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.     

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     

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     

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     

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     

Structures and properties of HMPBO fibers treated by oxygen plasma/polyhedral oligomeric silsesquioxane

The surface of high modulus poly(p‐phenylene‐2,6‐benzobisoxazole) (HMPBO) fibers were treated by the combination method of oxygen plasma/polyhedral oligomeric silsesquioxane (POSS). The chemical compositions and surface morphologies of HMPBO fibers were characterized by Fourier transform infrared, X‐ray photoelectron spectroscopy, thermogravimetric analyzer, and scanning electron microscopy. The interfacial shearing strength (IFSS) of the HMPBO/cyanate ester (HMPBO/CE) micro‐composites was measured by single fiber pull out test. Results showed that the POSS was grafted on the surface of HMPBO fibers, and the grafting amount was about 0.82 wt%. After the treatment, the HMPBO fibers became coarser and the diameter was also increased. Compared with that of pure HMPBO/CE micro‐composites, the IFSS of treated HMPBO/CE micro‐composites was increased by 20.7%. POLYM. COMPOS., 34:2026–2030, 2013. © 2013 Society of Plastics Engineers     

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     

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.     

The Effect of Particle Matrix Adhesion on the Mechanical Properties of Silica Filled Cyanate Ester Composites

Summary: The effect of silica and its surface treatment on the mechanical properties of composites was studied as part of the evaluation of cyanate ester matrices as potential electronic encapsulants. Three filler surface treatments were used, as a qualitative interfacial adhesion scale, in an attempt to gauge the magnitude of interfacial adhesion between untreated filler and the cyanate ester matrix. There was strong interfacial adhesion between matrix and untreated filler. The level of silica content most affected composite modulus and fracture toughness. Filler surface treatment most affected composite strength and fracture toughness/energy. Composite fracture was found to occur via crack pinning and/or crack blunting depending on the strength of adhesion. The composites evaluated were found to possess suitable mechanical properties for potential use as electronic encapsulants.

     

Optimization of the silane treatment of cellulosic fibers from eucalyptus wood using response surface methodology

Viscose cellulosic fibers from eucalyptus wood were treated with organosilanes to introduce specific functionalities on the fibers and enhance their wettability and adhesion with phenolic matrices in composites. Modeling procedures were employed to optimize the conditions of the treatments of the fibers with the silanes (3‐aminopropyl) trimethoxysilane (APS) and 3‐(2‐aminoethylamino) propyltrimethoxysilane (AAPS). The analyzed responses were relative intensities of the bands 1565/897 and 1120/897 cm⁻¹, measured by Fourier transform infrared spectroscopy, and the silicon amount incorporated into the cellulosic fibers, which was determined by energy dispersive X‐ray analysis. In addition, surface morphology of the silane treated fibers was observed using scanning electron microscopy. The treatments of the cellulosic fibers with 2.2% APS for 120 min and 1.5% AAPS for 100 min were selected as optimums. According to contact angle measurements, both treatments enhanced the wettability between the fibers and a resol‐type phenolic resin, revealing the possible use of the silane treated fibers as reinforcement in phenolic composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42157.     

Surface modification of aramid fibers via ammonia‐plasma treatment

In this article, aramid fibers III were surface modified using an ammonia‐plasma treatment to improve the adhesive performance and surface wettability. The surface properties of fibers before and after plasma treatment were investigated by X‐ray photoelectron spectroscopy, scanning electron microscopy, atomic force microscopy, and water contact angle measurements. The interfacial shear strength of each aramid fibers III‐reinforced epoxy composites was studied by micro‐debonding test. The ammonia‐plasma treatment caused the significant chemical changes of aramid fibers III, introducing nitrogen‐containing polar functional groups, such as ? C? N? and ? CONH? , and improving their surface roughness, which contributed to the improvement of adhesive performance and surface wettability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40250.     

低温等离子体对ＰＢＯ纤维表面改性的研究

 为提高ＰＢＯ纤维／环氧树脂复合材料的剪切强度,采用低温等离子体结合涂层技术对聚对苯撑苯并双唑（ＰＢＯ）纤维进行表面改性,分别用ＳＥＭ、ＩＲ对等离子体处理前后纤维表面形态、化学结构进行了表征,通过复合材料层间剪切强度测试,研究不同处理方式对复合材料层间剪切强度的影响。结果表明,等离子体处理后纤维表面粗糙度增加,极性增强。经低温等离子体结合涂层技术处理后,ＰＢＯ纤维／环氧树脂复合材料的层间剪切强度得到显著提高,较未处理样品提高了３９％。     

Enhanced interfacial adhesion of carbon fibers to vinyl ester resin using poly(arylene ether phosphine oxide) coatings as adhesion promoters

Poly(arylene ether phosphine oxide)s (PEPO) were prepared and utilized to coat carbon fibers to enhance the interfacial adhesion with vinyl ester resins. For comparison, poly(arylene ether sulfone) (PES), Udel^® P-1700, and Ultem^® 1000 were also used. The interfacial shear strength (IFSS) of thermoplastic polymer-coated fibers was measured via microbond pull-out tests. The interfacial adhesion between thermoplastics and as-received carbon fibers was also measured in order to investigate the adhesion mechanism. Thermoplastic polymer-coated fibers exhibited a higher IFSS than the as-received fibers with vinyl ester resin, and with thermoplastic polymers. PEPO-coated fibers showed the highest IFSS, followed by Udel^®, PES, and Ultem^®-coated fibers. The high IFSS obtained with PEPO coating could be attributed to the phosphine oxide moiety, which provided a strong interaction with functional groups in the vinyl ester resin and also on carbon fibers. A diffusion study revealed the formation of a clear interphase not only between PEPO and the vinyl ester resin, but also between Udel^® (PES or Ultem^®) and the vinyl ester resin, although the morphology of the two interphases differed greatly.     

Effects of Basic Chemical Surface Treatment on PBO and PBO Fiber Reinforced Epoxy Composites

The effects of chemical surface treatment on PBO fiber and its composite materials were investigated using a basic sodium hydroxide solution. We evaluated several important treatment parameters quantitatively, including treatment concentration, treatment temperature and treatment time. Both as-spun (AS) and high-modulus (HM) PBO fibers were studied. The results showed that PBO fibers exhibited minimum or negligible reduction in their tensile strengths after the proposed treatment processes. The fibers’ contact angles with several liquid media were greatly reduced and the surface free energy could be increased to 58 mJ/m² or by 17%. The interfacial shear strength between PBO fiber and the epoxy matrix was improved to 38 MPa or by 11% with the same treatment process. The composite’s failure mode also shifted from fiber/matrix interface adhesive failure to partly cohesive failure.     

Plasma etching and plasma polymerization coating of carbon fibers. Part 1. Interfacial adhesion study

Unsized AS-4 carbon fibers were etched by RF plasma and then coated via plasma polymerization in order to enhance their adhesion to vinyl ester resin. Gases utilized for plasma etching were Ar, N₂ and O₂, while monomers used in plasma polymerization coating were acetylene, butadiene and acrylonitrile. Plasma etchings were carried out as a function of plasma power (30–70 W), treatment time (1–10 min) and gas pressure (20–40 mtorr). Plasma polymerizations were performed by varying the treatment time (15–60 s), plasma power (10–30 W) and gas pressure (20-40 mtorr). The conditions for plasma etching and plasma polymerization were optimized by measuring interfacial adhesion with vinyl ester resin via micro-droplet tests. Plasma etched and plasma polymer coated carbon fibers were characterized by SEM, XPS, FT-IR and α-Step, dynamic contact angle analyzer (DCA) and tensile strength measurements. In Part 1, interfacial adhesion of plasma etched and plasma polymer coated carbon fibers to vinyl ester resin is reported, while characterization results including tensile strength of carbon fibers are reported in Part 2. Among the treatment conditions, a combination of Ar plasma etching and acetylene plasma polymer coating provided greatly improved interfacial shear strength (IFSS) of 69 MPa, compared to 43 MPa obtained from as-received carbon fiber. Based on the SEM analysis of failure surfaces and load-displacement curves, the failure was found to occur at the interface between plasma polymer coating and vinyl ester resin.     

Effect of fiber modification with a novel compatibilizer on the mechanical properties and water absorption of hemp‐fiber‐reinforced unsaturated polyester composites

Hemp‐fiber‐reinforced unsaturated polyester (UPE) composites were prepared by compression molding. The treatment of hemp fibers with N‐methylol acrylamide (NMA) and sulfuric acid as a catalyst significantly increased tensile strength, flexural modulus of rupture and flexural modulus of elasticity, and water resistance of the resulting hemp–UPE composites. Fourier transform infrared (FTIR) spectra revealed that some NMA was covalently bonded to hemp fibers. Scanning electronic microscopy graphs of the fractured hemp–UPE composites revealed that treatment of hemp fibers with NMA greatly improved the interfacial adhesion between hemp fibers and UPE. The chemical reactions between hemp fibers and NMA as well as the mechanism of improving the interfacial adhesion were proposed and discussed. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Surface modification of armos fibers with oxygen plasma treatment for improving interfacial adhesion with poly(phthalazinone ether sulfone ketone) resin

We introduce in this article oxygen plasma treatment as a convenient and effective method for the surface modification of Armos fibers. The effects of oxygen‐plasma‐treatment power on both the Armos fiber surface properties and Armos‐fiber‐reinforced poly(phthalazinone ether sulfone ketone) composite interfacial adhesion were investigated. The Armos fiber surface chemical composition, surface morphology and roughness, and surface wettability as a function of oxygen‐plasma‐treatment power were measured by X‐ray photoelectron spectroscopy, scanning electronic microscopy, atomic force microscopy, and dynamic contact angle analysis. The results show that oxygen plasma treatment introduced a lot of reactive functional groups onto the fiber surface, changed the surface morphology, increased the surface roughness, and enhanced the surface wettability. Additionally, the effect of the oxygen‐plasma‐treatment power on the composite interfacial adhesion was measured by interlaminar shear strength with a short‐beam bending test. Oxygen plasma treatment was an effective method for improving the composite interfacial properties by both chemical bonding and physical effects. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Plasma etching and plasma polymerization coating of carbon fibers. Part 2. Characterization of plasma polymer coated carbon fibers

Unsized AS-4 carbon fibers were subjected to RF plasma etching and/or plasma polymerization coating in order to enhance their adhesion to vinyl ester resin. Ar, N₂ and O₂ were utilized for plasma etching, and acetylene, butadiene and acrylonitrile were used for plasma polymerization coating. Etching and coating conditions were optimized in terms of plasma power, treatment time, and gas (or monomer) pressure by measuring the interfacial adhesion strength. Interfacial adhesion was evaluated using micro-droplet specimens prepared with vinyl ester resin and plasma etched and/or plasma polymer coated carbon fibers. Surface modified fibers were characterized by SEM, XPS, FT-IR, α-Step, dynamic contact angle analyzer (DCA) and tensile strength measurements. Interfacial adhesion between plasma etched and/or plasma polymer coated carbon fibers and vinyl ester resin was reported previously (Part 1), and characterization results are discussed is this paper (Part 2). Gas plasma etching resulted in preferential etching of the fiber surface along the draw direction and decreased the tensile strength, while plasma polymer coatings altered neither the surface topography of fibers nor the tensile strength. Water contact angle decreased with plasma etching, as well as with acrylonitrile and acetylene plasma polymer coatings, but did not change with butadiene plasma polymer coating. FT-IR and XPS analyses revealed the presence of functional groups in plasma polymer coatings.     

Plasma modification of man‐made cellulose fibers (Lyocell) for improved fiber/matrix adhesion in poly(lactic acid) composites

The present study investigates the influence of different plasma treatments on the tensile characteristics of lyocell fibers and the interfacial interactions of lyocell fibers in a poly(lactic acid) matrix. For the investigations, the fibers were coated by an amine‐functional, nanoporous layer (a‐C:H:N) using a gaseous mixture of NH₃:C₂H₄ of 1:1 and 5:3, respectively, an oxygen‐functional layer (a‐C:H:O) with CO₂:C₂H₄ and CO₂ posttreatment, or an oxygen‐functional layer (a‐C:H:O) comprising hydroxyl groups with H₂O:C₂H₄ and H₂O posttreatment. As reference, uncoated fibers and fibers coated with a crosslinked, amorphous hydrocarbon layer (a‐C:H) without functional group incorporation were investigated. While the different treatments maintained the tensile strength of the lyocell fibers, which were all in the range between 295 and 338 N/mm², the interfacial shear strength, measured by the pull‐out test, was clearly influenced. The best improvement of the fiber/matrix adhesion was obtained by a plasma treatment with a mixture of water vapor and ethylene resulting in an interfacial shear strength of 17.8 N/mm² in comparison to the untreated lyocell fiber with 10.3 N/mm². Amine‐functional plasma polymers (a‐C:H:N) were also found to be suitable for adhesion‐promoting interlayers on lyocell fibers in poly(lactic acid). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013