Rigid‐rod polymeric fibers

This paper traces the historical development of high temperature resistant rigid‐rod polymers. Synthesis, fiber processing, structure, properties, and applications of poly(p‐phenylene benzobisoxazole) (PBO) fibers have been discussed. After nearly 20 years of development in the United States and Japan, PBO fiber was commercialized with the trade name Zylon® in 1998. Properties of this fiber have been compared with the properties of poly(ethylene terephthalate) (PET), thermotropic polyester (Vectran®), extended chain polyethylene (Spectra®), p‐aramid (Kevlar®), m‐aramid (Nomex®), aramid copolymer (Technora®), polyimide (PBI), steel, and the experimental high compressive strength rigid‐rod polymeric fiber (PIPD, M5). PBO is currently the highest tensile modulus, highest tensile strength, and most thermally stable commercial polymeric fiber. However, PBO has low axial compressive strength and poor resistance to ultraviolet and visible radiation. The fiber also looses tensile strength in hot and humid environment. In the coming decades, further improvements in tensile strength (10–20 GPa range), compressive strength, and radiation resistance are expected in polymeric fibers. Incorporation of carbon nanotubes is expected to result in the development of next generation high performance polymeric fibers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 100: 791–802, 2006     

Influence of oxygen plasma treatment on interfacial properties of poly(p‐phenylene benzobisoxazole) fiber‐reinforced poly(phthalazinone ether sulfone ketone) composite

The influence of oxygen plasma treatment on both surface properties of poly(p‐phenylene benzobisoxazole) (PBO) fibers and interfacial properties of PBO fiber reinforced poly(phthalazinone ether sulfone ketone) (PPESK) composite were investigated. Surface chemical composition, surface roughness, and surface morphologies of PBO fibers were analyzed by X‐ray photoelectron spectroscopy (XPS), Atomic force microscopy (AFM), and scanning electron microscopy (SEM), respectively. Surface free energy of the fibers was characterized by dynamic contact angle analysis (DCAA). The interlaminar shear strength (ILSS) and water absorption of PBO fiber‐reinforced PPESK composite were measured. Fracture mechanisms of the composite were examined by SEM. The results indicated that oxygen plasma treatment significantly improved the interfacial adhesion of PBO fiber‐reinforced PPESK composite by introducing some polar or oxygen‐containing groups to PBO fiber surfaces and by fiber surface roughening. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of MWCNTs irradiation grafting treatment on the surface properties of PBO fiber

The aim of this article is improved the surface properties of Poly[p‐phenylenebenzobisoxazole] (PBO) fiber with epichlorohydrin hybridized carboxylic multi walled carbon nanotubes (MWCNTs‐Ecp) grafting by using γ‐ray irradiation technology. The surface chemical properties, the surface morphology, the amount of the grafted MWCNTs on PBO fiber and the surface free energy of PBO fibers have been analyzed. The results show that MWCNTs‐Ecp have been grafted on the surface of PBO fiber by γ‐ray irradiation treatment. The surface chemical inertness and the surface smoothness of PBO fiber are significantly improved by grafting MWCNTs‐Ecp chains, the amount of the grafted MWCNTs on PBO fiber is about 11.9%, and the surface free energy of PBO fiber has an increase of 42.6% by generating some active groups such as ? COOH, ? OH, and ? C? Cl on the surface of PBO fiber. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of a rigid-rod dihydroxy poly(<Emphasis Type="Italic">p</Emphasis>-phenylene benzobisoxazole) fiber with excellent surface and axial compression properties

A series of dihydroxy poly(p-phenylene benzobisoxazole) (DHPBO) were prepared by introducing binary hydroxyl polar groups into poly(p-phenylene benzoxazole) PBO macromolecular chains and the effects of hydroxyl polar groups on surface wettability, interfacial adhesion and axial compression property of PBO fiber were investigated. Contact angle measurement showed that the wetting process both for water and for ethanol on DHPBO fibers were obviously shorter than that on PBO fibers, implying DHPBO fibers have a higher surface free energy. Meanwhile, single fiber pull-out test showed that DHPBO fibers had higher interfacial shear strength than that of PBO fibers. Scanning electron microscope proved that there was more resin remained on the surface of DHPBO fibers than on PBO fibers after pull-out test. Furthermore, axial compression bending test showed that the introduction of binary hydroxyl groups into macromolecular chains apparently improved the equivalent bending modulus of DHPBO fibers.     

Compressive behaviour of rigid rod polymer fibres and their adhesion to composite matrixes

Abstract

The deformation behaviour of the new high performance polymer fibres, poly(p-phenylene benzobisoxazole) (PBO) and polypyridobisimidazole (PIPD) and their adhesion to an epoxy composite matrix have been investigated. Both fibres give well defined Raman spectra, and the deformation micromechanics of PBO and PIPD single fibres and composites were studied from stress induced Raman band shifts. Single fibre stress-strain curves were determined in both tension and compression, thus providing an estimate of the compressive strength of these fibres. It was found that the PIPD fibre has a higher compressive strength (~1 GPa) than PBO (~0·3 GPa) and other high performance polymer fibres, because hydrogen bond formation is possible between PIPD molecules. It has been shown that when PBO and PIPD fibres are incorporated into an epoxy resin matrix, the resulting composites show very different interfacial failure mechanisms. The fibre strain distribution in the PBO-epoxy composites follows that predicted by the full bonding, shear lag model at low matrix strains, but deviations occur at higher matrix strains due to debonding at the fibre/matrix interface. For PIPD-epoxy composites, however, no debonding was observed before fibre fragmentation, indicating better adhesion than for PBO as a result of reactive groups on the PIPD fibre surface.     

Fiber hybrid polyimide‐based composites reinforced with carbon fiber and poly‐p‐phenylene benzobisthiazole fiber: Tribological behaviors under sea water lubrication

Fiber hybrid polyimide‐based (PI‐based) composites reinforced with carbon fiber (CF) and poly‐p‐phenylene benzobisthiazole (PBO) fiber of different volume fractions were fabricated by means of hot press molding technique, and their mechanical properties and tribological behaviors under sea water lubrication were systematically investigated in relation to the synergism of CF and PBO fiber. Results showed that the incorporation of CF or PBO fiber improved the tensile strength, hardness, and wear resistance of PI. More importantly, because of the synergistic enhancement effect between CF and PBO fiber on PI matrix, the combination of 10%CF and 5%PBO fiber reinforced PI‐based composite had the best mechanical and tribological properties, showing promising application in ocean environment. POLYM. COMPOS., 37:1650–1658, 2016. © 2014 Society of Plastics Engineers     

两种高性能纤维研究进展

简介了聚对苯撑苯并双恶唑(PBO)纤维和聚二羟基苯撑并吡啶双咪唑(PIPD)纤维的发展历史、制备方法,性能及应用,着重对PBO纤维和PIPD纤维最近几年研究的热点和方向进行了综述.     

有机特种纤维介绍(二)

对有机特种纤维中的超高相对分子质量聚乙烯(UMHWPE)纤维、聚对苯撑苯并二噁唑(PBO)纤维、聚酰亚胺(P)I纤维、聚(2,5-二羟基-1,4-苯撑吡啶并二咪唑)(PIPD)纤维的结构与性能、发展情况、制备方法以及主要应用领域进行了简要介绍,最后简要展望了这4种特种纤维的发展前景。     

聚对苯撑苯并噁唑纤维的抗紫外光老化研究进展

综述了近年来聚对苯撑苯并噁唑(PBO)纤维抗紫外光老化改性的最新研究进展,探讨了紫外光降解老化过程和对光老化机理的推测,指出完善PBO纤维的内部结构和添加抗紫外光老化剂均可改善PBO纤维的紫外光稳定性。介绍了几种抗紫外光老化改性的方法,并讨论了它们各自的优缺点。目前抗紫外光老化研究主要集中在如何提高PBO纤维基体和抗紫外光老化剂之间的相容性。     

Poly(p‐phenylene benzoxazole) fiber chemically modified by the incorporation of sulfonate groups

Two kinds of modified poly(p‐phenylene benzoxazole) (PBO), the copolymer of TPA (SPBO) and p‐SPBO, containing ionic groups in the macromolecular chains were obtained by copolymerization from 1,3‐diamino‐4,6‐dihydroxybenzene dihydrochloride (DAR) and terephthalic acid (TPA), with the addition of selected amounts (1.5–5.0% molar ratio over DAR) of 5‐sulfoisophthalic acid monosodium salt or sulfoterephthalic acid monopotassium salt in place of the TPA, respectively, in poly(phosphoric acid) (PPA). The resultant PBO/PPA, SPBO/PPA, and p‐SPBO/PPA lyotropic liquid‐crystalline solutions were spun into fibers by a dry‐jet wet‐spinning technique. Chemically modified PBO fibers with sulfonate salt pendants in the polymer chains were obtained for the first time. The surface wetting behavior and interfacial shear strength between the fiber and epoxy resin were investigated. The interference of sulfonate salt pendants on the crystalline morphology was measured. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Environmental effects on poly‐p‐phenylenebenzobisoxazole fibers. II. Attempts at stabilization

Approaches to alleviate the environmental degradation of as‐spun poly‐p‐phenylenebenzobisoxazole (PBO AS) fibers by moisture, acidic conditions, and UV–visible radiation were implemented and tested for efficacy. The general approaches tested include: extraction and neutralization of residual phosphoric acid using supercritical carbon dioxide; the use of UV–visible light blocking coatings of exfoliated graphite, carbon black, and glassy titanium dioxide; and improvement of initial fiber properties by the application of forces tending to compact the fiber microstructure. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3819–3829, 2006     

Promoting the adhesion of high‐performance polymer fibers using functional plasma polymer coatings

Plasma‐copolymerized functional coatings of acrylic acid and 1,7‐octadiene were deposited onto high strength, high modulus, poly‐p‐phenylene benzobisoxazole (PBO) fibers. X‐ray photoelectron spectroscopy (XPS) with trifluoroethanol derivatization confirmed that the PBO fibers were covered completely with the plasma copolymer and that the coating contained a quantitative concentration of carboxylic acid groups. Microdebond single filament adhesion and interlaminar shear strength (ILSS) tests were used to evaluate the interfacial strength of epoxy resin composites containing these functionalized PBO fibers. Both the interfacial shear strength (IFSS) obtained from single filament tests, and the ILSS of high volume fraction composites were a function of the surface functionality of the fibers so that there was a good correlation between ILSS and IFSS data. The tensile strengths of single fibers with or without coating were comparable, demonstrating that the fiber surface was not damaged in the plasma‐coating procedure. Indeed, the statistical analysis showed that Weibull modulus was increased. Therefore, plasma‐polymerized coatings can be used to control the interfacial bond between PBO fibers and matrix resins and act as a protective size for preserving the mechanical properties of the fibers. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

X‐ray scattering study on the damage in fibers used in soft body armor after folding

The goals of the research effort described in this article are to develop a framework to evaluate improvements in next‐generation fibers used in soft body armor and to anticipate long‐term performance and potential fiber deterioration. This effort to date has included the effect of folding on the fibers and exploring the interaction between the specific fiber strain energy and their sound velocity. Previous work in this lab noted a severe drop‐off of tensile strength and strain‐to‐failure in poly(p‐phenylene benzobisoxazole) (PBO) fibers when subjected to repeated folding. Subsequent work on poly(p‐phenylene terephthalamide) (PPTA) fibers showed at most a slight drop‐off in these mechanical properties. Results from wide angle X‐ray diffraction indicated that both PPTA and PBO fibers showed no significant changes in the d‐spacing and the apparent crystal size. However, with small angle X‐ray scattering, it was found that the void and fibril sizes within PBO fibers may decrease after folding. Environmental scanning electron microscopy showed no damage to the fiber surfaces upon folding, and confocal microscopy revealed extensive internal damage to the PBO fibers that tracks well with the SAXS and mechanical testing results. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Effects of light stabilizer on the ultraviolet stability of poly-p-phenylenebenzobisoxazole (PBO) fibers

A UV-resistant PBO fiber containing light stabilizer OB-1(2,2??-(1,2-ethenediyldi-4,1-phenylene) bis-benzoxazole) is reported. OB-1/PBO Fiber, which had excellent mechanical properties as PBO was prepared via in situ polymerization and dry-jet wet-spinning technique. Effects of the light stabilizer (OB-1) on UV stability of PBO fiber and possible degradation mechanism were investigated by tensile testing, intrinsic viscosity measurement, SEM, and ATR-FTIR analysis. Under UV-accelerated aging, the tensile strength of PBO fiber declined sharply. After exposed to UV 340-nm light for 310?h, the strength retention was only 44.17?%. SEM analysis showed the smooth and compact surface with well-oriented microfibrils was damaged. Meanwhile, the photostability of PBO fiber could be enhanced greatly by adding a small amount (0.05?C0.2?%) of OB-1. Under the same conditions, the strength retention of 0.2?%OB-1/PBO fiber increased to 64.84?%, which was 47?% higher than that of PBO fiber. SEM observation showed the surface of OB-1/PBO fiber was also damaged, but it was not as so severe as PBO fiber. After UV irradiation, the intrinsic viscosity of PBO and OB-1/PBO fiber decreased which implies that mild chain scissions occurred. ATR-FTIR analysis revealed that oxazole rings in PBO and OB-1/PBO backbone were disrupted and formed amide linkages. These results indicated the loss of strength is mainly due to the break of microfibrils and fiber morphology, mild chain scission, and the disruption of oxazole rings.     

An excellent ablative composite based on PBO reinforced EPDM

Short poly(p-phenylene-2,6-benzobisoxazole) (PBO) fibers were first used to reinforce ethylene–propylene–diene terpolymer (EPDM) as thermal insulation materials. The effects of PBO fiber length and content on the mechanical and ablative properties of the composites were investigated in detail. Comparing with the severe breakage occurred in short aramid fibers as fillers, only some necking deformation is observed in PBO fibers filled EPDM after processed. After ablated by oxyacetylene flame, the carbonized PBO fibers still keep solid fibrous structure instead of hollow one of carbonized aramid fibers in the char layer. As a result, the PBO fibers/composites show significantly higher tensile strength and ablation resistant abilities than the aramid fibers/composites. Moreover, with the length and content of PBO fibers increasing, both the tensile strength and the ablation resistance of the composites increase gradually though the break elongation reduces sharply. Considering the properties requirement of thermal insulator, PBO fibers with 3.42–5.56 wt% in content and 3–4 mm in length are preferred. The mass loss rate and the erosion rate as low as 0.05 g s⁻¹ and 0.10 mm s⁻¹ are observed in the optimal samples, respectively, which is evidently lower than that of the best aramid fibers/EPDM-based insulations reported so far.     

Wettability assessment of plasma-treated PBO fibers based on thermogravimetric analysis

Changes in the surface wettability of poly(p-phenylene benzobisoxazole) (PBO) fibers were investigated by thermogravimetric analysis (TGA) following an air dielectric barrier discharge (DBD) plasma treatment. The results were then supplemented and confirmed by scanning electron microscopy (SEM), dynamic contact angle analysis (DCAA), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) measurements. After exposure to the DBD plasma at a pre-determined power level, TGA analysis showed that the residual rates retained by the PBO composites decreased, which meant an increase in the amount of resin coating the PBO fibers in the composites. Observations by SEM confirmed that there was more resin adhering to the treated PBO fibers and the wetting behavior of resin on the fibers was greatly improved. Meanwhile, DCAA for the treated fibers showed a significant enhancement in fiber surface free energy. XPS and AFM were performed in order to reveal any variations in fiber surface activity and surface morphology resulting from the surface treatment. The resulting data showed that increases in oxygen-containing polar groups and surface roughness on the plasma-treated PBO fibers contributed to the above improved wetting behavior. With comprehensive analyses, it was concluded that TGA could be used as a supporting method assessing the surface wettability of PBO fibers before and after air DBD plasma treatment.     

热处理工艺对PBO纤维拉伸性能影响

针对研究较少的聚对苯撑苯并双恶唑(PBO)纤维热处理工艺进行研究,通过控制热处理气氛、热处理温度、热处理停留时间和预加应力4个参数,对初纺丝PBO(PBO–AS)纤维的热处理工艺进行优化,得到拉伸性能大幅提高的PBO–HM纤维。利用电子织物强力仪对PBO–HM纤维的拉伸性能进行测试,发现热处理氛围为N2时PBO–HM纤维的性能更为优异;热处理温度控制在550℃以下时,热处理温度越高,热处理后得到的PBO–HM纤维的拉伸弹性模量越高,但热处理停留时间延长会使拉伸强度降低;预加应力有助于PBO–HM纤维拉伸弹性模量的增加。经分析得出,最优热处理温度为550℃,热处理停留时间为53.3 s,预加应力为5.48 c N/dtex,得到的PBO–HM的拉伸性能较优。     

Surface modification of PBO fibers by argon plasma and argon plasma combined with coupling agents

The methods of argon plasma and argon plasma combined with coupling agents were employed to modify the poly[1,4‐phenylene‐cis‐benzobisoxazole] (PBO) fiber surface. The interfacial shearing strength (IFSS) of PBO fibers/epoxy resin was measured by the single fiber pull‐out test. The surface chemical structure and surface composition of PBO fibers were determined by FTIR and X‐ray photoelectron spectroscopy respectively. The morphology of the fiber surface was investigated by scanning electron microscopy and the specific surface area of the fibers was calculated by B.E.T. equation. Furthermore, the wettability of PBO fibers was confirmed by the droplet profile analysis method. The results showed that the elemental composition ratio of the fiber surface changed after the modification. The IFSS increased by 42 and 78% when the fibers were treated by argon plasma and argon plasma combined with the coupling agents, respectively. Meanwhile, the specific surface areas of the treated fibers were improved. In addition, compared with the modification of argon plasma, the modification of argon plasma combined with the coupling agents inhibited the attenuation phenomena of the IFSS and the wettability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1428–1435, 2006     

Synthesis,structure and properties of carbon nanotube/poly(p‐phenylene benzobisoxazole) composite fibres

Carbon nanotube/poly(p‐phenylene benzobisoxazole) (CNT/PBO) composite fibres were prepared by in situ polymerization and dry‐jet wet spinning. The structure and properties of the CNT/PBO fibres were investigated. FTIR and viscosity measurements showed that the functional groups on the CNT surface took part in the polymerization and affected the chemical structure and molecular weight of the composite. CNT/PBO composites with high molecular weight could be obtained by controlling the amount and addition time of CNTs. Compared with PBO fibres containing no CNTs prepared under the same conditions, the thermal resistance of the CNT (2 wt%)/PBO fibres was higher and the tensile strength was also improved by 20–50%. WAXD and SEM measurements indicated that the orientation degree of the CNT (2 wt%)/PBO fibres was smaller than that of PBO fibres. The fracture surfaces of these two fibres were also different. CNT dispersion in the CNT (2 wt%)/PBO fibres was examined by TEM. A model of the interactions between CNTs and PBO is proposed, based on these results. Copyright © 2006 Society of Chemical Industry     

Synthesis and Properties of Poly[p-(2,5-dihydroxy)-phenylenebenzobisoxazole] Fiber

The novel polymer poly[p-(2,5-dihydroxy)-phenylenebenzobisoxazole] (PBOH) fiber was synthesized in the presence of 2,5-dihydroxyterephthalicacid (DHTA) and 4,6-diamino-1,3-benzenediol in poly(phosphoric acid) (PPA) using typical polycondensation conditions. The crystalline solutions of liquid PBOH in PPA were spun into fibers using dry-jet wet spinning. Furthermore, the thermostability and mechanical properties of PBOH were compared with poly(p-phenylene-2,6-benzoxazole) (PBO) in order to investigate the relationship between the chain structure and properties. The results indicated that the thermal degradation temperature of PBOH was above 750K and the tensile strength of the PBOH fiber was 3.1GPa, which were much lower than those of PBO fiber. The compressive strength of PBOH fiber was 331 M Pa, which was slightly higher than that of PBO fiber. In addition, molecular simulation was employed to explain why the compressive strength of PBOH fiber did not increase significantly compared to PBO fiber.