凹凸棒石/硅橡胶复合材料的热氧化降解和老化性能研究（英文）

本文采用高压均质结合对辊挤压工艺对天然凹凸棒石进行棒晶解离得到了纯度较高和比表面积较大(133.7 m2/g)的纳米解离凹凸棒石.进一步通过机械共混法分别将天然凹凸棒石和纳米解离凹凸棒石与硅橡胶生胶复合制备了天然凹凸棒石-硅橡胶和纳米解离凹凸棒石-硅橡胶材料,研究了天然凹凸棒石和纳米解离凹凸棒石对凹凸棒石/硅橡胶复合材料热氧化降解和老化性能的影响.结果表明,天然凹凸棒石-硅橡胶和纳米解离凹凸棒石-硅橡胶在300℃热氧老化处理0.5 h后,相比于纯硅橡胶,初始5%失重温度从385℃提高至396～399℃.系列表征结果表明,天然凹凸棒石和纳米解离凹凸棒石增强了纳米粒子与硅橡胶之间的相互作用从而抑制了纳米颗粒聚集,并且可显著提高硅橡胶侧链Si-CH_3的保存率,从而提高了该复合材料的热氧化降解和老化性能.此外,纳米解离凹凸棒石可大大抑制纳米粒子的长大;因此老化后,纳米解离凹凸棒石-硅橡胶表现出了比硅橡胶(10.6%、7.4%和5.0%)更高的拉伸强度、断裂伸长率和撕裂强度保留率(40.6%、34.9% 和30.1%).     

基于薄膜电极溶胶修饰的染料敏化太阳电池光电特性研究

染料敏化太阳电池(DSC)中的纳米薄膜电极 是决定太阳电池光电转换性能的重要组成部分. 为改善薄膜电极特性, 采用了不同浓度的TiO₂溶胶对DSC光阳极导电玻 璃和纳米TiO₂多孔薄膜进行不同方式的界面处理. 利用X射线衍射方法对制备得到的多孔薄膜以及溶胶经高温处理 后致密层中纳米TiO₂颗粒的尺寸及晶型进行了测试. 采用高分辨透射电子显微镜和场发射扫描电子 显微镜观察了纳米颗粒及薄膜微结构形貌. 采用强度调制光电流谱/光电压谱分析了TiO₂溶 胶的不同处理方式对电子传输和复合的影响. 在100 mW· cm^-2光强以及暗环境下分别测试了DSC的伏安输出性能以及暗电流. 结果表明, 不同浓度和处理方式均能较好地抑制暗电流. 溶胶处理后光生电子寿命τ_n延长, 电子传输平均时间τ_d相应缩短. 采用浓度为0.10 mol·L^-1的 溶胶对导电玻璃和多孔膜同时处理, DSC的宏观输出特性最佳, 短路电流密度J_sc提高了10.9%, 光电转换效率η提高了11.9%.     

尺寸和微结构效应对软锰矿红外光谱的影响

合成了纳米纤维状的软锰矿β-MnO₂,其研磨后粒子形貌由纳米纤维转变为纳米粒子,相结构并没有转变．纳米纤维状粒子中心锰离子局域环境有轻微改变．当粒子形貌从长纳米纤维变到短纳米纤维再到纳米粒子时,傅里叶转换红外光谱A_2u频率逐渐从514 cm^-1到574 cm^-1再到617 cm^-1．研究发现依据功能团分析无法确定额外的振动波段来源于不同尺寸和形状粒子的A_2u．通过X射线衍射的Rietveld精修和红外光谱,认为两种MnO₆的八面体构型,如4长+2短,4短+2长,在由不同路线合成的软锰矿中都会存在．微结构对软锰矿傅里叶转换红外光谱最大振动频率的影响是显著的．在红外和远红外区域的四个振动波段都做了分类.     

纳米多孔离子液体复合材料的合成及其在酯化反应中的应用

以溴化1-丁基-3-甲基咪唑离子液体和磷钨杂多酸(H₃PW₁₂O₄₀)为原料制备了杂多酸功能化离子液体复合材料催化剂(bmim-PW12),并用于催化乙酸与正丁醇酯化合成乙酸正丁酯的反应,考察了bmim-PW12不同热处理温度对其结构以及催化酯化反应活性的影响．结果表明,bmim-PW12在500 oC热处理时杂多酸 阴离子仍保持Keggin结构,但有机阳离子在350 oC以上发生了部分分解．bmim-PW12在400 oC热处理具有纳米多孔结构和较大的酸强度,且在丁醇与乙酸酯化合成乙酸丁酯反应中,具有较高的催化活性和较好的重复使用性能.     

超声喷雾共沉淀法制备的Lu3Al5O12∶Eu3+ 纳米粉体发光特性

采用新型超声喷雾共沉淀法技术,以Lu₂O₃、Eu₂O₃、Al(NO₃)₃·9H₂O为原料,制备了不同浓度Eu³⁺离子掺杂的Lu₃Al₅O₁₂纳米粉体.用X射线粉末衍射表征了获得纳米粉体的相,用扫描电镜观察了纳米粒子的形貌.测定了粉体的激发光谱、⁷F₀-⁵D₂声子边带谱与发射光谱.研究了不同高温烧结温度与Eu³⁺掺杂浓度对纳米粒子的发光强度与粒子形貌的影响规律.研究表明,当烧结温度高于900 ℃时,粉体发光强度明显增强,并且随着煅烧温度的增加,发光强度有所增强.Eu³⁺离子的最佳掺杂浓度为5~7 mol%.根据稀土离子Eu³⁺光学跃起矩阵元的特点,从发射光谱获得Eu³⁺光学跃起的J-O参量Ω₂与Ω₄.在Eu³⁺掺杂浓度均为5 mol%时,其强度参量达最小,电-声子耦合最强.然后随着掺杂浓度的进一步提高,强度参量略有增加,电-声子耦合减弱.说明Eu-O键强增加,共价性增强,Eu³⁺的局域环境对称性降低.Ω₂值低于Eu³⁺在玻璃与晶体基质中的情况,这是由于纳米粒子中存在着大量的缺陷以及晶体的结构畸变导致纳米粒子的对称性下降所致.     

Ag-Cu纳米颗粒修饰的N掺杂TiO2纳米棒阵列及其高效光催化CO2还原应用

本文采用微纳加工方法制备了负载高密度Ag-Cu纳米颗粒的N掺杂TiO₂纳米棒阵列样品. 通过TiO₂的N掺杂,可将其吸光范围调控至与Ag纳米颗粒的等离激元吸收频率相匹配的波段,从而实现复合材料中肖特基结与共振能量转移过程的协同作用. 与此同时,Cu纳米颗粒可以为CO₂还原提供活性位点. 在全谱光照射下,复合样品光催化CO₂还原的活性显著提高,CH₄生成速率可达720 μmol·g^-1·h^-1.     

5(6)羧基荧光素敏化TiO2纳米粒子的光致电子转移的荧光特性研究

通过水解TiCl₄制备了锐钛矿结构TiO₂纳米粒子, 并用时间分辨荧光光谱研究了5(6)CFL(5(6)-Carboxyfluorescein, 简称5(6)CFL)染料敏化TiO₂纳米粒子体系的光致电子转移动力学. 5(6)CFL染料敏化TiO₂纳米粒子能形成电荷转移复合物, 这归因于染料分子的激发电子态波函数Ψ(D^*)与电荷分离态波函数Ψ(D⁺ +e^-)之间的耦合作用. 当激发5(6)CFL染料敏化TiO₂纳米粒子体系时, 电子以两种不同方式注入TiO₂纳米粒子导带: 第一, 通过5(6)CFL染料分子的激发态注入; 第二, 从电荷转移复合物(5(6)CFL/TiO₂)直接注入. 时间分辨荧光光谱表明, 在水溶液中纯5(6)CFL染料的荧光以寿命为τ₁=41 ps (74.4%) 和τ₂=3.22 ns (25.6%) 的双e指数衰减, 而5(6)CFL染料敏化TiO₂纳米粒子体系的荧光分别以时间常数为τ₁=44 ps (90.4%), τ₂=478 ps (8.6%) 和τ₃=2.41 ns (1.0%) 的三e指数衰减. 本文的研究工作能够为染料敏化太阳能电池的光致电子转移机理提供有价值的参考.     

钙钛矿型中温固体氧化物燃料电池阴极Ba0.5Sr0.5Al0.1Fe0.9O3-δ

研究一种新型不含钴的钙钛矿型中温固体氧化物燃料电池阴极Ba_0.5Sr_0.5Al_0.1Fe_0.9O_3-δ (BSAF)材料的晶体结构、电导率以及在对称电池中的电极极化性能. 研究发现,BSAF阴极在空气中低于450 oC表现出典型的具有正温度系数的半导体行为,最高电导率达到14 S/cm;在450-750 oC,却表现出负温度系数,且电导率在750 oC下降到6 S/cm. 电化学研究表明,在基于混合离子导体的对称电池中,BSAF阴极在650-700 oC表现出良好的电极极化性能.以3%H₂O/H₂为燃料和空气为氧化剂,单电池在700 oC的开路电压和最大功率输出分别达到420 mW/cm².     

Ba0.98Ce0.8Tm0.2O3-α的离子导电性及其燃料电池性能

用高温固相反应法制备了Ba_0.98Ce_0.8Tm_0.2O_3-α钙钛矿型氧化物固溶体,粉末X射线衍射表明该固溶体为单相. 用交流阻抗谱技术和气体浓差电池方法研究了样品在500～900 oC、不同气体气氛中的导电性,以及该样品为固体电解质的氢-空气燃料电池性能. 该电池能稳定地工作,在900 oC时,电池的最大功率密度为110.2 mW/cm²,高于以Ba_xCe_0.8RE_0.2O₃^- (x≤1, RE=Y, Eu, Ho)为固体电解质的氢-空气燃料电池的功率密度     

铁和镧共掺杂纳米二氧化钛光催化剂的制备、表征及其光催化活性

以葡聚糖为模板,钛酸四正丁酯、硝酸铁和硝酸镧为前驱体采用模板法制备了一系列铁、镧单掺杂及共掺杂纳米TiO₂光催化剂. 利用SEM、XRD、BET比表面积测定和UV-Vis等技术对其形貌、晶体结构及表面结构、光吸收特性等进行了表征. 以甲基橙溶液的光催化降解为模型反应,考察了不同掺杂的样品在紫外和可见光下的光催化性能. TiO₂材料具有较大的比表面积(约150 m²/g),铁和镧共掺杂纳米TiO₂在可见光区域有较强的吸收,在紫外和可见光条件下较纯TiO₂和单掺杂TiO₂对甲基橙溶液具有更好的光催化降解效果,且铁和镧的掺杂量显著影响该材料的催化性能. 当铁掺杂量为0.5mol%、镧掺杂量为0.3mol%,在500 ℃焙烧2 h所得光催化材料的催化性能最佳,焙烧4 h即可使甲基橙的降解率达98.8%,且该复合材料有较高的循环回收利用率,重复使用4次仍可使甲基橙的降解率保持在88%以上.     

Investigation of ageing effects on the electrical properties of polyaniline/silver nanocomposites

Polyaniline(PANI)/Ag nanocomposites, synthesized by incorporation of separately prepared silver nanoparticles in 1-methyl-2-pyrrolidinone(NMP) solution of PANI, have been aged at the accelerated temperature of 120 oC to simulate a storage period of 2 years at 25 oC. The accelerated ageing of these materials is done by using the activation energy calculated from data collected using heat flow calorimetry (HFC). The impedance spectroscopic studies of NMP plasticized aged nanocomposite films suggest a microphase separation into reduced and oxidized repeat units. There is crosslinking of the PANI films during ageing thereby obstructing the charge transfer between PANI chains and silver nanoparticles. As a result, the resistivity is increased.     

Preparation and Characterization of Grafted Natural Rubber/Graphene Oxide Nanocomposites

Vinyltriethoxysilane (VTES) was grafted onto natural rubber (NR) in latex form, using potassium persulfate (KPS) as initiator. The VTES grafted NR (NR-g-VTES) was then further reinforced with graphene oxide (GO) by a mechanical mixing method with different GO loadings to get the rubber composite (GO/NR-g-VTES). The NR-g-VTES was characterized and confirmed by attenuated total teflectance-Fourier transforms infrared spectroscopy (ATR-FTIR). The effect of GO content on the curing characteristics and resulting mechanical properties of the GO/NR-g-VTES were studied and compared with neat NR filled with GO (NR/GO). The maximum and minimum torque and the tensile and tear strength of the NR-g-VTES/GO composites were higher than that of NR/GO. The samples containing low GO concentration showed maximum torque and tensile and tear strength. Dynamic mechanical analysis showed that the interaction between GO and NR-g-VTES was better than that of the GO-reinforced NR.     

Improved Dispersion of Carbon Nanoparticles Modified by Poly(Sodium 4-Styrenesulfonate) and Its Influence on the Properties of Natural Rubber Latex

A novel strategy of radical polymerization of sodium 4-styrenesulfonate on the surface of carbon black (CB) in the solid state was developed to prepare hydrophilic carbon nanoparticles (PNASS-CB). A high performance natural rubber latex (NRL)/PNASS-CB composite was produced by the latex compounding technique. Scanning electron microscope shows considerable improvement in the dispersion of PNASS-CB in rubber matrix. The lower degree of filler–filler networks and the stronger filler–rubber interaction of PNASS-CB in rubber matrix were confirmed by dynamic mechanical thermal analysis. Rheometric properties of NRL/PNASS-CB, like scorch time and optimum cure time, decreased. Tensile strength, tear strength, and elongation at break increased due to stronger interaction between the PNASS-CB and rubber matrix. Dynamic mechanical properties of the modified carbon nanoparticles further corroborated a significant contribution from the better dispersion and efficient load transfer of PNASS-CB on the static and dynamic mechanical properties of composites.     

Mechanical Properties and Corrosion Resistance of Vulcanized Silicone Rubber after Exposure to Artificial Urine

Medical devices, such as Foley catheters, which are commonly fabricated from silicone rubber, need to have excellent mechanical properties and physiological inertness. This study reports the development of a facile method to prepare silicone rubber with excellent long-term performance by controlling the vulcanization procedure parameters only. Mechanical, viscoelastic, and chemical properties of vulcanized silicone rubber were investigated. The corrosion resistance of vulcanized silicone rubber was assessed by exposure to artificial body urine for a period of up to 14 days. The mechanical properties of silicone rubber were changed via adjusting the vulcanization procedure parameters. The improved mechanical properties of silicone rubber are attributed to an increase in crosslink density resulting from the proposed vulcanization technology. After 14 days of immersion in urine, no significant changes in mechanical properties and internal structure were observed. This indicated that the as-prepared rubber samples had high tear resistance and physiological inertness. These long-term properties are important for their applications as semi-permanent implant materials, such as Foley catheter balloons in clinics. Our process of vulcanization of silicone rubber may have potential for fabrication of such medical devices.     

纳米填充硅橡胶超声干耦合特性*

针对工业超声无损检测领域干耦合材料种类匮乏,且声能透射率低的问题,论文在室温硫化硅橡胶基底材料中添加不同成份和配比的纳米颗粒,制备了不同种类的干耦合材料,给出了干耦合条件下超声波的传输模型,得到了声学传输规律,对比分析了干耦合材料种类、厚度、硬度、超声中心频率及载荷因素对声能传输特性的影响。搭建了声学特性测试实验平台,分别对添加氧化铝、铁和二氧化硅纳米颗粒制备的干耦合材料进行了测定,试验结果表明填充二氧化硅质量分数为5%时,所形成的纳米填充硅橡胶的声阻抗提高了13.5%,使用200kPa预载荷对试块测量时回波幅值提高了18.0%,具有良好的声耦合性能。可为实际超声检测时干耦合材料的制备及应用提供参考。     

纳米碳化硅/硅橡胶复合物非线性电导特性研究

将纳米碳化硅填加到硅橡胶中,可以获得具有非线性电导特性的纳米碳化硅/硅橡胶复合物. 本文研究了质量分数分别为5 wt%,15 wt%,30 wt%,45 wt%的纳米碳化硅/硅橡胶复合物的非线性电导特性,建立了电导率与场强的函数关系,分析了复合物的非线性电导机理,并测试了复合物的介电谱特性和击穿特性. 为了探讨非线性碳化硅/硅橡胶复合物应用于电缆终端和复合绝缘子以均匀其电场分布的可能性,应用COMSOL Multiphysics软件,对电缆终端和复合绝缘子中的电场分布进行了仿真分析. 仿真结果表明,将纳米碳化硅/硅橡胶复合物应用于电缆终端应力锥的绝缘部分,以及应用于复合绝缘子的端部,可以有效地降低其最大场强. 关键词： 纳米碳化硅/硅橡胶复合物 非线性电导特性 电场仿真     

Preparation of Silicon Carbide Nanoparticle/Butadiene Rubber/Silane Nanocomposites; Structural,Mechanical, Tribological and Thermal Properties

Silicon carbide nanoparticles (nano-SiC), in the amounts of 0, 3, and 5 parts per hundred of rubber (phr), were employed in a butadiene rubber (BR) based compound as a potential commercial rubber and the structure, mechanical, tribological and thermal properties of the samples were investigated. The use of 3 phr of nano-SiC, especially in the presence of silane, increased the crosslink density and improved the tensile strength (35%) and elongation at break (64%) of the BR. In addition; the abrasion resistance of the BR was improved about 120% and the coefficient of friction increased. Scanning electron microscopy (SEM) images revealed the use of silane resulted in an appropriate dispersion of the nano-SiC and improvement of its interaction with the matrix. The use of nano-SiC, especially with silane, increased the initial thermal decomposition temperature of the BR and decreased its rate of degradation.     

Natural rubber nanocomposites using polystyrene-encapsulated nanosilica prepared by differential microemulsion polymerization

In this study, nanocomposites of natural rubber (NR) and polystyrene (PS)-encapsulated nanosilica were prepared by latex compounding method. The nanolatex of PS-encapsulated silica was synthesized via in situ differential microemulsion polymerization. The resulted hybrid nanoparticles showed core-shell morphology with an average diameter of 40 nm. The silica hybrid nanoparticles were subsequently used as filler for the NR nanocomposite. The properties of NR were found to be improved as a result of the incorporation of PS-encapsulated nanosilica at 3 and 3-9 parts per hundred rubber (phr) for tensile strength and modulus at 300% strain, respectively, except the elongation at break, and up to 9 phr for flammability. The results from dynamic mechanical analyzer showed that the elastic properties of NR near the glass transition temperature increased with the inclusion of increasing concentration of the PS-encapsulated nanosilica, causing by the semi-interpenetrating nanostructure in the NR nanocomposites.     

与掺杂浓度相关的ZnS∶Mn纳米粒子的发光性质

采用溶胶法制备了Mn掺杂的ZnS纳米粒子,探讨了掺杂离子浓度对ZnS∶Mn纳米粒子的晶体结构和发光性质的影响。通过X射线衍射（XRD）对样品的结构进行了表征,结果表明：所制备的ZnS∶Mn纳米粒子为立方闪锌矿结构,其在Mn离子的掺杂浓度达到6%时不发生分相,但随着掺杂浓度的增加,纳米粒子的平均粒径会减小。光致发光光谱和荧光光谱的结果表明：通过改变掺杂离子的浓度可实现对ZnS∶Mn纳米粒子590 nm附近荧光发射波长的调节。此外,研究了温度对纳米粒子形貌和发光性质的影响。高分辨透射电子显微镜（HRTEM）观察发现,经过50℃陈化1 h后的ZnS∶Mn样品的平均粒径增大约为20 nm,且加热陈化有利于ZnS∶Mn纳米粒子中Mn2＋在590 nm处产生荧光。     

真空紫外辐照对MQ增强硅橡胶热性能及光学性能的影响

 采用空间综合辐照模拟设备研究了真空紫外辐照对MQ增强加成型硅橡胶的表面形貌、质量损失、热性能及光学性能的影响。试验结果表明：真空紫外辐照后,硅橡胶表面出现损伤裂纹,随辐照剂量的增加,裂纹的数量增多;真空紫外辐照后,硅橡胶的质量有所损失,其质损率随辐照剂量的增加而增加;真空紫外辐照后硅橡胶的耐热性随辐照剂量的增加先增加而后下降;真空紫外辐照对硅橡胶材料的体膨胀/收缩变形影响不大,但对材料的光学性能有较大影响,随着辐照剂量的增加,材料的光学透过率下降。