牵伸倍率对联苯型聚酰亚胺纤维形貌、取向及性能的影响

均苯四甲酸二酐(PMDA)和联苯二酐(BPDA)与3,3′-二甲基联苯二胺(OTOL)共聚得到聚酰亚胺(PI)溶液,通过干喷-湿法纺制成纤维.利用扫描电镜(SEM)、广角X射线衍射(WAXD)、纤维力学性能测试仪、动态力学分析仪(DMA)和热失重分析仪(TGA)等表征手段,研究不同牵伸倍率对联苯型聚酰亚胺纤维形貌结构、...     

Properties,Morphology and Structure of BPDA/PPD/TFMB Polyimide Fibers

The mechanical properties of fibers were notably improved by incorporating 2,2′-bis(trifluoromethyl)- benzidine(TFMB) into 3,3′,4,4′-biphenyltetracarboxylic dianhydride(s-BPDA) and p-phenylenediamine(PPD) backbone. The best strength and modulus of BPDA/PPD/TFMB polyimide(PI) fiber(diamine molar ratio of PPD/TFMB= 90/10) were 1.60 and 90 GPa, respectively, which was over two times that of BPDA/PPD PI fiber. SEM image showed that the cross-section of fibers at each stage was round and voids free. Besides, the “skin-core” and microfibrillar structure were not observed. The thermal properties of PI fibers were also investigated. The results showed that the fibers owned excellent thermal stability, moreover, the structural homogeneity of fibers were significantly improved by heat-drawn stage. The T_g values were found to be around 300℃ by dynamic mechanical analysis(DMA). Wide angle X-ray diffraction(WAXD) and small angle X-ray scattering(SAXS) experiments indicated that the order degree of longitudinal and lateral stacks, the molecular orientation and the structural homogeneity of fibers were improved in the preparation process of fibers.     

异相成核和拉伸诱导对生物基PHBV复合纤维结晶结构与力学性能的影响

采用熔融纺丝法制备了聚(3-羟基丁酸酯-co-3-羟基戊酸酯)(PHBV)/二硫化钨(WS_2)复合纤维.利用示差扫描量热仪(DSC)、热台偏光显微镜、二维广角射线衍射仪(2D-WXRD)、纤维强力仪研究了WS_2异相成核作用和牵伸诱导作用对纤维的结晶结构和力学性能的影响.研究表明,WS_2显著提高了PHBV的结晶温度,当使用2 wt%WS_2时,复合材料的结晶温度提高到115~130oC,比纯PHBV(99~105oC)提高了约25oC.WS_2不仅没有影响PHBV球晶的径向生长速率,且明显提高了PHBV/WS_2复合材料的晶核密度,熔体成核活性Φ由1.0降低为0.49.随着牵伸倍率和WS_2用量的增加,纤维的拉伸强度呈现出先增加后减小的趋势.当添加1 wt%WS_2并采用单向牵伸3.8倍时,纤维中的晶体取向产生了β晶结构,使复合纤维的拉伸强度由纯PHBV的37 MPa提高至155 MPa,断裂伸长率由2.4%增加至45%.     

聚酰亚胺纤维的研究进展

聚酰亚胺纤维由于分子主链含有刚性的芳杂环结构,赋予其优异的力学、热学、耐辐照、介电以及化学稳定性等性能,从而在航空航天、高温耐热、防火阻燃、电子器件、核能等领域具有广泛应用前景,并成为21世纪最具潜力的高性能纤维之一。近年来,随着单体来源、工艺条件的不断改善,聚酰亚胺纤维的研究得到更大关注和投入,极大促进了聚酰亚胺纤维的规模化制备和应用发展开发。本文综述了近年来高性能聚酰亚胺纤维的国内外研究成果,并针对不同化学结构、纺丝工艺以及亚胺化方法对纤维性能的影响进行阐述,同时也对其发展趋势进行展望。     

Polyimide nanocomposites based on functionalized graphene sheets: Morphologies,thermal properties,and electrical and thermal conductivities

Polyimide (PI) films were prepared by reacting 4,4′-(4,4′-isopropylidene-diphenoxy)-bis(phthalic anhydride) and 1,3-bis(4-aminophenoxy)benzene. The 4-phenylbutylamine-functionalized graphene sheets (PBA-GSs) used for the preparation of the PI nanocomposite films were prepared by mixing a dispersion of graphite oxide with a solution of the ammonium salt of 4-phenylbutylamine (PBA). PI nanocomposite films containing different amounts of PBA-GS (0–10 wt%) were compared in terms of their morphologies, thermal properties, and electrical and thermal conductivities. Only a small amount of PBA-GS was required to improve the thermal properties and thermal conductivities of the PI; the maximum enhancements in these parameters were observed at 1 and 3 wt% PBA-GS, respectively. In contrast, the electrical conductivity of the PI hybrid films continued to increase with increasing PBA-GS content from 1 to 10 wt%.     

化学改性氧化石墨烯交联的聚酰亚胺气凝胶

聚酰亚胺(PI)气凝胶是一类密度低、机械性能好、隔热性能优异的多孔材料, 通常使用昂贵的化学交联剂进行交联. 氧化石墨烯(GO)是近年来广受关注的用于聚合物增强的纳米功能填料. 以前报道的PI/GO 复合材料多是纤维或膜的形式. 为了获得PI/GO 复合气凝胶, 本文采用化学改性氧化石墨烯(m-GO)替代1,3,5-三(4-氨基苯氧基)苯(TAB)等常规的交联剂, 使之与4,4'-二氨基二苯基醚(ODA)和3,3',4,4'-联苯四羧酸二酐(BPDA)反应, 制得了m-GO交联的PI 气凝胶. GO的化学改性通过其与过量ODA在水热条件下反应实现. 通过扫描电子显微镜(SEM)研究了PI/m-GO气凝胶的微观结构. 分别通过氮气吸脱附测试、热重分析和热线法研究了m-GO对气凝胶的孔特性、热稳定性和热导率的影响. 测试结果表明, 所获得的PI/m-GO气凝胶保持了高的孔隙率、热稳定性和绝热性. 压缩测试结果显示, 与采用1.8% (质量分数, w)的TAB进行交联的PI 气凝胶相比,仅用0.6% (w)的m-GO交联所获得的气凝胶具有更高的比杨氏模量(杨氏模量/密度)、比屈服强度(屈服强度/密度)和更小的体积收缩率.     

丁腈羟增韧环氧树脂形态与力学性能

研究了丁腈羟增韧环氧树脂的力学性能和形态结构，丁腈羟的用量、丁腈羟中丙烯腈的含量、固化条件对所形成的微区尺寸都有较大影响，并进一步影响固化物的力学性能。     

BPDA/PPD/OTOL聚酰亚胺纤维的力学性能、形貌和结构

在3,3’,4,4’-联苯四酸二酐(BPDA)和对苯二胺(PPD)体系中引入3,3’-二甲基联苯胺(OTOL),显著改善了纤维的力学性能。当n(PPD)∶n(OTOL)=70∶30时,纤维的拉伸强度可达到改性前的2倍,其拉伸强度和拉伸模量分别为1.50和80 GPa。SEM照片显示了纤维的断面为圆形且没有孔穴,也没有明显的"皮芯"结构和原纤结构。WAXD和SAXS分析表明,纤维的轴向堆积和分子链取向在热牵伸过程中得到改善。     

耐高温可溶性聚酰亚胺树脂及其复合材料

制备了2种耐高温可溶型聚酰亚胺树脂(PI-1, PI-2)及其复合材料, 系统研究了树脂的工艺性, 纯树脂固化物的热性能及其复合材料的界面形貌、 介电性能和力学性能. 研究结果表明, 树脂低聚物在极性非质子溶剂中具有良好的溶解性, 且熔体黏度较低, 表明其具有优异的加工性能. 两种树脂固化物在空气中的5%热失重温度均高于550 ℃, PI-1树脂的玻璃化转变温度(T_g)为430 ℃, PI-2树脂的T_g为380 ℃. 石英纤维/PI-1和石英纤维/PI-2复合材料具有较低的介电常数和介电损耗. 碳纤维/PI-1复合材料在420 ℃下的弯曲强度保持率可达62%, 层间剪切强度保持率可达48%, 具有较优异的高温力学性能. 采用普通模压工艺制备了厚度高达45 mm的复合材料制件, 进一步证明这2种树脂具有优异的工艺性.     

含磷聚酰亚胺纤维的制备与性能

合成了一种含磷二胺单体, 二(4-胺基苯氧基)苯基膦氧(DAPOPO). 该单体与4,4'-二胺基二苯醚(ODA)、 均苯四酸二酐(PMDA)和3,3',4,4'-联苯四酸二酐(BPDA)共聚得到聚酰胺酸溶液, 通过干喷湿纺法纺丝得到聚酰胺酸纤维, 聚酰胺酸纤维经过热亚胺化和热牵伸得到含磷的聚酰亚胺纤维. 利用纤维强度仪、 扫描电子显微镜、 热失重分析仪和氧指数测定仪等研究了含磷聚酰亚胺纤维的力学性能、 形貌、 热稳定性能和阻燃性能. 结果表明, 随着含磷量的增加, 纤维的热稳定性明显提高, 而极限氧指数从35上升到了45, 说明纤维的阻燃性能得到很大提高.     

水热处理对聚酰胺6纤维结构和性能的影响

在150℃下对聚酰胺6(PA6)纤维进行了水热处理,通过二维广角X射线衍射(2D-WAXD)、二维小角X射线散射(2D-SAXS)、示差扫描量热法(DSC)、场发射扫描电子显微镜(FE-SEM)和单丝强力测试等表征方法,研究了水热处理对纤维结构、热学和力学性能的影响.水热条件下,随温度的增加,水分子渗透作用增强,分子链的运动加剧,纤维的内部结构发生变化.纤维晶区结构由原来的γ晶型转变成为α晶型,结晶度和晶区完善程度提高,微晶尺寸增加,从而使纤维的热稳定性提高,熔融温度和熔融焓增加.水热处理使得纤维形成了折叠链片晶结构.在拉伸过程中,纤维的长周期不断增加,片晶有序性排列程度提高.水热处理后PA6纤维非晶区体积分数降低,并伴随有微孔和大的孔洞的形成,纤维的断裂强度和断裂伸长率都有所降低.     

Preparation and Properties of Imidazole-containing Polyimide/Silica Hybrid Films

Imidazole-containing polyimide/silica（PI/SiO2） hybrid films were prepared from 3,3＇,4,4＇-biphenyltetra- carboxylic dianhydride（BPDA） and 2,2＇-di（p-aminophenyl）-5,5＇-bibenzimidazole in N,N-dimethylacetamide（DMAc） by sol-gel method and thermal imidization. The hybrid film with high silica mass fraction up to 40% was transparent. Scanning electron microscope（SEM） and transmission electron microscope（TEM） results of the film indicate a ho- mogeneous dispersion of silica nanoparticles in the polyimide matrix. One hybrid film PI/SiO2 with 15% SiO2 exhi- bits better mechanical properties with a tensile strength of 222 MPa, an elongation at break of 12%, and a tensile modulus of 5.66 GPa. The reinforced mechanism on mechanical Drooerties was also studied.     

PEDOT-PSS/Co-Fe_3O_4/PVA电磁功能复合纤维结构与性能

将化学共沉淀法合成的Co掺杂的Fe_3O_4(Co-Fe_3O_4)磁性粒子和化学氧化法合成的聚苯乙烯磺酸钠(PSS)掺杂的聚(3,4-乙撑二氧噻吩)(PEDOT-PSS)与聚乙烯醇(PVA)混合制备复合纺丝原液,然后经过湿法纺丝得到具有电、磁性能的PEDOT-PSS/Co-Fe_3O_4/PVA复合纤维.通过SEM、FTIR、XRD、TG、VSM以及电导率和机械性能的测试研究了不同牵伸倍率对复合纤维的结构和性能的影响.结果表明,随着牵伸倍率的增加,复合纤维的结晶性能、热稳定性能和机械性能都有所提升,其电导率则成倍增加,而其饱和磁化强度(M_s)则变化不大,约为1.7 A·m~2/kg.当牵伸倍数为4倍时,复合纤维的电导率可达到2.3 S/cm.     

膨化柞蚕丝内部形态和结构的研究

利用扫描电镜(SEM), 结合拉曼(Raman)光谱、 衰减全反射傅里叶变换红外(ATR-FTIR)光谱和X射线衍射(XRD)等方法研究了膨化型柞蚕丝的内部形态和结构, 表征了其热性能和力学性能. 结果表明, 虽然经过了相应的膨化处理, 柞蚕丝素蛋白分子链仍表现出具有高度取向的反平行β-折叠构象, 而其单丝是由许多带状微纤沿纤维轴平行组装而成, 且具有较高力学性能的纤维.     

Preparation of reflective and electrically conductive surface-silvered polyimide films from silver(I) complex and PMDA/ODA via an in situ single-stage technique

Optically reflective and/or electrically conductive surface-silvered polyimide films have been prepared by thermal curing of the (1,1,1-trifluoro-2,4-pentadionato) silver(I) (AgTFA)-containing poly(amic acid) derived from pyromellitic dianhydride (PMDA) and 4,4′-oxydianiline (4,4′-ODA) in dimethylacetamide. Films with specular reflectivity of 20-40% and surface electrical resistivity less than 7 Ω/sq were obtained. Two different thermal curing cycles were applied for the imidization and silver reduction process, and film conductivity were only obtained under rapid thermal treatment. The metallized films exhibit mechanical properties close to that of the parent polyimide films. Films were characterized by dynamic mechanical thermal analysis, X-ray diffraction, transmission electron microscopy, atomic force microscopy and mechanical measurements.     

柔性交联型聚酰亚胺气凝胶的制备及性能

利用溶胶-凝胶反应制备了聚酰亚胺凝胶, 经过超临界干燥得到了聚酰亚胺气凝胶. 研究了固含量和交联剂比例对气凝胶性能的影响规律. 结果表明, 聚酰亚胺气凝胶的密度和线收缩率都随着固含量和交联剂比例的增加而增加; 随着固含量的增加, 气凝胶的室温热导率呈现出先降低再增加的趋势(0.026~0.033 W·m^-1·K^-1), 气凝胶的力学刚度和强度明显提升; 交联剂的加入, 可以提高材料的韧性, 断裂应变最高达21.7%; 制得的柔性聚酰亚胺气凝胶具有良好的热稳定性, 是满足尖端武器以及空间飞行器对于轻质、 柔性热防护要求的理想材料之一.     

以2-苯基-4,4'-二氨基二苯醚为基础的热固性聚酰亚胺树脂及其复合材料

以2-苯基-4,4'-二氨基二苯醚(p-ODA)、异构二苯醚二酐(ODPA)和苯乙炔基苯酐(PEPA)为原料,通过两步法合成了聚合度分别为1,2和3的酰亚胺树脂低聚物,并通过模压成型法制备了单向碳纤维增强的聚酰亚胺复合材料.表征了酰亚胺树脂低聚物的溶解性、熔体黏度及其固化物聚酰亚胺树脂的热性能,结果表明,聚酰亚胺树脂具有良好的溶解性,在N,N-二甲基乙酰胺(DMAc)、四氢呋喃(THF)及1,4-二氧六环等溶剂中的溶解度大于30%;所有酰亚胺树脂低聚物的最低熔体黏度均在10 Pa·s以下,具有良好的成型工艺性;聚酰亚胺树脂具有良好的热性能,玻璃化转变温度(Tg)最高可达300℃,5%热失重温度(T5%)最高可达545℃,碳纤维增强聚酰亚胺复合材料PIC-4,4'-ODPA-2具有最佳的高低温力学性能.     

Synthesis of PP-g-PIP and Properties of PP/PP-g-PIP Binary Blends

The polypropylene-graft-polyisoprene(PP-g-PIP) copolymers with different side chain length were synthesized by the combination of solid phase graft and anionic polymerization. The copolymers were characterized by nuclear magnetic resonance spectrum(~1H-NMR), gel permeation chromatography(GPC) and differential scanning calorimetry(DSC). Five PP/PP-g-PIP blends with PP-g-PIP as a flexibilizer to toughen PP were prepared and characterized by scanning electron microscope(SEM), dynamic mechanical analysis(DMA), DSC, wide-angle X-ray diffraction(WAXD). Their morphologies, glass transition temperatures, crystallinity and mechanical properties were investigated. All the results pointed out that the covalent bonding of PP and PIP increased the compatibility and interfacial adhesion, which led to PIP well dispersed in the system and small size PIP particles in the binary blends. In addition, the toughness of PP was improved while its tensile strength slightly decreased.     

Effect of melt temperature on the phase morphology, thermal behavior and mechanical properties of injection-molded PP/LLDPE blends

<正>The phase morphology and thermal behavior of various isotactic polypropylene(PP)/linear low density polyethylene(LLDPE) blends were investigated with aid of scanning electron microscopy(SEM) and differential scanning calorimetry(DSC),respectively.The effect of barrel(melt) temperature on the morphology,thermal behavior and the resultant mechanical properties of the injection molded bars was the research focus,and the influence of LLDPE composition was also taken into account.It was found that the mechanical properties,especially the tensile ductility and the impact strength,were greatly affected by the processing temperature.The samples obtained at low temperatures had the highest elongation at break and impact strength,while those molded at high temperatures had the poorest toughness.Two reasons were responsible for that:first,the phase size in the samples increased with the processing temperature;second, possible orientation existed in the samples obtained at low processing temperatures.     

可溶性聚酰亚胺共聚物的制备及其性能

通过共缩聚及改变单体加料顺序和方法,得到了两系列共聚型聚酰亚胺,并应用Fr-IR、UV、X射线衍射、TGA、机械性能测试等方法,对所得聚酰亚胺树脂的性能进行了表征。结果表明,所得共聚型聚酰亚胺树脂成膜性能良好,能够得到坚韧且具有弹性的薄膜材料,其在400～450nm区域的透过性能良好,在有机溶剂中的溶解性能显著增强,并保持了聚酰亚胺特有的良好机械性能及耐热性能。