HDPE氧化交联与动态流变行为

研究了高密度聚乙烯(HDPE)熔体在200℃的动态流变行为,比较了空气、氮气及加入抗氧剂B215情况下体系动态粘弹行为的差异.研究表明,在空气环境中,HDPE在低频区域出现特征粘弹行为.随着测试前热处理时间的延长,动态储能模量(G')明显增加,在低频率(ω)区域lgG'～lgω关系呈现平台特征.同时损耗角tanδ变小并出现极大值.在氮气环境中,上述特征粘弹行为存在但不明显.在加入抗氧剂的条件下,特征粘弹行为完全消失.这些现象归因于高温下HDPE的氧化导致其发生交联.     

Bi4(Ti1/3Sn2/3)3O12掺杂BaTiO3基X8R陶瓷微观结构与介电性能

研究了Bi4(Ti1/3Sn2/3)3O12掺杂对钛酸钡基陶瓷微观结构和介电性能影响。结果表明,掺杂Bi4(Ti1/3Sn2/3)3O12后钛酸钡基陶瓷晶粒明显长大,同时烧结温度可由1 280℃降低至1 180℃。系统的介电性能和Bi4(Ti1/3Sn2/3)3O12的掺杂量有密切关系。当Bi4(Ti1/3Sn2/3)3O12的掺杂量从0.5mol%增加到2mol%,体系的居里峰被明显压低和展宽,当掺杂量为2mol%时居里峰变得不明显。当Bi4(Ti1/3Sn2/3)3O12的掺杂量从0.5mol%增加到2mol%,系统的居里温度由131℃升高至139℃。当Bi4(Ti1/3Sn2/3)3O12的掺杂量为1mol%时,钛酸钡基陶瓷介电常数为1 930,介电常数温度变化率为5%(-55℃),13%(134℃),-8%(150℃),满足X8R标准。     

Preparation of Single-handed Helical and C-Shaped 3-Aminophenol-formaldehyde Resin Nanotubes and Single-handed Helical Carbonaceous Nanotubes

Single-handed helical and C-shaped 3-aminophenol-formaldehyde resin nanotubes were prepared via a supramolecular templating approach. The chiral templates and 3-aminophenol were initially organized into helical nanoribbons, followed by the adsorption of formaldehyde onto the surfaces of the helical nanoribbons. Subsequent to polymerization and further thermosetting of the resin oligomers, 3-aminophenol-formaldehyde resin nanotubes were obtained after removing the templates. When low amounts of 3-aminophenol were added, straight C-shaped 3-aminophenol-formaldehyde resin nanotubes were obtained. Increasing the amount of added 3-aminophenol led to the formation of single-handed helical nanotubes instead. When the single-handed helical resin nanotubes were carbonized at 900℃ under Ar, single-handed helical carbonaceous nanotubes were obtained. Raman spectrum indicates that this carbon is predominantly amorphous. Circular dichroism spectra illustrate that both the helical resin nanotubes and the carbonaceous nanotubes exhibit optical activity. This work indicates that the added amount and the edge-adsorption mode of the precursors on the templates determine the final morphology and chirality of the products.     

Dielectric response of ferroelectric*C liquid crystals in a bias electric field

The dielectric response of the ferroelectric chiral smectic C phase in a bias electric field is studied theoretically within the Landau model using the constant amplitude approximation. It is argued that the response consists of two modes, one of which is related to the unwinding of the helix (the unwinding mode), whereas the other mode is associated with the distortion of the polarization distribution at constant pitch of the helix (the Goldstone mode). The relaxation frequency of the unwinding mode (fu), which is inversely proportional to the square of the sample dimension along the helical axis, is estimated to be of the order of 10^-4Hz for a sample of length l≈ 1 mm along the helical axis. Consequently, in dielectric experiments performed usually at frequencies higher than fu, only the Goldstone mode contribution is detected. In this way, we can explain the behaviour of the measured static dielectric susceptibility which goes to zero as the critical field is approached from below, although the model predicts that the total static dielectric susceptibility, being a sum of the Goldstone mode and the unwinding mode contribution, diverges at the critical field.     

聚(金属酞菁)酰亚胺/碳纳米管复合材料的制备及介电性能

以四氨基铜(锌)酞菁为四胺单体, 与4,4'-二苯醚二胺(4,4'-ODA)和二苯醚四酸酐(ODPA)进行共聚, 合成了聚(金属酞菁)酰亚胺. 由于金属酞菁的引入, 聚(铜酞菁)酰亚胺和聚(锌酞菁)酰亚胺的介电常数均高于传统聚酰亚胺(PI). 以聚(铜酞菁)酰亚胺为基体, 采用溶液共混的方法, 制备了一系列碳纳米管/聚(铜酞菁)酰亚胺复合材料, 碳纳米管较为均匀地分散在聚合物基体中. 复合材料具有良好的介电性能, 掺杂碳纳米管质量分数为20%的复合材料的介电常数达到200, 介电损耗为2.25.     

预烧温度对CaO-Li_2O-Sm_2O_3-TiO_2微波介质陶瓷介电性能的影响

用固相反应法制备了CaO-Li2O-Sm2O3-TiO2(CLST)微波介质陶瓷。通过改变预烧温度(1 000~1 200℃)研究其对CLST微波介质陶瓷介电性能的影响。研究过程中,对预烧粉体与烧结陶瓷进行XRD与SEM分析,对陶瓷的介电性能εr、Q、τf进行了测试。结果表明,预烧温度对CLST微波介质陶瓷介电性能有较大影响,在预烧温度1 150℃,烧结温度1 340℃时可获得较好的介电性能:εr=112,Q=845,τf=52×10-6/℃。     

以吡啶为原料制备氮掺杂碳纳米管

在700～800 ℃,以吡啶为原料用CVD方法制备出了管径在20～40 nm的竹节状碳纳米管. EDX和XPS结果都表明氮掺杂到碳纳米管中. HRTEM研究发现掺氮碳纳米管的竹节由数层石墨片弯曲而成,纳米管外层石墨层逐渐消失.从Raman谱图的对照中发现,与相似条件下制备出的纯碳纳米管相比,氮掺杂碳纳米管的D谱带对G谱带的相对强度增加, TGA研究发现掺杂纳米管在较低温度下即被氧化,这些结果都说明氮掺杂使得纳米管的缺陷增加.     

新型乙炔封端聚酰亚胺的制备及性能

用双酚A型二醚二酐(BPADA)和3-乙炔基苯胺(m-APA)进行缩聚反应合成了乙炔基封端的聚酰亚胺预聚体, 并对预聚体的熔体黏度、稳定性和热性能等进行研究. 结果表明, 此类预聚体具有较宽的加工窗口和较低的加工温度, 适合模压成型工艺制备树脂基复合材料. 预聚体经250 ℃固化后显示了优异的热性能, 动态力学分析显示其玻璃化转变温度为363 ℃, 在氮气和空气气氛下5%热失重温度分别为490和492 ℃.     

Barium Titanate-reinforced Acrylonitrile-Butadiene Rubber: Synergy Effect of Carbon-based Secondary Filler

Acrylonitrile rubber(NBR) composites filled with barium titanate(BT) were prepared using an internal mixer and a two-roll mill. Also, a secondary filler, namely carbon nanotubes(CNT), was added in order to find a potential synergistic blend ratio of BT and CNT. The cure characteristics, tensile and dielectric properties(dielectric constant and dielectric loss) of the composites were determined. It was found that NBR/BT composites with CNT secondary filler, at a proper BT:CNT ratio, exhibited shorter scorch time(t_(s1)) and cure time(t_(c90)) together with superior tensile properties and reinforcement efficiency, relative to the one with only the primary filler. In addition, the NBR/BT-CNT composite with 80 phr BT and 1-2 phr CNT had dielectric constant of 100-500, dielectric loss of 12-100 and electrical conductivity below 10~(-4) S/m together with high thermal stability. Thus, with a proper BT:CNT mix and filler loading, we can produce mechanically superior rubber composites that are easy to process and low-cost, for flexible dielectric materials application.     

低温固态反应制备纳米Ba_(1-y)Sr_yTi_(1-x)Zr_xO_3介电材料及性能研究

将TiCl4的水解产物与固体Ba(OH)2按摩尔比1∶1混合,混合物经室温研磨、100℃烘干,得到钛酸钡纳米晶;按相同工艺掺杂,合成了一系列Ba1-ySryTi1-xZrxO3(0x≤0.3,0y≤0.4)固溶体;采用X射线衍射分析了产物的晶体结构,采用透射电镜观察了其形貌;并测定了系列固溶体的室温介电常数、介电损失.结果表明,所制备的Ba1-ySryTi1-xZrxO3为完全互溶取代固溶体,由平均粒径70 nm的球形微粒组成.经低温固态反应掺入适量锆、锶后,BaTi O3的室温介电常数由3 000提高到20 000左右.     

Optical study of porphyrin-doped carbon nanotubes

Porphyrin-doped carbon nanotubes in sodium dodecylbenzenesulfonate (NaDDBS) aqueous solution were obtained from NaDDBS/carbon nanotube aqueous dispersions. Several phonon-assisted absorption and recombination processes seem to occur, including one-phonon and two-phonon processes, and remain present even upon porphyrin doping. Power-law scaling of exciton binding energies and environmental dielectric screening effects are used to infer the doping from photoluminescence maps. The dielectric constant of the 5,10,15,20-tetrakis(4-trimethylammonium phenyl) porphyrin (H₂TTMAPP) in NaDDBS aqueous solution seems to be higher than the one of NaDDBS/aqueous solution apparently because the counterions have opposite net charges.     

Beta-1,3-glucan polysaccharides as novel one-dimensional hosts for DNA/RNA, conjugated polymers and nanoparticles

Beta-1,3-glucan polysaccharides have triple-stranded helical structures whose sense and pitch are comparable to those of polynucleotides. We recently revealed that the beta-1,3-glucans could interact with certain polynucleotides to form triple-stranded and helical macromolecular complexes consisting of two polysaccharide-strands and one polynucleotide-strand. This unique property of the beta-1,3-glucans has made it possible to utilize these polysaccharides as potential carriers for various functional polynucleotides. In particular, cell-uptake efficiency of the resultant polysaccharide/polynucleotide complexes was remarkably enhanced when functional groups recognized in a biological system were introduced as pendent groups. The beta-1,3-glucans can also interact with various one-dimensional architectures, such as single-walled carbon nanotubes, to produce unique nanocomposites, in which the single-walled carbon nanotubes are entrapped within the helical superstructure of beta-1,3-glucans. Various conductive polymers and gold nanoparticles are also entrapped within the helical superstructure in a similar manner. In addition, diacetylene monomers entrapped within the helical superstructure can be photo-polymerized to afford the corresponding poly(diacetylene)-nanofibers with a uniform diameter. These findings indicate that the beta-1,3-glucans are very attractive and useful materials not only in biotechnology but also in nanotechnology. These unique properties of the beta-1,3-glucans undoubtedly originate from their inherent, very strong helix-forming character which has never been observed for other polysaccharides.     

低温-低压水热合成Ba1-xSrxTi1-ySnyO3纳米材料及其 结构与性能研究

采用低温-低压水热法,在150℃,0.5MPa以下合成了一系列Ba1-xSrxTi1-ySnyO3固溶体纳米粉末(0≤x≤0.5≤y≤0.4),经XRD物相分析和d-间距-组成图证明,产品为立方晶系的完全互溶取代固溶体,结果符合Vegard定律,TEM形貌观察,粒子为均匀球形,平均粒径80nm。通过制陶实验,分别测定了该系列固溶体的室温介电常数、介电损失以及介电常数随温度的变化。结果发现,用该方法在BaTiO3中掺入适量锶和锡,由于掺杂离子均匀进入母体晶格,引起Tc降低,介电性能改善显著,当x=0.1,y=0.08时,室温介电常数达17000,比BaTiO3纯相提高10倍,而介电损失却降低88%。     

DIELECTRIC PROPERTIES OF 1, 2-POLYBUTADIENES

The dielectric permittivity and loss tangent of 1,2-polybutadienes with different chain structures were determined as a function of temperature from-180℃ to 100℃ at different frequencies, and the frequency and structure dependence of the dielectric propertie of 1,2-polybutadienes have been investigated. It is found that a maximum of the permittivity occurs in the glass-transition region. The width of the glasstransition peak increases with increasing frequency while its height has little change. With a rise in the content of 1,2-units, the permittivity decreases and the height of the glass-transition peak slightly grows. A maximum of the width of the glass-transition peak appears when the content of 1,2-units is about 45%. Both the permittivity and dielectric loss drop down as the growth of the content of syndiotactic 1,2-units.     

Self-assembled nanotubes and helical tapes from diacetylene nonionic amphiphiles. Structural studies before and after polymerization

We synthesized new amphiphiles comprised of a single diacetylenic chain and an oligoethylenoxide polar chain linked by an amide bond. In aqueous medium, they are not soluble at room temperature but form weak gels. Electron microscopy studies have shown that they self-assemble into helical tapes or nanotubes with lengths of several micrometers, and inner and outer diameters of 50 ± 1 and 59 ± 1 nm, respectively. The wall has a thickness of 10 ± 1 nm for both kinds of objects and has an amphiphile bilayer structure. The hydrophobic chains are ordered, and the amide groups are linked with each other by H-bonds. The dissociation of the tubes is a first-order transition with an enthalpy of ca. 40 kJ mol(-1). The nanotubes were photopolymerized to yield purple solutions consisting of helical tapes and almost flat ribbons. The polymers exhibit irreversible thermochromism upon heating.     

硅油的结构和时域介电谱

有机物结构常分级描述．频域介电谱方法只能觉察一级结构的极化，对二和三级结构很不灵敏．时域介电谱方法则可分辨出高级结构的丰富信息．在水和甘油等极性液体中，极谱电流的存在使时域测量无法进行．但苯和正烷系列非极性液体却存在有意义的时域谱[1]．硅油具有强的极性键，     

阳极氧化法制备TiO_2纳米管及其光催化性能

纳米TiO_2对诸多环境污染物有显著的光催化降解作用,光催化已发展成为新型环境污染治理技术.本文采用阳极氧化法制备出TiO_2纳米管,对比了四种电解液组成(A氟化铵+硫酸铵+水;B氟化铵+硫酸铵+乙酸+水;C氟化铵+硫酸铵+甘油+水;D氢氟酸+二甲基亚砜(DMOS)+乙醇)对催化剂表面形貌及光催化性能的影响.结果表明,电解液A和C都制备出了形貌清晰的TiO_2纳米管,管径约为60～74 nm.样品经400℃煅烧,TiO_2晶型主要为锐钛矿相;经500℃煅烧,出现少量金红石相;经700℃煅烧,晶型全部为金红石相.具有良好形貌的TiO_2纳米管同时具有良好的紫外光吸收能力.当亚甲基蓝初始浓度为10mg·L~(-1),经500℃煅烧的TiO_2纳米管光催化活性最佳,光照30 min亚甲基蓝的降解率达89.98%.亚甲基蓝光催化降解反应符合一级反应动力学,反应速率常数为0.079 30.     

Effect of sulphur on both thermal and dielectric properties of pre-compressed FEF black-loaded SBR vulcanizates

The thermal properties (thermal conductivity λ, thermal diffusivity a, and specific heat C_p) as well as the dielectric constant ε′ and dielectric loss ε′ of conductive styrene butadiene rubber loaded with different concentrations of sulphur were measured. It was found that both λ and C_p increase gradually at around 1 phr of sulphur content. Meanwhile, the dielectric constant ε′, showed a pronounced peak at 2 phr of sulphur content. Moreover, the effect of hydrostatic pressure on the dielectric constant ε′ and dielectric loss ε′ was found to rise with pre-compression.     

Dielectric properties of aqueous solutions of the ammonium heptamolybdate-poly(vinyl alcohol)-water system

The microwave dielectric properties of aqueous solutions of the ammonium heptamolybdate (AHM)-poly(vinyl alcohol)-water ((NH₄)₆Mo₇O₂₄-PVA-water) system are studied along sections with constant concentrations of the components in the frequency region in which the dispersion peak of the dielectric constant of water falls (13–25 GHz) at 298 and 313 K. The static dielectric constant ε_s and the dielectric relaxation time τ of the solutions are found. The dielectric characteristics along the sections vary additively as a function of concentration with respect to the relationships observed in the AHM-water and PVA-water binary systems. The rotational mobility of water molecules is mainly controlled by polymer additives. We suggest that two (water and polymer-ion) subsystems exist in the solution in this case; these subsystems only weakly affect each other.     

钐掺杂对钛酸钡锶陶瓷结构和介电性能的影响

采用溶胶-凝胶法制备了系列Sm掺杂的Ba(0.8-3x/2)SmxSr0.2TiO3(x=0,0.001,0.003,0.006,0.008 and 0.010)粉体及陶瓷。利用X射线粉末衍射、扫描电子显微镜和精密阻抗分析表征了样品的结构和性质。X射线衍射结果表明Ba(0.8-3x/2)SmxSr0.2TiO3粉体在800℃预烧2 h后为单一的钙钛矿结构;通过对陶瓷微观形貌研究发现,Sm掺杂可以明显地抑制陶瓷晶粒生长,随着Sm掺杂量的增加,晶粒尺寸由40μm减小到2μm;居里温度随着Sm掺杂量的增加而线性降低,移动速率为10℃/mol%,室温下介电常数呈现先增加后减小的趋势,并在x=0.006时达到最大值7800。