PEO/PPC/Nano TiO_2-PMMA复合聚合物电解质膜的制备及性能

以聚甲基乙撑碳酸酯(PPC)和聚氧化乙烯(PEO)为基体材料,添加经聚甲基丙烯酸甲酯(PMMA)接枝改性的纳米TiO2(nano TiO2-PMMA),采用溶液浇铸法制备了锂离子电池PEO/PPC/TiO2-PMMA复合聚合物电解质(CPE)膜。用热重分析、红外光谱、交流阻抗、扫描电镜等方法研究了nano TiO2-PMMA对复合聚合物电解质膜的电化学性能影响。结果表明,当TiO2的接枝率为8.0%时,PEO/PPC/TiO2-PMMA复合聚合物电解质膜具有良好的电化学性能:室温离子电导率达到1.3×10-5 S/cm,电化学稳定窗口达到4.5V以上,锂离子迁移数为0.49。     

P(MMA-AN)的合成及其凝胶电解质的制备与性能

以甲基丙烯酸甲酯(MMA)和丙烯腈(AN)为单体,自由基引发聚合合成了聚(甲基丙烯酸甲酯-丙烯腈)[P(MMA-AN)]无规共聚物。采用红外光谱分析及元素分析法对共聚物的结构进行了表征。然后以此P(MMA-AN)无规共聚物为基体制备共聚物含量分别为30%、40%、50%(质量分数)的凝胶聚合物电解质(GPE)。采用交流阻抗法对其电性能进行表征。结果发现当MMA与AN投料比为1:3且共聚物在凝胶聚合物电解质中质量分数为30%时,GPE体系电导率达到最大值。     

原位复合法制备TiO2 / ( PEO)8LiClO4 聚合物电解质

以聚氧化乙烯/ 高氯酸锂络合物( ( PEO)₈LiClO₄ ) 为基体, 通过钛酸四丁酯的水解缩合反应在基体中原位生成TiO₂粒子, 制备了TiO₂ / ( PEO)₈LiClO₄复合聚合物电解质膜。采用SEM、DSC 和交流阻抗方法分别研究了电解质膜的表面形貌、热性能和离子导电性能。结果表明, 原位生成的TiO₂ 粒子均匀分散于PEO 基体中。复合TiO₂后电解质膜的玻璃化转变温度和结晶度降低。电解质膜的离子导电行为满足Arrhenius 方程, 并在5 %TiO₂含量时体系的电导率出现最大值5. 5 ×10 -5 S/ cm (20 ℃) 。以此膜为电解质组装的全固态聚合物锂电池放电时电压平稳, 20 次循环后放电容量保持在107 mAh/ g。      

溶胶-凝胶法制备微孔复合聚合物电解质

使用钛酸丁酯作为前驱体,在聚偏氟乙烯-六氟丙烯溶液中分解为T iO2,与聚合物基体进行复合,制备的聚合物膜吸附电解质溶液后成为微孔复合聚合物电解质(M CPE)。用SEM、DSC、FT-IR、XRD等方法对复合聚合物膜进行表征,并测试了M CPE的离子电导率,发现当复合聚合物膜中T iO2粒子的质量分数为8.2%时,聚合物电解质具有最高的离子电导率1.27×1-0 3S/cm。     

原位复合法制备P(AALi-AN-BA)/LiX/SiO2聚合物电解质及其导电性

共聚单体丙烯酸锂(AAL i)、丙烯腈(AN)、丙烯酸丁酯(BA)聚合的同时前驱体正硅酸乙酯(TEOS)水解缩合,在聚合物基体原位生成S iO2粒子,添加复盐L iX(L iC lO4-L iNO3-L iB r共熔盐)后制备了P(AAL i-AN-BA)/L iX/S iO2复合聚合物电解质,用IR和DTA-TG对其进行了表征,采用交流阻抗法研究了电解质膜的离子导电性能。结果表明,原位复合S iO2后体系的热稳定性提高,锂离子传输表观活化能Ea明显降低,电导率增大,当S iO2添加量为10%,L iX含量为75%时,体系的室温电导率达到最大值6.26×10-4S/cm(20℃)。     

含氟聚合物纳米TiO2复合涂层性能研究

为了深入探讨含氟聚合物纳米TiO2复合涂层性能,在γ-甲基丙烯酰氧基丙基三甲氧基硅烷(MPT-MS)、N-甲基全氟辛基磺酰基胺基丙烯酸乙酯(MPSAEA)、甲基丙烯酸甲酯(MMA)的共聚物中利用原位复合技术引入纳米TiO2微粒,制备了均匀透明的TiO2纳米复合含氟聚合物材料.用红外光谱(FT-IR)、紫外光谱(UV-vis)、透射电镜(TEM)等表征了复合材料的形貌和结构.将聚合物用作涂层材料,用接触角测定仪、多功能电子能谱仪(XPS)和原子力量显微镜(AFM)测定了涂层与水的接触角、涂层表面的化学成分和涂层的形貌.结果表明,纳米复合聚合物可在玻片表面形成均匀光滑的涂层,涂层具有优异的疏水性.     

纳米 SiO 2/ LiClO 4/ PVDF2 HFP复合凝胶聚合物电解质的制备及其电化学性能

为了解决液态电解质锂离子电池存在的安全性问题 , 以偏氟乙烯和六氟丙烯的共聚物( PVDF2 HFP)为基体 , 通过加入高氯酸锂(LiClO 4) 、 增塑剂(碳酸丙烯酯和碳酸二甲酯) 、 纳米二氧化硅等 , 制备出了具有高电导率的复合凝胶聚合物电解质。用 X射线衍射仪测试聚合物电解质的结构 , 用交流阻抗法测定其电导率 , 用线性伏安扫描法研究了该聚合物电解质体系的电化学稳定性 , 并以其为电解质制备成锂离子电池进行充放电测试。结果- 3表明 , 在 20℃ 时复合凝胶聚合物电解质的电导率最高可达 7. 56×10 S/ cm , 该电解质在 41 6 V 以下电化学窗口稳定 , 以其为电解质的锂离子电池具有良好的电化学性能 , 说明纳米 SiO 2/ LiClO 4/ PVDF2 HFP复合凝胶聚合物电解质能满足锂离子电池的应用。     

聚氨酯/SiO_2复合凝胶聚合物电解质的制备与性能

将聚氨酯(PU)与纳米SiO_2复合,采用相转移法制备了不同SiO_2含量的PU/SiO_2复合凝胶聚合物电解质。材料微观结构、热性能和电化学性能等测试结果表明,相转移法得到了多孔结构的聚合物膜,SiO_2颗粒较均匀地分散于PU基体中;随着SiO_2含量逐渐增加,电解质的吸液率和拉伸强度呈先上升后下降的趋势;差示扫描量热分析和热重分析测试结果表明,复合多孔电解质膜的玻璃化转变温度和热分解温度较纯PU有明显提高;SiO_2质量分数为5%时制备的PU/SiO_2复合多孔凝胶聚合物电解质综合性能最优,吸液率为163%,拉伸强度为5.45 MPa,5%分解温度高达324℃,20℃时离子电导率为3.02×10-3S/cm,电化学稳定窗口为5.32 V,显示了较好的应用前景。     

纳米SiO2/LiClO4/PVDF-HFP复合凝胶聚合物电解质的制备及其电化学性能

为了解决液态电解质锂离子电池存在的安全性问题,以偏氟乙烯和六氟丙烯的共聚物(PVDF-HFP)为基体,通过加入高氯酸锂(LiC1O4)、增塑剂(碳酸丙烯酯和碳酸二甲酯)、纳米二氧化硅等,制备出了具有高电导率的复合凝胶聚合物电解质.用X射线衍射仪测试聚合物电解质的结构,用交流阻抗法测定其电导率,用线性伏安扫描法研究了该聚合物电解质体系的电化学稳定性,并以其为电解质制备成锂离子电池进行充放电测试.结果表明,在20℃时复合凝胶聚合物电解质的电导率最高可达7.56×10-3S/cm,该电解质在4.6 V以下电化学窗口稳定,以其为电解质的锂离子电池具有良好的电化学性能,说明纳米SiO2/LiC1O4/PVDF-HFP复合凝胶聚合物电解质能满足锂离子电池的应用.     

聚氨酯/SiO_2复合凝胶聚合物电解质的制备与性能EI北大核心CSCD

将聚氨酯(PU)与纳米SiO_2复合,采用相转移法制备了不同SiO_2含量的PU/SiO_2复合凝胶聚合物电解质。材料微观结构、热性能和电化学性能等测试结果表明,相转移法得到了多孔结构的聚合物膜,SiO_2颗粒较均匀地分散于PU基体中;随着SiO_2含量逐渐增加,电解质的吸液率和拉伸强度呈先上升后下降的趋势;差示扫描量热分析和热重分析测试结果表明,复合多孔电解质膜的玻璃化转变温度和热分解温度较纯PU有明显提高;SiO_2质量分数为5%时制备的PU/SiO_2复合多孔凝胶聚合物电解质综合性能最优,吸液率为163%,拉伸强度为5.45 MPa,5%分解温度高达324℃,20℃时离子电导率为3.02×10-3S/cm,电化学稳定窗口为5.32 V,显示了较好的应用前景。     

磷酰胆碱共聚物的合成及膜的生物相容性

为了研究磷酰胆碱类聚合物的生物相容性,以偶氮二异丁腈(AIBN)为引发剂,采用自由基聚合制备了系列2-甲基丙烯酰氧乙基磷酰胆碱(MPC)与甲基丙烯酸丁酯(BMA)、甲基丙烯酸异辛酯(EHMA)的共聚物PMB、PMEH.用红外光谱、元素分析、核磁共振等方法对其结构进行了表征并探讨了其在不同溶剂中的溶解性,为该类物质的提纯提供依据;通过溶剂挥发法制备了共聚物薄膜,血小板黏附实验显示,含有MPC的聚合物薄膜比不含MPC的聚合物薄膜有更好的血液相容性;溶胀度测试显示MPC聚合物薄膜有非常好的吸收水的能力,且平衡含水量(EWC)会随着MPC在聚合物薄膜中含量的增加而增加,当MPC在PMB20中的摩尔含量为18%时,平衡含水量可以达到47%,这是磷酰胆碱类聚合物薄膜具有优良生物相容性的原因之一.     

Surface modification of nanoporous alumina membranes by plasma polymerization

The deposition of plasma polymer coatings onto porous alumina (PA) membranes was investigated with the aim of adjusting the surface chemistry and the pore size of the membranes. PA membranes from commercial sources with a range of pore diameters (20, 100 and 200?nm) were used and modified by plasma polymerization using n-heptylamine (HA) monomer, which resulted in a chemically reactive polymer surface with amino groups. Heptylamine plasma polymer (HAPP) layers with a thickness less than the pore diameter do not span the pores but reduce their diameter. Accordingly, by adjusting the deposition time and thus the thickness of the plasma polymer coating, it is feasible to produce any desired pore diameter. The structural and chemical properties of modified membranes were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM) and x-ray electron spectroscopy (XPS). The resultant PA membranes with specific surface chemistry and controlled pore size are applicable for molecular separation, cell culture, bioreactors, biosensing, drug delivery, and engineering complex composite membranes.     

Organophilic Boehmite nanoparticles by ATRP methacrylates polymerization: synthesis, characterization and dispersion in polypropylene

Boehmite nanoparticles covered with a polymer shell enhancing the organophilicity of the surface were prepared by physical adsorption of a polyelectrolyte atom transfer radical polymerization (ATRP) macroinitiator followed by graft-polymerization of methyl methacrylate or 2-hydroxyethyl methacrylate. The presence of polymer chains adsorbed/grafted on the Boehmite was confirmed by attenuated total reflection infrared (ATR-IR) spectroscopy and by thermo-gravimetric analysis (TGA), which showed a significant amount of polymer covering the particles. The methodology of polymerization and the kinetics suggested the possibility to modulate the amount, type and thickness of grafted polymer shell. These organic-inorganic hybrid materials were melt compounded in a Brabender mixer with isotactic polypropylene in the presence of functionalized polypropylene. The dispersion degree of Boehmite nanoparticles in the polypropylene matrix as well as their reinforcing effect were studied by morphology characterization [scanning electron microscopy (SEM) and X-ray diffraction (XRD)], whereas thermal and thermo-mechanical properties were assessed by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA).     

Elimination of dimer formation in InIIIporphyrin-based anion-selective membranes by covalent attachment of the ionophore

The spontaneous hydroxy-bridged dimer formation of metalloporphyrins in ion-selective membranes gives rise to a short sensor lifetime (typically days), triggered by solubility problems, the occurrence of a super-Nernstian response slope, and a pH cross response. This dimer formation is eliminated here by covalent attachment of the ionophore to the polymer matrix. Specifically, two different indium(III)porphyrins containing polymerizable groups, the chloride-selective chloro(3-[18-(3-acryloyloxypropyl)-7,12-bis(1-methoxyethyl)-3,8,13,17-tetramethylporphyrin-2-yl]propyl ester)indium(III) and the nitrite-selective Chloro(5-(4-acryloyloxyphenyl)-10,15,20-triphenylporphyrinato)indium(III), were synthesized and copolymerized with methyl methacrylate and decyl methacrylate. The covalent attachment of the ionophore to the polymer matrix indeed prevents the metalloporphyrin from forming dimeric species, as confirmed by UV/visible spectroscopy. The ion-selective membranes with grafted indium porphyrin showed Nernstian response slopes to chloride, nitrite, perchlorate, and thiocyanate anions, with a selectivity comparable to membranes with freely dissolved or underivatized metalloporphyrin. The membranes containing grafted ionophores showed a lifetime of at least two months, apparently since crystallization of the poorly soluble dimeric species may no longer occur. This is one of the first examples where the covalent attachment of an ionophore drastically improves on a number of important sensor characteristics.     

Polymer electrolytes based on grafted inorganic nanoparticles for dye-sensitized solar cells

Inorganic nanoparticles such as TiO2 and SiO2 were grafted with poly(oxyethylene methacrylate) (POEM) and blended with poly(ethylene glycol) (PEG), 1-methyl-3-propylimidazolium iodide (MPII) and iodine (I2) to prepare polymer electrolytes for dye-sensitized solar cells (DSSC). The effects of the grafted nanoparticles on the coordination interactions and structures of electrolytes were investigated using FT-IR spectroscopy and differential scanning calorimetry (DSC). The energy conversion efficiencies were obtained as 3.3 and 2.9% for TiO2 and SiO2 based electrolytes, respectively. Good interfacial contact between the electrolyte and the electrodes was also confirmed by field emission scanning electron microscopy (FE-SEM).     

化学交联及物理缔合对聚丙烯酸增稠剂的作用

采用反相乳液聚合法合成聚丙烯酸类增稠剂,比较了交联型单体及疏水型共聚单体对聚合产物在水中粘度及耐电解质的影响。结果指出,一定量的交联型单体及疏水型长链单体都能明显增加粘度。疏水单体中甲基丙烯酸十六酯（ＨＭ）的影响大于甲基丙烯酸十二酯（ＬＭ）的影响。含疏水型长链单体的缔合型交联增稠剂比非缔合型交联增稠剂的性能更优良。此外,还研究了两种类型的聚合物浓度及反相剂对粘度的影响以及用扫描电镜（ＳＥＭ）观察了     

Novel transparent ternary nanocomposite films of trialkoxysilane-capped poly(methyl methacrylate)/zirconia/titania with incorporating networks

Novel ternary nanocomposite trialkoxysilane-capped poly(methyl methacrylate)/zirconia/titania optical films were successfully prepared through a nonaqueous in situ sol–gel method. The acrylic monomers used were methyl methacrylate (MMA) and 3-(trimethoxysilyl)propyl methacrylate (MSMA). PMMA/ZrO₂–TiO₂ incorporating networks formed from alcoholysis of poly(MMA-co-MSMA), zirconium n-butoxide and titanium isoproproxide. The structure, morphology and property of the obtained nanocomposite films were investigated by X-ray photoelectron spectra, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, scanning probe microscopy, thermogravimetric analyses, UV–vis spectrum and spectro-ellipsometer. The nanoparticle size, roughness, thermal stability, UV-shielding property, and refractive index of nanocomposite films increase with the increasing of inorganic contents. The formation mechanism and reason of such improvements were examined and interpreted in a theoretical model. The nanocomposite films possess interesting properties in thermal stability and optical response due to the uniform incorporating networks between organic polymer chains and inorganic clusters.     

硅表面接枝含氟聚合物刷的动力学与表面性能

利用表面原子转移自由基聚合(SI-ATRP)法,在硅基体表面接枝了以甲基丙烯酸甲酯(MMA)和甲基丙烯酸十二氟庚酯(DFHM)为单体的嵌段聚合物刷(Si-g-PMMA-b-PDFHM)。通过衰减全反射傅里叶变换红外光谱和X射线光电子能谱分析了聚合物刷的化学结构,采用气相色谱研究了2种聚合路线的反应动力学。进而通过扫描电子显微镜、原子力显微镜和接触角测量仪表征了聚合物刷的表面形貌及润湿性。结果表明,硅片表面引发SI-ATRP的反应动力学为典型的可控聚合反应,A、B方法的反应速率常数分别为0.04916/h和0.03731/h,转化率分别为55%和45%,聚合物刷的厚度分别为4.2μm和4.8μm。硅片表面生长聚合物刷后,粗糙度增加,疏水性能明显提高。     

Instabilities in nanoporous media

Rayleigh instabilities in thin polymer films confined within nanoporous alumina membranes were studied. Thin films of poly(methyl methacrylate) (PMMA) were prepared by filling cylindrical nanopores in an anodic aluminum oxide (AAO) membrane with a PMMA solution in chloroform followed by solvent evaporation. When the PMMA nanotubes were annealed above the glass transition temperature (Tg), undulations in the film thickness were observed that were induced by a Rayleigh instability. The amplitude of the undulations increased with time and eventually bridged across the cylindrical nanopore in the AAO membrane, resulting in the formation of polymer nanorods with periodic encapsulated holes. A similar behavior was observed when PMMA films were confined within carbon nanotubes (CNTs). The Rayleigh instabilities in these confined geometries offer a novel means of controlling and fabricating the polymer nanostructures. These compartmentalized nanorods may have potential applications as delivery devices.     

Superhydrophobic thin films with nanostructured surface prepared with Au nanoparticle masks

The hydrophobicity of a perfluoropolyether bisurethane methacrylate polymer film was investigated along with the formation of nano-hairs on its surface through reactive ion etching using gold nanoparticles (Au NPs) as masks. It was found that the hydrophobicity of the polymer film was strongly dependent on the number density of the nano-hairs which was determined by that of the Au NPs. The superhydrophobic surface was obtained when the number density was higher than 250 microm(-2). The effects of surface functionalization, Au NP immobilization, and etching time on the hydrophobicity of the polymer film were also examined extensively and discussed based on the results of the contact angle measurements and the scanning electron microscopy.