Self-assembled lamellar nanochannels in polyoxometalate-polymer nanocomposites for proton conduction

The construction of nanostructured ion-transport channels is highly desirable in the design of advanced electrolyte materials,as it can enhance ion conductivity by offering short ion-transport pathways.In this work,we present a supramolecular strategy to fabricate a nanocomposite electrolyte containing highly ordered lamellar proton-conducting nanochannels,by the electrostatic self-assembly of a polyoxometalate H_3 PW_(12)O_(4 O)(PW) and a comb copolymer poly(4-methlstyrene)-graft-poly(N-vinyl pyrrolidone).PW can effectively regulate the self-assembling order of polymer moieties to form a large-ra nge lamellar structure,meanwhile,introducing protons into the nanoscale lamellar domains to build proton transport channels.Moreover,the rigid PW clusters contribute a remarkable mechanical reinforcement to the nanocomposites.The lamellar nanocomposite exhibits a conductivity of 4.3 × 10~(-4) S/cm and a storage modulus of 1.1 × 10~7 Pa at room temperature.This study provides a new strategy to construct nanostructured ion-conductive pathways in electrolyte materials.     

受限于两平行板间的对称星形共聚物Am Bm熔体相行为的格子自洽场理论研究

采用格子自洽场理论计算研究了受限于2个平行板间的对称星形共聚物AmBm(m=1,2,3,4,5)熔体形成的层状相结构.在给定的相互作用下(χNAB不变,χ为Flory-Huggins相互作用参数,NAB=(N?1)/m为单个聚合物分子中一对AB臂的总链节数目),针对平行板间距为体相周期的情况,系统考察了共聚物链长N和单个聚合物分子中A(或B)臂数目m对受限层结构细节及层取向的影响.由计算结果,当N或NAB不变时,受限层的归一化界面宽度随m的增大而减小.受限板为中性时,垂直层结构的单链自由能比平行层结构的低.随着板对共聚物中一种嵌段的选择作用Λ的增大,体系发生垂直层到平行层的转变,该转变为一阶相变.当m不变时,N越小,上述转变出现在越大的Λ值处,体系越容易保持垂直层结构.并且N越小,层状结构周期越小.当N或NAB不变时,m越大体系越容易保持垂直层结构.总之,星形共聚物的链长越短、臂数越多时,垂直层稳定的Λ区间越大、层状结构的界面宽度越小.这些结论可以指导刻蚀应用中对体系参数的选择.     

DRDF analysis of wide-angle x-ray scattering of natural rubber

A differential radial distribution function (DRDF) of molten natural rubber (NR) was derived from its wide-angle x-ray scattering (WAXS) data. Three peaks with Bragg spacings 4.85, 2.31, and 1.23 Å corresponding, respectively, to interchain, C₁-C₃ and C₁ -C₂ distances are present in the corrected WAXS curve. The derived DRDF, which is shown to be greatly improved than the ones published so far, contains six peaks located at 1.51, 2.48, 3.98, 5.68, 10.65, and 15.25 Å. Maximum contributions of intramolecular atomic distances to the radial distribution peaks were estimated and compared with the experimental results. The comparison shows that the first three peaks are intramolecular in origin and the remaining peaks are predominantly due to intermolecular regularities. A periodicity of an approximately constant interval of 5.26 Å is found between the intermolecular peaks and is attributable to the organizations of more or less parallel chain segments in the material. This finding provided additional evidence for the presence of local lateral ordering to the extent of about 30 Å in molten-state natural rubber.     

锂离子电池片状四氧化三钴负极的合成及改性

采用液相沉淀法结合低温固相热解法合成了锂离子电池片状Co3O4负极.通过X射线粉体衍射(XRD)、Brunauer-Emmett-Teller(BET)比表面积分析、扫描电子显微镜(SEM)及恒电流充放电等表征手段,发现该Co3O4为立方相,结晶完整且无杂质,由直径为1.5-3.0μm、厚度约为100-300 nm的不规则片状颗粒组成,比表面积约为30.5 m2·g-1;其比容量高且容量保持率好,在0.1C倍率下,首次放电容量高达1444.5 mAh·g-1,50次循环后充电容量仍大于1100.0 mAh·g-1;但在高倍率(1C)下,50次循环后充电容量保持率仅为75.3%,倍率性能一般.故采用碳纳米管(CNTs)掺杂改性,结果表明:在1C倍率下,70次循环后复合材料充电容量保持率为96.3%;在2C倍率下,50次循环后充电容量保持率仍高达97.0%,倍率性能显著提升.     

辊速辊温对高密度聚乙烯拉伸微孔膜及其片晶结构的影响

采用熔融挤出片材—退火—冷拉伸—热拉伸—热定形的方法来制备高密度聚乙烯(HDPE)微孔膜,利用FTIR、SEM和DSC等测试方法来研究辊速辊温对HDPE拉伸微孔膜及其片晶结构的影响.研究结果表明,所选树脂的分子量、分子量分布以及弛豫时间能够满足现有加工条件,形成片晶取向度较高的预制膜;在相同辊温下,随辊速增加,退火前预...     

Solution Crystallization Behavior of Linear and Star-shaped Poly(ethylene glycol)-b-Poly(ε-caprolactone) Block Copolymers简

Lamellar crystals of diblock, triblock and four-arm poly（ethylene glycol）-b-poly（ε-caprolactone） （PEG-b-PCL） crystalline-crystalline copolymers were successfully obtained from their solution. Morphology and structure of lamellar crystals of crystalline-crystalline copotymers were investigated using tapping-mode atomic force microscopy （AFM） and selected area electron diffraction （SAED）. All of these samples showed the truncated-lozenge multilayer basal shapes with central screw dislocation or central stack, which were all obtained simultaneously from the oil bath. The diffraction pattern of PEG block lamellar crystal is attributed to the （120） diffracting planes and the pattern of PCL block lamellar crystal is attributed to the （1 I0） diffracting planes and （200） diffracting planes according to the SAED results. Four （110） crystal growth planes and two （200） crystal growth planes are discovered for the PCL blocks, but the （120） crystal growth planes of PEG blocks are hided in the figure of AFM. The crystalline structure of the four-arm copolymers （FA） is more disorder and confused than that of the diblock （DI） copolymer and the striated fold surface structures of lamellar crystals of four-arm copolymers （FA） are smoother than these of linear analogues, owing to the confused crystallization of blocks caused by the mutual restriction of blocks and the hindrance of the dendritic cores. In addition, the aspect ratio of FA is greater than that of the others. It is hypothesized that there are two reasons for the change of aspect ratios. First, the （200） diffracting planes of PCL crystals grew slowly compared to their （110） diffracting planes because of difference in the energy barrier. Secondly, edge dislocations on the （200） diffracting planes are also responsible for the variation of the aspect ratio. Consequently, the crystalline defects are augmented by the competing blocks crystallized simultaneously and the hindrance of the dendritic cores.     

Estimation of the Interfacial Tension Between the Lamellar and the Sponge Phases of a Lyotropic System

In lyotropic systems, the sponge and the lamellar phases possess the same local structure: a membrane made of a bilayer of surfactants. In the quasiternary lyotropic system CPCl/brine/hexanol, the bilayer is continuous through the interface between the lamellar and the sponge phases. A model based on this phenomenon has predicted a very low value of the interfacial free energy. The study of hydrodynamic relaxation time of distorted spherical lamellar droplets gives an estimation of the interfacial tension value. Results confirm the validity of the model and the dependence on membrane volume fraction is explained by a simple scaling law.     

多重网络增强的层状光子晶体水凝胶及应力变色响应

基于PDGI/PAAm (PDGI/SN)层状光子晶体水凝胶,制备了多重网络PDGI/PAAm-PAMPS-PAAm(PDGI/TN)水凝胶,将水凝胶浸入6 : 4(V/V)乙醇水溶液中去溶胀,记为凝胶PDGI/TN-0.6。结果表明,引入多重网络之后,PDGI/TN凝胶的溶胀率从PDGI/SN的850% ± 45%提高到1070% ± 50%,颜色从蓝色(λ_max=450 nm)变为透明,去溶胀后Bragg衍射峰为670 nm,实现凝胶的Bragg衍射峰在450－670 nm间调控。拉伸和压缩实验说明,PDGI/TN-0.6力学性能优异,拉伸强度和压缩强度分别达到0.99和37.0 MPa。同时,PDGI/TN-0.6具有优异应力变色响应性,压缩应变(ε_c)从0增加到0.5,Bragg衍射峰发生蓝移,响应范围覆盖可见光;当撤去应力后,立即恢复初始状态,可重复多次。利用扫描电镜(SEM)进一步研究了层状光子晶体水凝胶层微观结构。     

二维层状分子筛前驱体的合成、改性及催化应用

二维层状分子筛前驱体具有三维分子筛的层结构单元,具备母体分子筛的特性,其开放二维片层骨架结构给合成新分子筛以及基于其改性得到新衍生结构分子筛提供新机遇,是近年来分子筛研究领域一个新热点。大量二维片层前驱体可直接合成或通过三维分子筛后处理获得,基于二维片层前驱体人们发展了溶胀、剥层、柱撑、原子扩孔、层重组等层操纵的策略,通过这些策略一些常规方法难以合成或不符合理论规则的分子筛被合成出来,这极大地丰富了二维层状分子筛前驱体的研究领域,扩展了其应用范围。本文概述了二维层状分子筛前驱体的结构特点,系统总结了近年来二维层状分子筛前驱体的合成方法,在此基础上着重阐述了其改性获得新结构分子筛的新策略,并介绍了在多相催化反应中的应用。     

原位X射线研究拉伸过程中间规聚丙烯晶体熔融与晶体取向关系

间规聚丙烯熔体(sPP)淬冷至液氮温度并保持5 min, 于20, 40, 80, 120 ℃下等温退火10 h, 制备出具有不同片晶厚度的样品. 在室温条件下, 利用原位X射线在线研究sPP样品拉伸过程中应力诱导的晶体熔融和晶体取向关系. 结果表明, 在单轴拉伸过程中, 应力导致的晶体熔融和晶体取向同时发生, 即两者在同一应变、 同一应力下同时发生, 这一特性不受片晶厚度的影响. 随着片晶厚度的增加, 晶体熔融和取向需要的临界应力不断增大, 在所研究范围内, 该临界应力的增加和片晶厚度基本呈线性关系. 另外, 随着片晶厚度增大, 样品的弹性模量、 屈服强度和应变硬化模量均有一定程度的增大.