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.     

Adhesive and flame resistance behavior of poly(arylene ether phosphine oxide) (PEPO) and PEPO‐modified epoxy resins

Poly(arylene ether phosphine oxide) (PEPO) with controlled molecular weights and amine end‐groups was synthesized, and used as an adhesive, a coating material for adherend or a modifier for diglycidyl ether of bisphenol A (DGEBA)‐based epoxy resins. Closely related poly(arylene ether sulfone) and commercial polyethersulfone, Udel® P‐1700, were also utilized for comparison purposes. Adhesive behavior was measured via single lap shear samples as a function of coated polymer type, test temperature (R.T. and 100°C), and aging condition in boiling distilled water or 5% salt water. Flame resistance of PEPO and PEPO‐modified epoxy resin was evaluated by TGA and a flame test. PEPO exhibited better adhesive properties than PES or Udel® P‐1700. PEPO coating on an Al adherend markedly improved adhesive property of PES and Udel® even at 100°C, and after aging study failure mode changed from adhesive to cohesive with the PEPO. Aminophenyl terminated PEPO‐modified epoxy resins also exhibited highly improved adhesive behavior and flame resistance, compared to control samples. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1198–1205, 2001     

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.     

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     

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.     

New coating systems based on vinyl ether‐ and oxetane‐modified hyperbranched polyesters

A series of hyperbranched aliphatic‐aromatic polyesters has been synthesized which contain vinyl ether or oxetane functionalities as curable groups. We investigated the curing behavior of these multifunctional polymers in the presence of reactive diluents in order to analyze the possibility of their application in high solids coatings. The vinyl ether‐modified hyperbranched polyesters with a high degree of modification yield the best coatings. Furthermore, coating systems containing vinyl ether‐modified hyperbranched polyesters and triethyleneglycol divinyl ether (DVE‐3) as reactive diluent showed a better performance compared to those containing 4‐hydroxybutyl vinyl ether (HBVE). Real time FT‐IR studies revealed a high conversion of functional groups (76%) for the cationic curing with DVE‐3. On the other hand, the curing reaction of the functional hyperbranched polymers without the presence of any reactive diluent stopped at 32% conversion of functional groups due to the reduced mobility of the polymer. The vinyl ether‐modified hyperbranched polyester could be cured also radically in the presence of diethyl maleate (DEM) as reactive diluent, whereas the curing of the oxetane‐modified polyesters was very slow and incomplete in all attempts.     

Electrostatic deposition of silica nanoparticles between E‐glass fibers and an epoxy resin

The achievement of optimum adhesion between a thermoset and an inorganic material is an important goal for the composites and coatings industries. There is a growing interest in the use of structural surface modifiers, such as nanotubes, nanoparticles, and whiskers, to improve this adhesion. Here, a method for electrostatically depositing poly(ethylene imine)‐functionalized silica nanoparticles onto E‐glass fibers was developed. The deposition of 26‐nm functionalized particles onto glycidyloxypropyltrimethoxysilane (GPS)‐functionalized E‐glass fibers and then their embedding in a resin of diglycidyl ether of bisphenol A and m‐phenylene diamine increased the interfacial shear strength (IFSS) 35% over that of bare fibers and 8% over that of GPS‐functionalized fibers. IFSS was highly dependent on the particle size; the 16‐nm functionalized particles had little effect on the IFSS. When the particles size was increased to 71 and 100 nm, this led to increasingly poor IFSS values, whereas the 26‐nm particles produced the best results. Similar results were seen with the transverse flexural strength of the unidirectional composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41516.     

Relating the heat-of-mixing of analog mixtures to the miscibility of hydrogen-bonding polymers

The prediction of polymer/polymer miscibility is addressed using analog calorimetry and molecular modeling. For each polymer, an analog compound representing one or two repeat units was chosen. Heat-of-mixing was measured for liquid mixtures of analog compounds and then used in a binary interaction model to predict polymer miscibility. Specifically, we have measured exothermic heats-of-mixing for 4-ethyl phenol, an analog of poly(vinly phenol), with several analogs containing ether, ester, or ketone functional groups. The exothermic heat-of-mixing results are consistent with the observed miscibility of poly(vinyl phenol) with polymers containing these functional groups. Using interaction parametes derived from the analog calorimetry in the binary interaction model or using premixes of 4-ethyl phenol in ethyl benzene, we correctly predict the magnitude and relative order of the fraction of vinyl phenol units in copolymers with styrene required for miscibility with poly(methyl methacrylate), polyacetal, and a polyketone. the miscibility trends for poly(vinyl phenol) blends predicted from analog calorimetry and the binary interaction model are in reasonable agreement with those predicted from the association model of Painter and Coleman, despite the different bases of the two approaches. We have used molecular modeling to complement the analog calorimetry and to assess steric effects on hydrogen-bonding ability for models of poly(n-butyl acrylate) and poly(t-butyl acrylate) with phenol. The modeling results suggest that, in some cases, steric effects and the three-dimensional structure of the polymer can significantly influence the hydrogen-bonding ability of polymers relative to their analogs.     

Concerning the miscibility of poly(vinyl phenol) blends — FTi.r. study

The results of a Fourier transform infrared study of poly(vinyl phenol) (PVPh) blends containing a number of chemically and structurally dissimilar polymers are presented. These polymers include the polyesters poly(ε-caprolactone) and poly(?-propiolactone); poly(vinyl alkyl ethers) where the alkyl groups are methyl, ethyl and isobutyl respectively; poly(ethylene oxide) and poly(vinyl pyrrolidone). All of these PVPh blends, with the exception of that containing poly(vinyl isobutyl ether), exhibit infrared spectral features consistent with a significant degree of mixing. Intermolecular hydrogen bonding interactions involving the PVPh hydroxyl group and either the carbonyl or ether oxygen moieties of the other polymers in the blend are identified. The relative strengths of these intermolecular interactions are discussed together with ramifications pertinent to the overall subject of polymer miscibility.     

Modulus-Graded Interphase Modifiers in E-Glass Fiber/Thermoplastic Composites

A process for coating E-glass fibers with polystyrene–polyethyleneimine (PEi) core–shell particles was developed, and uniform monolayers of particles of 143 and 327 nm diameter were covalently bonded to the glass surface. The effect of the particle coatings on the mechanical properties of fiber-reinforced composites of poly(vinyl butyral) (PVB) was investigated. The interfacial shear strength (IFSS) was measured for specimens containing one to 20 fibers each using the tensile fiber fragmentation test, and significant enhancements were found, in particular for samples containing larger numbers of fibers. The smaller-particle (143 nm) coatings in the 20-fiber specimens produced approximately a 100% enhancement in IFSS over equivalent specimens with bare or aminosilane-treated fibers, while the 327 nm particle coatings produced only approximately a 25% enhancement. The greater effectiveness of the smaller particles was attributed, at least in part, to the larger effective interfacial area they provide and their relatively greater shell-to-core ratio, providing greater interphase stiffness. The greater enhancements achieved for the multi-fiber vs single-fiber specimens suggest that the coatings produce a more uniform fiber–fiber spacing and, therefore, a more thorough wetting of the fibers by the resin in the multi-fiber samples. Composites formed using fiber tows of 3200 fibers each showed more than a 100% increase in composite toughness and 35% increase in ultimate tensile strength as compared to samples with bare fibers due to the presence of the 143 nm particle coatings, and somewhat more modest increases for the 327 nm particle coatings.     

Properties of carbon fiber sized with poly(phthalazinone ether ketone) resin

We studied thermoplastic poly(phthalazinone ether ketone) (PPEK) resin as a sizing agent on carbon fiber, with emphasis on its thermal stability, surface energy, wetting performance, and interfacial shear strength (IFSS). X‐ray photoelectron spectroscopy characterization was carried out to study the chemical structure of sized/unsized carbon fibers. Scanning electron microscopy and atomic force microscopy were used to characterize surface topography. TGA was used to analyze the thermal stability. Meanwhile, contact angle measurement was applied to analyze the compatibility between the carbon fibers and PPEK and the surface energy of carbon fibers. IFSS of carbon fiber/PPEK composite was examined by microbond testing. It is found that carbon fibers uniformly coated with PPEK resin had better thermal stability and compatibility with PPEK resin than the uncoated fiber. The contact angle is 57.01° for sized fibers, corresponding to a surface energy of 49.96 mJ m^?2, much smaller than that for unsized ones with contact angle value of 97.05°. The value of IFSS for sized fibers is 51.49 MPa, which is higher than the unsized fibers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Polymeric systems for acoustic damping. III. Blends of poly(vinyl chloride), segmented poly(ether ester), and poly(methyl acrylate)

A solution blend of poly(vinyl chloride) and a segmented poly(ether ester) and blends containing these two polymers plus poly(methyl acrylate) were investigated by dynamic mechanical analysis and electron microscopy. The binary blend, which contained 75% by weight of the poly(ether ester), showed only one loss peak, but also evidence of some phase separation. It is believed that the polyether sequences of the poly(ether ester) are extensively mixed with poly(vinyl chloride). Poly(methyl acrylate) was added to spread the damping range and produce a material of potential use as an acoustic damper. It is evident from both electron microscopy and dynamic mechanical analysis that poly(methyl acrylate) is substantially incompatible in the other polymers.     

Improvement of interfacial properties of carbon fiber‐reinforced poly(phthalazinone ether ketone) composites by introducing carbon nanotube to the interphase

This article aims to improve interfacial properties of carbon fiber‐reinforced poly(phthalazinone ether ketone) (PPEK) composites by means of preparing carbon nanotube (CNT)/carbon fiber hybrid fiber. XPS was used to characterize the chemical structure of unsized carbon fiber and SEM was used to observe the surface topography of carbon fibers. Specific area measurement, dynamic contact angle, and interfacial shear strength (IFSS) testing were performed to examine the effect of CNT on the interfacial properties of carbon fiber/PPEK composites. By the introduction of CNT to the interphase of carbon fiber‐reinforced PPEK composites, an enhancement of IFSS by 55.52% was achieved. Meanwhile, the interfacial fracture topography was also observed and the reinforcing mechanism was discussed. POLYM. COMPOS., 36:26–33, 2015. © 2014 Society of Plastics Engineers     

Towards the simulation of poly(vinyl phenol)/poly(vinyl methyl ether) blends by atomistic molecular modelling

Molecular simulations of poly(vinyl phenol)/poly(vinyl methyl ether) (PVPh/PVME) blends were performed and their degree of miscibility evaluated as a preliminary step before orientation simulations. A minimum of three periodic boundary condition amorphous models was constructed and analysed in terms of solubility parameter, X-ray pattern, pair correlation function, hydrogen bond fraction and backbone conformation. The values obtained are consistent with miscibility of the systems, although it is suggested that the degree of mixing is not uniform for the different models.     

Binary and ternary polymer blends containing poly(vinylidene chloride‐co‐acrylonitrile)

Poly(vinylidene chloride‐co‐acrylonitrile) (Saran F), poly(hydroxy ether of bisphenol A) (phenoxy), poly(styrene‐co‐acrylonitrile) (PSAN), and poly(vinyl phenol) (PVPh) all have the same characteristic: miscibility with atactic poly(methyl methacrylate) (aPMMA). However, the miscibility of Saran F with the other polymer (phenoxy, PSAN, or PVPh) is not guaranteed and was thus investigated. Saran F was found to be miscible only with PSAN but not miscible with phenoxy and PVPh. Because Saran F and PVPh are not miscible, although they are both miscible with aPMMA, aPMMA can thus be used as a potential cosolvent to homogenize PVPh/Saran F. The second part of this report focused on the miscibility of a ternary blend consisting of Saran F, PVPh, and aPMMA to investigate the cosolvent effect of aPMMA. Factors affecting the miscibility were studied. The established phase diagram indicated that the ternary blends with high PVPh/Saran F weight ratio were found to be mostly immiscible. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3068–3073, 2004     

Miscibility of poly(vinyl chloride) with ethylene-ethyl acrylate-carbon monoxide terpolyrners

Ethylene/ethyl acrylate/carbon monoxide ter polymers (E/ EA/CO) can exhibit a very high degree of miscibility with poly(vinyl chloride) as determined from dynamic mechanical measurements. The blends yield transparent films and show a large amorphous phase which exhibits only one major glass transition. However, some crystallinity can be detected and has been measured by differential, scanning calorimetry. Residual crystallinity is at least partially due to the somewhat non-uniform nature of the terpolymerization. The acrylate monomer exhibits faster polymerization rates than the other two constituents. By contrast, ethylene/ethyl acrylat copolymers are not miscible with poly(vinyl chloride). The addition of carbon monoxide to the termpolymer structure is believed to yield miscibility with poly(vinyl chloride) via specific interaction of the ketone carbonyl of the terpolymer (proton acceptor) and the tertiary hydrogen of poly(vinyl chloride) (proton donor). This specific interaction allows for a broad range of terpolymer compositions which retain miscibility with polyvinyl chloride. Similar results are also observed with ethylene/vinyl acetate/carbon monoxide (E/VA/CO) as well as ethylene/2-ethylhexyl acrylate/carbon monoxide termpojymers. The vinyl acetate terpolymers (and their blends) display a lower degree of crystallinity than the E/EA/ CO. This is consistent with the more uniform nature of the E/VAJCO terpolymerization.     

Effect of temperature on aggregation/dissociation behavior of interpolymer complexes stabilized by hydrogen bonds

The effect of temperature on the aggregation/dissociation behavior of interpolymer complexes based on poly(acrylic acid) and various nonionic polymers—poly(vinyl pyrrolidone), poly(ethylene oxide), poly(acrylamide), hydroxypropylcellulose, hydroxyethylcellulose, poly(vinyl methyl ether), poly(vinyl ether of ethyleneglycol), and vinyl ether of ethyleneglycol‐co‐vinyl butyl ether—has been studied in aqueous solutions. It was shown that nonionic polymers could be classified into two groups according to the stability of their polycomplexes with respect to temperature. The first group of nonionic polymers forms interpolymer complexes, which are stable and undergo further aggregation upon increase in temperature. The second group forms polycomplexes, which dissociate at higher temperatures. The nature of forces stabilizing different interpolymer complexes in aqueous solutions is discussed. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1946–1950, 2004     

Synthesis and properties of nonlinear optical polymers based on poly(ether imides) for electrooptical devices

Summary : Nonlinear optical poly(ether imides) with an adequate thermal stability has been synthesized by direct coupling of hydroxy poly(ether imides) and NLO chromophores with a quantitative yield. The resultant amorphous NLO poly(ether imides) exhibited good solubility in common organic solvents, providing optical-quality thin films by spin coating. The glass transition temperatures of the polymers are at around 180 °C. The electrooptic coefficients (r₃₃, @1.3μm) of PEI-DR1 was 12.3 pm/V with an electrical poling field of 100 V/μm and it decayed about 10 % over 10 months at 90 °C under atmospheric conditions. Received: 23 February 1999/Revised version: 26 March 1999/Accepted: 29 March 1999     

Synthesis,spectral, and thermal characterization of photosensitive poly(ether–ester)s containing α,β‐unsaturated ketone moieties in the main chain derived from 2,6‐bis[4‐(3‐hydroxypropyloxy)‐3‐methoxybenzylidene]cyclohexanone

A series of photosensitive poly(ether–ester)s containing α,β‐unsaturated ketone moieties in the main chain were synthesized from 2,6‐bis[4‐(3‐hydroxypropyloxy)‐3‐methoxybenzylidene]cyclohexanone (BHPMBCH) and aliphatic and aromatic diacid chlorides. The diol precursor, BHPMBCH, was synthesized from 2,6‐bis(4‐hydroxy‐3‐methoxybenzylidene)cyclohexanone and 3‐bromo‐1‐propanol. The solubility of the polymers was tested in various solvents. The intrinsic viscosity of the synthesized polymers, determined by an Oswald viscometer, was found to be 0.06–0.80 g/dL. The molecular structures of the monomer and polymers were confirmed by Fourier transform infrared, ultraviolet–visible, ¹H‐NMR, and ¹³C‐NMR spectral analyses. The thermal properties were studied with thermogravimetric analysis and differential scanning calorimetry. The thermogravimetric analysis data revealed that the polymers were stable up to 220°C and started degrading thereafter. The thermal stability initially increased with increasing spacer length and then decreased due to negative effects of the spacer. The self‐extinguishing properties of the synthesized polymers were studied by the determination of the limiting oxygen index values with Van Krevelen's equation. In addition, the photocrosslinking properties of the polymer chain were studied with UV spectroscopy, and we observed that the rate of photocrosslinking increased significantly with increasing methylene carbon chain length of the acid spacer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Miscibility of poly(vinyl acetate) and vinyl acetate-ethylene copolymers with styrene-acrylic acid and acrylate-acrylic acid copolymers

Poly(vinyl acetate) and vinyl acetate-ethylene (VAE) copolymers compose one of the more important polymeric materials, widely employed in coating and adhesive applications. A new class of miscible polymer blends involving poly(vinyl acetate) and VAE with styrene-acrylic acid and acrylate-acrylic acid copolymers has been found. Experimental windows of miscibility as a function of the ethylene content for VAE copolymers and the acrylic acid content of the acrylate-acrylic acid copolymers are observed (acrylate = methyl acrylate, ethyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate). Employing well-established analog heat of mixing measurements, predicted windows of miscibility were compared with experimental results. Fair qualitative agreement was observed and supported the hypothesis that specific rejection arguments can be employed to explain the observed miscibility. Failure to quantitatively predict miscibility based on the analog heat of mixing measurements may be due to the higher association tendencies of the model compounds relative to acrylic acid units in the high molecular weight polymers. No miscible combinations were found for methyl methacrylate-acrylic acid copolymers or acrylate-methacrylic acid copolymers in admixture with poly(vinyl acetate) or the VAE copolymers, thus indicating the sensitivity of phase behavior to minor structural changes. VAE (30 wt % ethylene) copolymers were also noted to be miscible with several polymers previously noted to be miscible with poly(vinyl acetate), namely, poly(vinylidene fluoride), poly(ethylene oxide), and nitrocellulose. © 1995 John Wiley & Sons, Inc.