亲水、无毒、生物相容性好、对蛋白质吸附有排斥作用的丙烯酰吗啉(ACMO)对聚偏氟乙烯(PVDF)本体进行亲水改性,研究了凝固浴中不同乙醇含量(乙醇:去离子水的质量比分别为0∶100,15∶85,30∶70,45∶55)对PVDFg-PACMO共聚物膜抗污染性能的影响。结果表明,随着凝固浴中乙醇含量的增加,膜断面孔结构向海绵状转变,膜平均孔径和孔隙率增大,纯水通量增加,牛血清蛋白(BSA)截留率降低,膜表面亲水性增加,抗污染性能提高。当凝固浴中乙醇质量分数为45%时,膜表面BSA的吸附量由115.4μg/cm2降至20.6μg/cm2,通量恢复率高达97.6%,总污染指数低至0.148。因此,通过改变凝固浴中乙醇的含量,能使PVDF-g-PACMO膜表面亲水性明显提高,制得了具有良好抗蛋白质污染能力的改性PVDF膜。