牵伸作用对尼龙6纤维晶型结构及力学性能的影响

利用广角X射线衍射仪(WAXD)、傅里叶变换红外光谱仪(FTIR)、示差扫描量热仪(DSC)、声速取向测量仪、扫描电镜(SEM)以及纱线强伸度仪研究了不同牵伸倍数尼龙6复丝的晶型结构、熔融行为、取向度、表面形貌以及力学性能.结果表明,随着牵伸倍数的增加,伴随着γ晶型片晶的生长以及非晶区链段重排诱导α晶型的生成,尼龙6复丝的结晶度不断的提高,在牵伸倍数达到3倍时,样品中出现了α晶型的特征衍射峰,导致了其熔融温度的提高以及多重熔融峰的出现.同时,牵伸作用也增加了分子链沿纤维轴向的取向程度,消除了纤维表面的残余应力,改善了纤维的表面缺陷.在这些因素的共同作用下,尼龙6复丝的力学性能得到了一定程度的提高,当牵伸倍数为3倍时,拉伸强度与拉伸模量分别达到了5.0 c N/dtex和28.9 c N/dtex,与较低牵伸倍数相比较均有所提高.     

一个低分子量聚氧化乙烯从亚稳态的折叠链片晶向稳态的伸直链片晶转化增厚过程的研究

报道分子量为5000的聚氧化乙烯(PEO)从熔融态淬火到液氮温度后形成的两次链折叠(2-FC)片晶增厚过程的研究结果.在升温和恒温条件下,采用小角X射线散射(SAXS)在位地跟踪了2-FC片晶增厚成一次链折叠(1-FC)和进一步成为伸直链(EC)片晶的增厚过程.通过对SAXS数据以及它们的一维相关函数的数据的分析,发现在52℃以下,2-FC片晶主要增厚为1-FC片晶;在52℃以上,2-FC片晶则主要增厚为EC片晶;在58℃到EC片晶的熔点的温度区域里,已经形成的1-FC片晶还会熔融,完全转化为EC片晶.利用偏光显微镜(PLM)和扫描电子显微镜(SEM)观察晶体的形貌,比如球晶,获得的研究结果表明,没有发生大范围的晶体破坏后再形成的变化,也就是说片晶的增厚过程是一个发生在球晶内部的薄片晶熔融后转化为厚片晶的过程.     

硬弹性聚丙烯的排状堆积片晶

用广角X射线衍射、小角X光散射等手段对硬弹性聚丙烯中排状堆积片晶的形成及结构进行了研究。结果表明,应力场下聚丙烯熔体结晶,得到的硬弹性聚丙烯具有垂直于挤出方向而又平行堆积的片晶结构(即排状堆积片晶)。熔融温度越高,排状堆积片晶所需的熔体拉伸比越高。而随着熔体所受拉伸比的增加,片晶厚度有所增加。随着熔融温度升高,片晶厚度下降。热处理温度在110-120℃之间,片晶厚度随热处理温度升高明显增加。     

偏氟乙烯-六氟丙烯共聚物纤维结构与性能表征

采用熔融纺丝技术制备偏氟乙烯-六氟丙烯共聚物[P(VDF-HFP)]初生纤维,在90°C下分别拉伸2、4、6倍,用X射线衍射(XRD)、傅里叶红外光谱(FTIR)、热重分析(TG)、示差扫描量热分析(DSC)、拉伸试验等研究了纤维结晶、热性能、力学性能、弹性回复性能等.结果表明:P(VDF-HFP)纤维晶区主要源于偏氟乙烯(VDF)链段,具有α和β2种晶型;随着拉伸倍数的增大,α晶型转变为β晶型并逐步增加,纤维结晶度提高;拉伸倍数为6倍时,P(VDF-HFP)纤维在氮气氛围下的热分解温度为452.3°C,熔融温度为126.9°C,断裂强度为502.6 MPa,定伸长为20%时,重复拉伸50次的弹性回复率为81%.     

熔融-拉伸法制备亲水聚丙烯/聚乙烯醇缩丁醛中空纤维膜

以聚丙烯(PP)为基材,聚乙烯醇缩丁醛(PVB)为亲水改性剂,聚丙烯接枝马来酸酐(PP-g-MAH)为增容剂,通过熔融-拉伸法(MS-S)制备亲水PP/PVB中空纤维膜.采用差示扫描量热(DSC)和水接触角(WCA)测试考察了PVB添加量对PP/PVB共混物结晶行为及亲水性的影响;采用广角X射线衍射(WAXD)和小角X射线散射(SAXS)研究了PP/PVB中空纤维热处理后片晶微观结构;采用场发射扫描电镜(FESEM)观察了PP/PVB中空纤维膜内表面孔结构的变化,测试了PP/PVB中空纤维膜的孔隙率及纯水通量.研究结果表明,随着PVB含量的增加,PP/PVB共混物的WCA从103°降低到76°,表明PP/PVB共混物亲水性得到明显改善.同时,PVB可以起到异相成核作用,但由于MAH与PVB发生键合作用,过量添加PVB会阻碍PP分子链段运动,导致晶体结构不完善,这与WAXD和SAXS分析结果相同.PP/PVB2.5(PVB质量分数为2.5%)中空纤维膜热处理后结晶度、片晶取向度、厚度及Shish-kebab结构完善度均高于纯PP样品.对应膜孔隙率为66%,纯水通量达到320 L/(m2·h),比纯PP膜提高了76.8%.     

不同初始结构间规聚丙烯纤维熔融过程中的结晶转变行为

通过熔融纺丝及随后的热处理制备了具有不同初始结构的间规聚丙烯纤维(sPP).采用差示扫描量热仪(DSC)和变温广角X-射线衍射仪详细研究了sPP纤维在升温过程中的结构转变和熔融行为.结果表明,不同初始结构sPP纤维的晶型不同,卷绕纤维和退火处理纤维以Ⅰ型和Ⅱ型晶型为主,牵伸纤维介晶相占优;升高温度导致Ⅰ型和Ⅱ型两种晶型直接熔融,没有出现Ⅱ型向Ⅰ型的晶型转变;初始结构为介晶相的纤维在升温过程中部分介晶相直接转变为Ⅱ型晶型,还有一部分介晶相直接熔融,并在随后的升温过程中,形成Ⅰ型晶型.sPP纤维的多重熔融行为与其初始结构和纤维制备条件密切相关.     

在高压CO_2中聚乙二醇-聚己内酯嵌段共聚物的结晶行为

通过广角X射线衍射(WAXD)和小角X射线散射(SAXS)方法研究了PEO-b-PCL在CO2中的结晶形貌和片晶厚度的变化,利用高压示差扫描量热仪(HP DSC)考察了压力对熔融和等温结晶过程的影响.结果表明,PEO-b-PCL的结晶度、片晶厚度、熔融温度均随压力的升高而减小,结晶结构变得不完善.在等温结晶过程中,结晶速率随压力的升高而下降,结晶过程处于成核控制区,Avrami指数n在3.7~4.7,表明晶体的生长方式为三维生长.     

基于“甲壳”效应、不同尾链长度的离子液晶高分子的相行为和相结构

考察了一系列基于"甲壳"效应的离子液晶高分子poly(2,5-bis{[6-(4-butoxy-4?-imidazolium phenyl)k-alkyl]oxy carbonyl}styrene bis(fluoroborate)salts)Pk-6-BF4(k=4,8,12,16)的相行为和相结构.热重分析结果表明,该系列聚合物的热分解温度都在320?C以上,说明其均具有优异的热稳定性能.示差扫描量热仪结果表明,P4-6-BF4和P8-6-BF4仅表现出一个玻璃化转变,随着尾链的增长,P12-6-BF4和P16-6-BF4具有一个结晶熔融峰.偏光显微镜、一维广角X衍射、二维广角X衍射结果表明,该系列聚合物均形成稳定的近晶A相结构,并且随着烷烃尾链的增长,层间距增加、近晶结构内部分子堆积形式有所改变.     

聚L-乳酸/4,4'-二羟基二苯硫醚共混物的分子间相互作用及结晶和熔融行为

利用红外吸收光谱(FTIR)研究了聚乳酸(PLLA)/4,4'-二羟基二苯硫醚(TDP)熔融共混物的分子间相互作用,结果表明,PLLA的羰基与TDP的羟基之间形成了分子间氢键.通过差示扫描量热(DSC)研究了共混物的玻璃化转变行为及非等温结晶和熔融行为.结果表明,样品的玻璃化转变温度(Tg)随TDP含量的增加呈线性下降.共混物的熔融结晶温度(Tc)、结晶焓(ΔHc)、熔融温度(Tm)及熔融焓(ΔHm)均随TDP含量的增加呈下降趋势,而冷结晶温度的变化趋势则相反.当TDP达到40%(质量分数)时,共混物的DSC曲线既未出现结晶峰,也未出现熔融峰,表明该样品已完全成为非晶态物质.广角X射线衍射(WAXD)分析结果表明,TDP的加入未改变PLLA的晶型,但导致其晶面间距变大,晶体结构变得松散.因此共混物熔点的下降归因于分子间氢键的形成降低了PLLA分子链的运动能力及晶体的紧密程度而非晶型的改变.     

聚丙烯催化合金(PP-c)的晶体结构及其影响因素

用差示扫描量热法(DSC)和广角X射线衍射(WAXD)研究了两种乙烯含量不同的聚丙烯反应合金(PP-c)等温结晶下的晶体结构及PPβ晶含量的影响因素.结果表明,在通常的等温结晶条件下,乙烯含量较高的试样(PEP40)的熔融曲线出现双熔融峰.WAXD分析证明,其熔融双峰分别代表均聚聚丙烯(PP)的α晶和β晶.计算结果表明,PEP40中β晶含量与结晶温度有关,124℃结晶时β晶含量最高.在220℃对PP-c熔体进行热处理可显著提高PEP40中β晶的含量;在相同温度下热处理后,较低乙烯含量的试样(PEP20)也出现晶型异构.比较200℃与220℃下热处理对PEP20等温结晶的结晶形态的影响,发现后者使微晶尺寸明显变小,并呈现较完善的β球晶形态.     

系列磺丁基甜菜碱的表征及表面活性

用FT-IR、1H NMR和元素分析对自制的3种磺丁基甜菜碱(SBm-4)的结构进行了表征,研究了它们的表面性能、泡沫性能和乳化性能。 获得SB12-4的cmc为2.20×10-3 mol/L,γcmc为31.48 mN/m;SB14-4的cmc为2.80×10-4 mol/L,γcmc为29.68 mN/m;SB16-4的cmc为2.30×10-5 mol/L,γcmc为32.06 mN/m。 3种磺丁基甜菜碱的cmc值随着烷基链长增加逐渐减小,γcmc先减小后增加,三者的起泡性随浓度增加而增加,到一定值后保持不变;泡沫稳定性随浓度增加逐渐增强,起泡性随着温度的增加有缓慢增加趋势,泡沫稳定性随温度增加逐渐降低。 3种表面活性剂的乳化能力随浓度增加先增加后降低。     

A study of magnetic,antibacterial and antifungal behaviour of a novel gold anchor of polyaniline/itaconic acid/Fe3O4 hybrid nanocomposite: Synthesis and characterization

The objective of the present investigation is to fabricate the gold anchor polyaniline (PANI) based nanocomposites which is prepared using itaconic acid (IA) with Fe₃O₄ by the simple polymerization reaction. The developed multi responsive antibacterial magnetic polymeric composite is represented as Au@PANI–IA–Fe₃O₄. Further, the chemical structure, thermal and magnetic properties such as FT-IR, TGA/DTA, and VSM analysis are studied. The TEM and SEM/EDX are used to find the shape and composition of gold nanoparticles. The enhanced magnetic properties of ferrite composite are exhibited and the antibacterial properties are determined using E. coli (gram -ve) and S. aureus (gram +ve) bacteria’s. The results of biological properties such as antifungal and antimicrobial are also studied critically conferred. Based on the experimental results, the fabrication method of Au@/PANI/IA/Fe₃O₄ magnetic nanocomposites, and the relationship between the structure and biological properties are discussed in detail.     

核壳型纳米粒子合成方法及其性能的研究进展

核壳纳米粒子作为复合纳米粒子一个重要的分支,由于其光、磁和催化等方面的优异性能,近年来引起了人们广泛的关注.本文主要介绍了核壳纳米粒子的制备方法及诸多性能,并对核壳纳米粒子的发展进行了展望.     

羟基卟啉化合物的电化学、顺磁共振及时间分辨光电压性质

通过循环伏安法、电子顺磁共振谱和时间分辨电压光谱研究了羟基取代基数目和位置的不同对羟基苯基卟啉化合物的电化学、电子顺磁共振和时间分辨光电压性质的影响. 研究结果表明, 所有氧化还原反应都是在卟啉环上进行的. 卟啉周边取代基数目的增加使得卟啉共轭体系平均电子云密度增大, 导致体系易氧化而难以还原. 对称性增强可能使卟啉化合物的半波电位值向正方向移动, 羟基取代基的给电子效应对于卟啉化合物电化学性质的影响起主导作用. 常态下卟啉分子没有EPR信号, 在光的激发下, 卟啉分子由原来的逆磁性分子变成顺磁性的激发三重态分子, 这种激发三重态分子在分子轨道上具有两个未成对电子, 这两个电子相距很近, 彼此之间发生很强的相互作用而产生电子, 它的g值随卟啉共轭体系平均电子云密度增大而变大. 时间分辨光电压是由分子中的自由光声载流子的存在而产生的, 光电压的衰减与分子结构密切相关, 它们的电荷分离速度基本上随卟啉周边羟基取代基数目的增加而减慢.     

Effect of Cadmium Substitution on Structural and Magnetic Properties of Nano Sized Nickel Ferrite

The structure and crystal phase of the nanocrystalline powders of Ni_1-xCd_xFe₂O₄ (0≤x≤0.5) mixed ferrite, synthesized by wet chemical co-precipitation method, were characterized by X-ray diffraction. Results showed that the lattice parameter increased with increasing Cd concentration. Microstructure was studied by scanning electron microscopy. TG/DTA stud-ies were carried out on co-precipitated sulphate complexes. These studies revealed the low ferritization temperature (650 oC) of the ferrite system synthesized by presently adopted route of synthesis and occurrence of simultaneous decomposition and ferritization processes.Further studies by infrared spectroscopy were also conducted. Moreover, magnetic properties of the prepared nanoparticles were studied by magnetization and a.c. susceptibility mea-surements. The response of prepared Ni_1-xCd_xFe₂O₄ mixed ferrites to magnetic field was investigated. Results show that, magnetic susceptibility, Curie temperature, and effective magnetic moment decreased as the Cd content increases.     

Influence of Backbone Structure on Properties of Directly Polymerized Phenoxy Resins from Epichlorohydrin and Various Aromatic Dihydric Phenols Monomers

A series of phenoxy resins was directly prepared through the polymerization of each of the various aromatic dihydric phenols and epichlorohydrin.FTIR and 1H NMR spectra were recorded to characterize the structures of the re-sins.The GPC curves were used to determine the molecular weight distribution.In addition,the thermal properties of the resins were studied with differential scanning calorimetry(DSC)and thermal gravimetric analysis(TGA).The thermal stabilities of the polymers increased with the content of the benzene ring,pendant group increasing or biphenyl groups emerging.The adhesive properties of the polymers were evaluated in terms of the lap shear strength with Fe-Fe adherends.The fracture mechanisms were determined by SEM observation and it was found that there was an important participation of cohesive fracture mechanisms.Also,it has been demonstrated that the extension of these micro-cohesive mechanisms is directly correlated with the adhesive strength.According to these results,the phenoxy resin containing biphenyl groups presented a higher adhesive strength and could improve the adhesive property of the epoxy/phenoxy system to a certain extent.     

Synthesis, Mesogenic and Spectroscopic Properties of 2,5-Disubstituted Thiophene Derivatives

Two series of 2,5-disubstituted thiophene derivatives （series 1： 2,5-bis（p-alkoxyphenylethynyl）thiophene and series 2： 2,5-bis[p-（p-alkoxyphenylethynyl）（phenylethynyl）]thiophene） were synthesized and characterized by ^1H NMR, ^13C NMR, HRMS and elemental analysis. The relationship between the structure and the mesogenic and spectroscopic properties has been discussed. The results show that compounds 1a-1f all exhibited an enantiotropic nematic mesophase, which was confirmed by the polarized optical microscopy （POM）, differential scanning calorimeter （DSC） and variable temperature powder X-ray diffraction （PXRD）. In contrast, the extended conjugated analogues 2a-2b had no liquid crystal properties. As for the spectroscopic properties, incorporating more phenylethynyl units results in red-shifted absorption and emission spectra, greatly enhanced quantum efficiency.     

分子基磁体Cr[N(CN)2]2电子结构和半金属性的第一性原理研究

The electronic structure and half-metallicity of molecule-based ferromagnet Cr[N(CN)₂]₂ have been investigated using first-principles with generalized gradient approximation. The total energy, spin-polarized electronic band structure, density of states (DOSs) and spin mag-netic moments were all calculated. The calculations reveal that the compound Cr[N(CN)₂]₂ is a really half-metallic ferromagnet with a integral magnetic moment of 2.0000 μB per molecule in the optimized lattice constant. Based on the spin distribution and the DOS, it is found that the total magnetic moment is mainly from the Cr²⁺ with relative small contribution from C and N atoms. The sensitivity of the half-metallicity to small change in lattice constant is also discussed.     

含V和Ni灰高温流动性的调控研究

以三种含V和Ni灰为研究对象,探索通过添加助剂和配煤两种途径来调控含V和Ni灰的流动性,利用XRD、SEMEDX和三元相图等分析方法,探究了两种方法调控含V和Ni灰流动性的机理。结果表明,灰中V和Ni在高温下形成难熔物钒氧矿和单质镍,配煤和添加CaO降低了V和Ni的含量,同时可降低除V和Ni以外灰组成的液相温度,进而降低灰的熔融温度。当灰中V和Ni的总含量低于30%时,配入助熔剂CaO可明显降低灰的熔融温度,但其黏温曲线转变为结晶渣类型。当灰中V和Ni含量高于30%时,需通过配入低熔点煤灰降低熔融温度,在满足气流床排渣要求的煤灰中配入5%的该灰后,其黏温特性仍满足气流床液态排渣的要求,但配比达到10%时,降温过程中析出大量的富钒尖晶石,使灰渣黏温曲线转变为结晶渣类型,其不再适合气流床液态排渣的要求。     

中空TiO_2微球的制备及对聚丙烯酸酯薄膜性能的影响

采用阳离子聚苯乙烯微球作为模板,钛酸四丁酯为钛源,氨水为催化剂,制备了中空TiO_2微球.采用X射线衍射、扫描电镜及比表面测定仪对其形貌和结构进行了表征,并考察了模板粒径、钛源用量以及催化剂用量对中空TiO_2微球形貌的影响.通过物理共混法将其引入至聚丙烯酸酯乳液中并成膜,研究了复合薄膜的保温性能、抗紫外性能及力学性能.结果表明,锐钛矿相中空TiO_2微球模板粒径、钛源用量以及催化剂用量影响中空TiO_2微球的空心尺寸、壁厚及壳层致密性.中空TiO_2微球可显著提升聚丙烯酸酯薄膜的保温性能、抗紫外性能和力学性能.采用不同粒径的模板制备的中空TiO_2微球对复合薄膜的各项性能均有影响,其中模板粒径为140 nm时复合薄膜性能最优,光反射率提升63%,导热系数降低27%,且在波长小于360 nm范围内,紫外透过率几乎为0,抗张强度增加100%,断裂伸长率提升62%.