高性能PBO纤维表面改性及抗紫外光性能研究

采用多聚磷酸(PPA)的乙酸溶液和PPA的乙醇溶液对对苯撑苯并二噁唑纤维(PBO纤维)进行表面改性,研究了PPA对PBO纤维表面改性的影响;采用添加紫外光吸收剂的脂环族环氧树脂涂料对PPA表面改性后的PBO纤维进行涂覆处理,采用环境扫描电镜(SEM)以及力学性能测试等表征手段探讨紫外光吸收剂对PBO纤维抗紫外性能的影响。研究结果表明,PPA溶液对PBO纤维表面的溶胀与刻蚀作用随着溶液中PPA质量分数增加而增加,PBO纤维的拉伸强度随PPA质量分数增加不断减小。PBO纤维经含有紫外光吸收剂UV-328的脂环族环氧树脂的涂料涂覆处理后,UV-328和脂环族环氧树脂的协同作用使PBO纤维的抗紫外光性能有显著的提高,PBO纤维拉伸强度的下降速度随着涂料中UV-328的质量分数的增加而减慢。当脂环族环氧树脂的涂料中UV-328的质量分数为5%时,PBO纤维在400h的加速老化后其拉伸强度保留率可提高至60.3%。     

氩气低温等离子体处理对PBO纤维的表面改性

采用低温等离子体表面处理技术对聚苯撑苯并二口恶唑(PBO)纤维表面进行改性.选用氩气作为处理气氛,研究了气压、功率和处理时间等参数对纤维表面性质的影响.采用FT-IR和SEM等方法对处理前后纤维表面化学结构及形态结构进行了表征,并通过单丝拔出试验测定了改性前后PBO纤维与环氧树脂基体的界面剪切强度(IFSS),对纤维与树脂的界面粘结性进行了初步评价.同时,采用液滴形状法对纤维表面亲水性进行了表征.通过研究发现,经低温氩气等离子处理后,PBO纤维表面亲水性增强,PBO纤维/环氧树脂的IFSS较未处理样品提高了42%.     

PBO纤维紫外老化行为研究

研究了聚对苯撑苯并二噁唑(PBO)纤维在313nm波段的紫外光辐照下结构与性能的变化。采用红外光谱(FTIR)、扫描电子显微镜(SEM)、X射线能谱(EDS)、单丝拉伸测试、X射线衍射(XRD)对老化前后PBO纤维的形貌和结构进行了表征。结果表明:紫外光对PBO纤维的形貌和结构有显著的影响,紫外老化200h后,表层已经明显出现了剥离现象,紫外老化1000h后,PBO纤维表面脱落严重,纤维内部化学键发生断裂,红外谱图上显示有酯羰基出现,结晶度降低,纤维拉伸强度迅速下降,纤维强力保持率仅约为17%。     

MWNTs/PBO共混纤维的制备及性能

通过原位分散方法将不同含量的多壁碳纳米管（MWNTs）引入聚对苯撑苯并二噁唑（PBO）聚合体系,共混产物采用液晶纺丝法纺制成高性能MWNTs/PBO纤维。用偏光显微镜观察了MWNTs的分散状况,发现将MWNTs先预分散在多聚磷酸（PPA）中再添加可以有效地改善其分散性,热失重分析仪、强力仪研究了纤维的热稳定性能和力学性能。结果表明,MWNTs质量分数为2%的共混纤维的拉伸强度和模量分别达到4.69 GPa和128.8 GPa,比相同卷绕速度下PBO纤维提高了24.2%和23.5%,起始热分解温度也从668.9℃提高到700.8℃。MWNTs的质量分数达到5%时由于团聚严重,降低了PBO的可纺性,影响了纤维的性能。      

芳纶纤维的磷酸表面处理及其树脂基复合材料界面性能

采取不同浓度的磷酸水溶液对芳纶纤维进行表面处理, 并对不同处理条件下芳纶纤维的单丝强度、表面性质及其环氧树脂复合材料的界面性能进行了分析和测试。结果表明: 20 wt %磷酸溶液处理的芳纶纤维, 纤维表面含氧官能团含量最高; 继续提高磷酸溶液的浓度, 含氧官能团含量下降, 纤维表面趋于平整, 单丝强度上升。用20 wt %磷酸溶液处理芳纶纤维, 纤维/ 环氧树脂基复合材料的层间剪切强度达到62 MPa , 界面剪切强度提高18 % , 是一种简单有效的表面处理方法。纤维表面粗糙度和纤维表面含氧官能团的数量是影响芳纶纤维/ 环氧树脂复合材料界面结合性能的关键因素。      

聚对苯亚基苯并双(噁)唑纤维生产工艺研究

对聚对苯亚基苯并双(噁)唑(PBO)纤维生产工艺中的主要过程进行了研究,对影响PBO纤维强度等性质的因素进行了分析.PBO纤维制备:以4,6-二氨基间苯二酚(DAR)的盐酸盐为单体原料,与对笨二甲酸(TPA)混合,经过中和反应、脱色处理、干燥后制成复合盐;再以多聚磷酸为溶剂,添加五氧化二磷和抗氧化剂,经过预聚合反应制备出PBO聚合物;聚合物通过双螺杆挤出机进一步进行聚合,然后通过喷丝板挤出,在磷酸水溶液中凝固成型,经过洗涤、干燥等过程,最终卷绕成型.制成的纤维强度最高可达30cN/dtex以上,制成的PBO聚合物特性黏度最大可达40dL/g以上.DAR单体盐的质量,聚合条件、纺丝过程是影响最终纤维产品性能的主要因素.     

氧气DBD等离子体处理PBO纤维表面及其对双马树脂基复合材料界面性能的影响

采用氧气介质阻挡放电(DBD)等离子体处理PBO纤维表面,用以改善PBO纤维与双马来酰亚胺(BMI)树脂之间的界面粘结性能。结果表明,用氧气等离子体处理PBO纤维能大幅度提高PBO/BMI复合材料的层间剪切强度(ILSS)值,最佳处理条件为功率30 W/m³、时间24 s,ILSS值从43.9 MPa提高到62.0 MPa。经过氧气DBD等离子体处理的PBO纤维其表面的氧含量明显提高,氮含量变化不大,甚至在过度处理时降低;官能团-O-C=O基团的含量从0提高到3.16%,-C-O-的含量也明显提高;在氧气DBD等离子体处理后的PBO纤维表面产生大量凹凸不平和沟壑,使纤维表面的粗糙度提高。而表面氧含量的提高和表面形貌与粗糙度的变化,是PBO/BMI复合材料ILSS值提高的重要原因。单丝拉伸实验结果表明,适当的DBD等离子体处理不会对PBO纤维表面产生不良影响,不影响其在复合材料中的作用。     

电晕处理对高性能PBO纤维的表面性能及其界面粘接性能的影响

对高性能PBO纤维表面进行了电晕处理,优化了其处理工艺。用XPS,FT-IR和SEM研究了处理前后纤维表面化学结构及物理结构的变化,通过单丝拔出试验和短梁剪切试验评价了PBO纤维与树脂基体的微宏观界面粘接性能。结果表明:经电晕处理后,PBO纤维表面含氧量增多,表面浸润性得到改善,单丝拔出的PBO-环氧界面剪切强度(IFSS)提高了25.6 ％,但短梁剪切强度(ILSS)的提高不明显。     

聚对苯撑苯并双噁唑纤维的表面改性及疏水性涂层制备EI北大核心CSCD

采用偶联剂KH-560对聚对苯撑苯并双噁唑(PBO)纤维进行表面活化,并用含有十七氟癸基三甲氧基硅烷(HFTES)的涂层对偶联剂改性后的PBO纤维表面进行疏水性处理。利用X射线光电子能谱、扫描电镜等对PBO纤维表面结构和性能进行表征,考察了偶联剂KH-560质量分数对PBO纤维表面改性效果的影响,同时分析了HFTES质量分数对PBO纤维疏水性的影响。研究结果表明,采用KH-560改性PBO表面时,PBO纤维表面形成了薄层偶联剂涂层,纤维表面粗糙度增加,PBO纤维表面引入的环氧基活性基团增强了纤维表面活性。随着HFTES浓度的提升,PBO纤维吸水率下降。经HFTES处理后PBO纤维的吸水率大幅度下降,经含有HFTES的有机硅改性环氧树脂涂层处理后的PBO纤维表面水接触角可达132°。     

聚多巴胺修饰聚对苯撑苯并双噁唑纤维增强其抗老化性与功能性

高性能纤维聚对苯撑苯并双噁唑(PBO)容易受紫外光照射而导致其性能显著下降。为了提高PBO材料的抗老化性能,文中通过简易方法在纤维表面直接修饰富含酚羟基的纳米厚度的聚多巴胺薄层,并比较研究了初始纤维与多巴胺修饰纤维在紫外光照射前后的力学性能、热稳定性能、结晶取向等性能的变化。结果表明,未经修饰的PBO纤维的力学等性能在紫外光照射后显著下降,如拉伸强度下降了67%;而表面经过修饰的PBO纤维在经过紫外光照射后,其性能变化显著减小,如拉伸强度仅下降了33%。并且,聚多巴胺修饰的PBO纤维对污染物罗丹明B染料等具有一定的吸附性能,吸附24 h的吸附容量达0.25 mg/g。因此,在材料表面修饰聚多巴胺层可有效改善PBO纤维的抗紫外光老化性能,提高了材料的功能性。     

High electrical conductivity and high corrosion resistance fibers with high modulus and high strength prepared by electroless plating of gold on the surface of poly (<Emphasis Type="Italic">p</Emphasis>-phenylene benzobisoxazole) (PBO)

In an attempt to produce glittering gold fibers with high modulus and high strength, gold plating on the surface of poly(p-phenylene benzobisoxazole) (PBO) fibers was carried out by using an electroless plating method. Due to the difficulty in plating gold directly on organic and inorganic fibers, gold plating was carried out on the surface of copper-plated and nickel-plated fibers; for the latter the nickel was plated on the copper-plated fibers. Namely, composite fibers, termed PBO/Cu/Au and PBO/Cu/Ni/Au, were prepared. The morphology of plated fibers was studied by X-ray diffraction, scanning electron microscopy with energy dispersive spectroscopy and electrochemical polarization measurements. It was found that gold was uniformly plated on the PBO fiber, and the gold-plated fibers have good corrosion resistance. The electrical conductivities of the two kinds of gold-plated fibers were higher than 4 × 10⁴ S/cm, and their tensile strengths and Young’s moduli were greater than 1.9 GPa and 130 GPa, respectively, when estimated in terms of a single composite fiber.     

Atmospheric air plasma treated PBO fibers: Wettability,adhesion and aging behaviors

Poly (p–phenylene-2, 6-benzobisoxazole) (or PBO) fibers were modified by air dielectric barrier discharge plasma (air-DBD) with different treatment time. The wettability of the PBO fibers were enhanced evidently, which was proved by dynamic contact angle analysis (DCAA), the contact angle in water of the fibers treated by air-DBD plasma decreased from 77.52° to 34.05°, while the surface free energy increased from 44.73 mJ/m² to 64.04 mJ/m². The surface morphology changes and variations of chemical components of PBO fibers were detected by scanning electron microscopy (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the fiber surface morphology became rougher and some newly polar groups were introduced onto the fiber surfaces. They contributed to the enhancement of the wettability. Furthermore, the interfacial adhesion between PBO fibers and bismaleimide (BMI) resin was improved obviously, which revealed by the increased ILSS of the PBO/BMI composites. Nevertheless, the ILSS of PBO/BMI composites decreased to 47.0 MPa after PBO fibers were stored in air for 7 days and there were little changes for 7–30 days.     

Effect of oxygen plasma treatment of PPTA and PBO fibers on the interfacial properties of single fiber/epoxy composites studied by Raman spectroscopy

The interfacial micromechanics of single poly(p-phenylene terephthalamide (PPTA) and poly(p-phenylene benzobisoxazole (PBO) fibers embedded in an epoxy resin has been investigated by determining the interfacial shear stress distributions along the fiber length. The effects of an oxygen plasma treatment on the interfacial shear stress of the fiber-epoxy systems are analyzed. Raman spectroscopy was used to map the stress distributions along the fiber when the composite is subjected to a small axial tensile strain (3.5% for PPTA and 2.5% for PBO). The quality of the interface or adhesion was improved after the surface treatment, supporting the ability of plasma oxidation to enhance the adhesion of high-performance fibers to epoxy resins. The tensile behavior of fiber-reinforced systems was different in each case. PPTA reinforcements underwent fragmentation, likely by fiber microfailure, whereas debonding or bridging is the most probable fragmentation mechanism in the case of PBO.     

PBO纤维性能及表面改性的研究进展

目的综述聚对苯撑苯并二唑(PBO)纤维的性能及其表面改性方法的研究进展。方法从PBO纤维的力学性能、热稳定性、化学稳定性及光稳定性等方面进行简单说明;从化学表面刻蚀、共聚改性、偶联剂处理、等离子体处理、辐射处理及生物载体处理等对PBO纤维表面改性方法进行阐述。结果 PBO纤维性能优异,但纤维表面化学惰性极强,必须对其进行表面改性;各种改性方法各有优缺点。结论目前的PBO纤维表面改性方法仍然存在较多的不足,有待发现一种环保且高效的改性方法。     

Adhesion of PBO fiber in epoxy composites

A composite of poly p-phenylene-2,6-benzobisoxazole (PBO) fiber and epoxy resin has excellent electrical insulation properties. However, it is a challenging issue to improve its mechanical properties because of poor adhesion between PBO fiber and matrix. The relatively smooth and chemically inactive surface of PBO fiber prevent efficient chemical bonding in the composite interface. Here, we report the surface modification of PBO fibers by UV irradiation, O₂ and NH₃ plasma, as well as acidic treatments. We found that the surface free energy and roughness are increased for both sized and extracted fibers after plasma treatments together with maleic anhydride grafting. The sized fiber shows marginal improvement in adhesion strength and no change in fiber tensile strength because of the barrier effect of the finish. For the extracted fiber, however, the tensile strength of the fiber is sensitive to surface treatment conditions and considerable strength reduction occurred, particularly for cases of acidic treatments and UV irradiation. This is because that the treatments increase the surface roughness and introduce more surface flaws. The extracted fiber surface has no adequate wetting and functional groups, which in turn results in coarse interface structures and causes reduction or no apparent variation of the adhesion strength. The fracture surfaces after single fiber pull-out tests exhibit adhesive interfacial failure along the fiber surface, which is further confirmed by similar adhesion strength and interlaminar shear strength values when the fiber was embedded in various epoxy resins with different temperature behavior.     

PBO纤维表面空气冷等离子体改性

采用等离子体处理方法对PBO(聚对苯撑苯并二 口 恶 唑)纤维表面进行改性。用XPS和AFM测试分析等离子处理时间对PBO纤维表面组成和表面形貌的影响规律;首次采用浸润性测试和IR测试分析等离子体处理前后纤维浸润性和表面官能团的变化。用Microbond测试方法表征了纤维与树脂基体的界面剪切强度,并用SEM观察微复合材料破坏形貌。结果表明:等离子体处理后纤维浸润性得到改善,纤维表面苯环上引入了很多羟基。等离子体处理最佳条件下(170 W,10 min),纤维表面粗糙度最大,纤维表面O元素含量最大, O/C比率提高了50.5 %, IFSS值提高了64.7 %。     

电化学氧化对炭纤维界面性质的影响

对粘胶基炭纤维进行电化学氧化表面处理，对表面处理前后的炭纤维进行强力测试，分析表面处理条件对炭纤维强度的影响，通过测定炭纤维与几种浸润液的接触角，分析了电化学氧化表面处理对炭纤维浸润特性的影响，在电镜下观察表面处理前后炭纤维表面形貌的变化，并测其比表面积的变化，分析处理条件对其表面粗糙度的影响，通过炭纤维的拉曼散射，分析表面处理前后炭纤维表面微晶大小的变化，最后，对处理前后炭纤维的相关性能指标进行比较，分析其性能变化的机理及其性能变化对炭纤维复合材料界面粘结性能的影响。     

Hierarchical poly(p-phenylene benzobisoxazole)/graphene oxide reinforcement with multifunctional and biomimic middle layer

A new hierarchical reinforcement developed by coating biomimic polydopamine (PDA) on the surface of poly(p-phenylene benzobisoxazole) (PBO) fibers, which served as a platform for the graphene oxide (GO) grafting, using branched polyethyleneimine (b-PEI) as a bridging agent. The surface morphologies and chemical structures of PBO fibers were characterized for confirming the formation of covalent bond between GO and PBO fibers. The surface roughness (R_a) and wettability of the obtained fibers, denoted as PBO@PDA-PEI-GO, were obviously increased in comparison with those of untreated one. The reinforcement offered a 68.8% enhancement in the interfacial shear strength (IFSS) without degrading the base fiber. The PDA layer on the PBO fiber surface led to improved UV resistance. The hydrothermal aging resistance of PBO/epoxy composite was also greatly improved. This biomimic surface modification approach is facile to prepare, highly efficient to enhance interface, adaptable to all high-performance fibers, and meaningful in multifunctional applications.