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     

低温等离子体对PBO纤维表面的改性

采用硅烷偶联剂处理聚对苯撑苯并双噁唑(PBO)纤维,利用常压射频低温等离子体对PBO纤维进行了表面处理,通过扫描电镜、红外光谱、光学显微镜等研究了处理时间对PBO纤维表面官能团和表面形貌的影响规律,通过单丝拔出实验测定PBO纤维基复合材料的界面剪切强度。结果表明:经过常压射频低温等离子体处理后,PBO纤维的表面形成了大量的极性基团,表面产生明显的凹坑,PBO纤维与树脂的粘接性能提高50%,纤维的拉伸强度下降5%。     

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     

Improvement of interfacial adhesion between PBO fibers and cyanate ester matrix

Poly(p‐phenylene benzobisoxazole) (PBO) fibers were activated by the horseradish peroxidases (HRP) and then treated by 3‐Glycidoxypropyltrimethoxysilane (KH‐560) to improve the wettability and the interfacial adhesion between PBO fibers and cyanate ester matrix. The chemical compositions of PBO fibers were characterized and analyzed by FTIR and XPS. Surface morphologies of PBO fibers were examined by SEM. The wettability of PBO fibers was evaluated by the dynamic contact angle analysis test. The mechanical properties were evaluated by tensile strength and interfacial shear strength, respectively. The results demonstrated that hydroxyl groups and epoxy groups were introduced onto the surface of PBO fibers during the treatments. These treatments can effectively improve the wettability and adhesion of PBO fibers. The surface free energy of PBO fibers was increased from 31.1 mN/m to 55.2 mN/m, and the interfacial adhesion between PBO fiber and cyanate ester resin was improved to 10.77 MPa. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40204.     

Effect of Surface Modification on Mechanical and Tribological Performance of Poly-p-phenylenebenzobisoxazole Fiber-Reinforced Polyimide Composite

This work examined the effect of coupling agent surface modification of Poly-p-phenylenebenzobisoxazole (PBO) fibers on mechanical and tribological performance of PBO fiber-reinforced thermoplastic polyimide (PBO/PI) composites. The results show that tensile strength and flexural strength are largely improved by coupling agent treatment. Under dry sliding conditions, coupling agent treatment is effective to reduce the wear of PBO/PI composite. The principle of improvement in interfacial adhesion between PBO fiber and PI matrix after coupling agent treatment was discussed. The surface characteristics of PBO fibers were characterized by X-ray photoelectron spectroscopy (XPS). It is found that the content of polar groups on the surface of PBO fiber treated by coupling agent increases compared with the untreated fiber. The presence of polar groups is probably leading to an increment of interfacial binding force between fibers and matrix in a composite system, and accordingly enhances the mechanical and tribological properties.     

Improvement of the interfacial adhesion between PBO fibers and PPESK matrices using plasma‐induced coating

This work deals with the plasma‐induced coating process on the surface of PBO fibers to obtain a strong interfacial adhesion between the poly(p‐phenylene benzobisoxazole) (PBO) fibers and the poly(phthalazinone ether sulfone ketone) (PPESK) matrices. The process consisted of four steps: (a) plasma preactivation of PBO fibers; (b) immersion in an epoxy resin solution; (c) drying and then soaking with the PPESK solution; (d) shaped by compression molding technique. The orthogonal experiments used in this study enable the determination of the significant experimental parameters that influence efficiency of the process by comparing the values of ILSS. The order of their influences was the concentration > power > treating time > treating pressure. The results of the interlaminar shear strength (ILSS) and water absorption showed that the ILSS of the composite increased by 56.5% after coating, meanwhile the water absorption declined to 0.32%. The changes of the surface chemical composition, the surface morphology, and the surface free energy of fibers were studied by FTIR spectroscopy, atomic force microscope (AFM), and dynamic contact angle analysis (DCAA), respectively. Fracture mechanism of the composite was examined by scanning electron microscope (SEM). The results indicated that plasma‐induced coating process was an efficient method to enhance the interfacial adhesion of PBO fibers and PPESK matrices. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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.     

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     

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     

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     

Fabrication of uvioresistant poly(p-phenylene benzobisoxazole) fibers based on hydrogen bond

The poly(p-phenylene benzobisoxazole) (PBO) fiber with excellent performance is vulnerable to the irradiation of UV light, which significantly limits their application in advanced composites. Therefore, finding feasible and efficient ways to improve the uvioresistant properties of PBO fiber is of significance. In this work, a facile one-pot method is developed for continuously preparing the PBO/poly(2,5-dihydroxy-1, 4-phenylpyridimidazole) (PIPD) copolymer fiber to greatly enhance the anti-UV properties of PBO fibers. The experimental results demonstrate that the fabricated PBO/PIPD copolymer fiber (molar ratio of 7:1) with greatly improved surface wetting properties (the maximum increase can reach about 179%) possesses satisfactory and desired uvioresistant performance, which is 30.8% higher than that of pure PBO fibers after 480 h UV aging irradiation. The fabricated PBO/PIPD copolymer fiber with improved UV stability has the potential to be applied to many important application areas even in a severe and harsh environment. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48432.     

PBO超级纤维研究进展及其表面处理

介绍了PBO（聚苯撑苯并二恶唑）超级纤维的制备,其结构、性能以及应用等方面的研究进展,并结合PBO纤维的特点,评述了PBO纤维表面处理的研究概况。     

Improvement of the interfacial shear strength of poly(p‐phenylene benzobisoxazole) fiber/epoxy resin composite via a novel surface coating agent

Poly(p‐phenylene benzobisoxazole) (PBO) fiber with a smooth surface exhibits limited interfacial interaction with resin matrix. One of the effective strategies to improve the adhesion between the fiber and resin matrix is through surface modification of the fiber. In this study, we have proposed a novel surface treatment agent based on phosphoester cross‐linked castor oil (PCCO) for effective surface treatment of PBO fibers. The surface treatment agent was prepared by a simple cross‐linking reaction between hydroxy phosphorylated castor oil (PCO) and epoxy resin, with alcohol as the solvent at 65°C. Once the PBO fiber was treated with this agent, the interfacial adhesion between the PBO fiber and the epoxy resin could then be improved. Systematic analyses suggest that the surface treatment with (PCO + epoxy)/alcohol solution improves the interaction of the PBO fiber with the epoxy resin matrix. The PCCO coated onto the surface of PBO fiber acts as a coupling agent, improving the interfacial shear strength (IFSS) of the PBO fiber/epoxy resin composite. Results indicate a 156% increase in IFSS without compromising the mechanical properties of the fiber. POLYM. COMPOS., 37:1198–1205, 2016. © 2014 Society of Plastics Engineers     

Theoretical investigations on some rigid-rod polymers used as high-performance materials

This review focuses on a new type of para-catenated aromatic polymer being used in the preparation of high-performance films and fibers of exceptional strength, thermal stability, and environmental resistance, including inertness to essentially all common solvents. Polymers of this type include cis and transpoly(p-phenylene benzobisoxazole) (PBO), and the cis and trans forms of the corresponding poly(p-phenylene benzobis-thiazole)(PBT). The purpose of this paper is to summarize the authors' theoretical work on the structures, conformational energies, intermolecular interactions, and electronic properties of PBO and PBT chains, including the protonated forms known to exist in strong acids. The emphasis is on how such studies provide a molecular understanding of the unusual properties and processing characteristics of this new class of materials.     

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     

Mechanical properties of carbon fiber composites modified with nano-SiO2 in the interphase

The performance of carbon fibers-reinforced composites is dependent to a great extent on the properties of fiber–matrix interface. To improve the interfacial properties in carbon fibers/epoxy composites, nano-SiO₂ particles were introduced to the surface of carbon fibers by sizing treatment. Atomic force microscope (AFM) results showed that nano-SiO₂ particles had been introduced on the surface of carbon fibers and increase the surface roughness of carbon fibers. X-ray photoelectron spectroscopy (XPS) showed that nano-SiO₂ particles increased the content of oxygen-containing groups on carbon fibers surface. Single fiber pull-out test (IFSS) and short-beam bending test (ILSS) results showed that the IFSS and ILSS of carbon fibers/epoxy composites could obtain 30.8 and 10.6% improvement compared with the composites without nano-SiO₂, respectively, when the nano-SiO₂ content was 1 wt % in sizing agents. Impact test of carbon fibers/epoxy composites treated by nano-SiO₂ containing sizing showed higher absorption energy than that of carbon fibers/epoxy composites treated by sizing agent without nano-SiO₂. Scanning electron microscopy (SEM) of impact fracture surface showed that the interfacial adhesion between fibers and matrix was improved after nano-SiO₂-modified sizing treatment. Dynamic mechanical thermal analysis (DMTA) showed that the introduction of nano-SiO₂ to carbon fibers surface effectively improved the storage modulus of carbon fibers/epoxy.     

Study on photoaging of poly(p‐phenylene benzobisoxazole) fiber

As a kind of rig‐rod‐like polymer, poly(p‐phenylene benzobisoxazole) (PBO) has received great interest because of its excellent mechanical properties and good thermal stability. The use of PBO fibers, however, is limited due to its low sunlight stability. In this work, the photoaging of PBO fibers, as well as the effects of oxygen and moisture on their photoaging, is investigated by tensile strength measurements, infrared spectroscopy, molecular mass determination, and scanning electron microscopy. It is first time to find that the photoaging of PBO fibers includes two development stages. The physical aging is the dominate factor at the first stage of photoaging relative to the second stage, in which the chemical aging is the dominate factor. In the first degradation stage, long defects appear and develop parallel to the fiber axis. Little chemical change occurs in this stage. In the second degradation stage, the molecular mass of PBO decreases and chemical degradation occurs. Oxygen accelerates the occurrence of chemical degradation. It is also found PBO fibers are more stable for photoaging when moisture and oxygen are isolated. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

热处理温度对PBO纤维性能的影响

PBO纤维因其具有高强度、高模量、高耐热性以及高化学稳定性等性能而被公认为目前综合性能最好的有机纤维。对自制的初生PBO纤维分别在500℃、550℃、600℃、650℃和700℃进行高温热处理,并对处理后纤维的力学性能、耐热性能、表面形貌以及界面性能进行测试。结果表明,500℃下热处理后PBO纤维拉伸强度最大为4.72GPa,随着热处理温度升高,纤维的力学性能下降;600℃下热处理后PBO纤维的初始分解温度最高为641.3℃;随着热处理温度的提高,PBO纤维的表面粗糙度在增加,同时其界面剪切强度(IFSS)也随着温度的升高而增大。     

Surface modification of ultra-high strength polyethylene fibers for enhanced adhesion to epoxy resins using intense pulsed high-power ion beam

The effects of intense pulsed high power ion beam (HPIB) treatment of ultra-high strength polyethylene (UHSPE) fibers on the fiber/epoxy resin interface strength were studied. For this study, argon ions were used to treat Spectra? 1000 (UHSPE) fibers in vacuum. Chemical and topographical changes of the fiber surfaces were characterized using Fourier transform infrared spectroscopy in attenuated total reflectance mode (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), dynamic wettability measurements, and scanning electron microscopy (SEM). The fiber/epoxy resin interfacial shear strength (IFSS) was evaluated by the single fiber pull-out test. The FTIR-ATR and XPS data indicate that oxygen was incorporated onto the fiber surface as a result of the HPIB treatment. The wettability data indicate that the fibers became more polar after HPIB treatment and also more wettable. Although the total surface energy increased only slightly after treatment, the dispersive component decreased significantly while the acid-base component increased by a similar amount. SEM photomicrographs revealed that the surface roughness of the fibers increased following the HPIB treatment. The single fiber pull-out test results indicate that HPIB treatment significantly improved the IFSS of UHSPE fibers with epoxy resin. This enhancement in IFSS is attributed to increased roughness of the fiber surface resulting in mechanical bonding and in increased interface area, increased polar nature and wettability, and an improvement in the acid-base component of the surface energy after the HPIB treatment.     

Improvement of interfacial shear strengths of polybenzobisoxazole fiber/epoxy resin composite by n‐TiO2 coating

Smooth polybenzobisoxazole (PBO) fiber has limited interfacial interaction with resin matrix. In this article, nano‐TiO₂ coating on PBO fiber is applied to improve the interfacial adhesion between PBO fiber and epoxy resin. The test results suggest that the PBO fiber had good interaction with epoxy resin matrix after its treatment with n‐TiO₂ sol. Nano TiO₂ particle embedded onto PBO fiber surface, acting as a chock, which made fiber implanted into the resin better. This greatly improved the shear strengths (IFSS) of PBO fiber/epoxy resin composite. It has been found that a 56% increase in interfacial IFSS has achieved without sacrificing mechanical properties of fiber. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013