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.     

Effect of woody biomass surface free energy on the mechanical properties and interface of wood/polypropylene composites

The aim of this study is to investigate the effect of surface free energy of wood flour (WF) and silanized WF on the mechanical properties and interface of wood/polypropylene (PP) composites. The contact angles of three probe liquids against unmodified and modified spruce WF were tested by capillary rise method based on the Washburn equation. Then the surface free energy and its corresponding dispersion and polar components were calculated according to the method developed by Owens–Wendt–Kaelble. The tensile strength and flexural strength of the wood/PP composite samples made with unmodified and modified WF were tested and the flexural fracture surfaces were analyzed by scanning electron microscopy (SEM). The results showed that the surface free energy of WF increased from 26.0 to 36.1?mJ/m², which was higher than that of PP (29.4?mJ/m²), and its corresponding polar component decreased from 13.1 to 4.4?mJ/m², and the dispersion component increased from 12.9 to 31.7?mJ/m² after the modification with 4 wt.% vinyltriethoxy silane, which makes it possible for spreading of PP on the surface of WF, the tensile strength and flexural strength of wood/PP composites made with modified WF were obviously improved. In addition, the improved compatibility between WF and PP was well confirmed by SEM.     

Thermal oxidation of high-modulus carbon fibers impregnated with potassium nitrate

Thermal oxidation of ultra-high-modulus Sigrafil UHM-3 carbon fibers (C-fibers) was performed by using potassium nitrate as an oxidizing agent. The impregnating solution consisted of 0.5–10 wt% KNO₃ in a water/methanol (3:1) mixture. Thermal treatment of the impregnated C-fibers was performed at 600 or 800°C in nitrogen or air, respectively. Furthermore, the influence of a subsequent treatment with 60% sulfuric acid was investigated. The thermal treatment of the impregnated C-fibers in nitrogen caused no change in their mechanical properties, whereas in the case of treatments in air, fiber damage was observed as indicated by a decrease in the tensile strength as well as by an increase of the BET surface area. Therefore, further investigations were carried out in a nitrogen atmosphere. An increase of the C-fibers' interlaminar shear strength (ILSS) from 22 to 40 MN/m² without loss of mechanical properties was achieved by impregnation with solutions of <5 wt% KNO₃. Impregnating solutions with higher concentrations damaged the fibers, however. A further increase of the ILSS to 57 MN/m² was obtained by subsequent treatment after the salt decomposition step with 60% sulfuric acid.     

Effects of XeCl excimer laser treatment of Vectran® fibers and their adhesion to epoxy resin

Vectran^® fibers, made using liquid crystalline polyester, were treated with pulsed XeCl excimer laser (308 nm) to alter their surface characteristics and, thus, improve their adhesion to epoxy resin. The treatments were carried out in air using varying numbers of pulses at different laser fluences. The effects of laser treatment on the fiber surface topography, chemistry and wettability have been investigated. Fiber/epoxy resin interfacial shear strength was measured using the microbead test. The surface roughness was characterized qualitatively and quantitatively using scanning electron microscopy (SEM) and atomic force microscopy (AFM), respectively. Changes in the surface energy were characterized using the Wilhelmy technique. Based on the SEM micrographs, the threshold fluence for the formation of surface structure was found to be less than 36 mJ/(pulse ? cm²). The laser treatments at fluences higher than the threshold fluence introduced periodic roll (wavy) structures on the fiber surface transverse to the fiber axis. From the AFM results, the fiber surface roughness was found to increase by up to 3.5 times the control fiber after the laser treatment. The dispersion component of the surface energy decreased, while the acid–base component of the surface energy increased significantly from 0 to 8.8 mJ/m² after the laser treatment. The Vectran^® fiber/epoxy resin IFSS increased by up to 75% after the laser treatment. This improvement is mainly attributed to higher surface roughness of the fiber.     

Inverse gas chromatography characterization of polyaniline complexes: application to volatile organic compounds sensing

Surface thermodynamic characteristics of two polyaniline complexes with inorganic and organic acids were investigated using inverse gas chromatography technique. Thirteen solutes were injected into two separate chromatographic columns packed with polyaniline (PANI) complexes as stationary phases without any chromatographic support. The retention volumes of these solutes were measured to show their strong retention with both PANI complexes, particularly the xylene isomers: ortho, meta and para. The free energy of adsorption, $\Updelta G_{a}$ Δ G a , consisting of dispersive term $\Updelta G_{a}^{d}$ Δ G a d and the acid–base interaction term, $\Updelta G_{a}^{s}$ Δ G a s was also determined showing that it is mainly based on its dispersive contribution. The dispersive surface energy of hydrochloric acid polyaniline complex is ranging from 70.39 mJ/m² at 130 °C to 65.75 mJ/m² at 150 °C while the surface energy of dodecylbenzenesulfonic acid polyaniline complex has shown slight upper difference ranging from 70.90 to 66.23 mJ/m² in the same temperature’s interval, thus reflecting a behavior comparable to that of high surface energy materials. Furthermore, the obtained PANI complexes powders were characterized using fourier transform infrared spectrometry, Raman spectroscopy, UV–visible, XRF and SEM techniques. The measured retention volumes were combined with linear solvation energy relationship (LSER), called Abraham law, to determine physicochemical parameters describing dispersive, polar and acid–base properties, the surface of both polyaniline was found out exhibiting a basic nature.     

Characterization of cellulose surface free energy

The thin-layer wicking technique was used to determine the surface free energy components and the surface character of three celluloses (Sigmaccll 101, Sigmacell 20, and Avicel 101), using an appropriate form of the Washburn equation. For this purpose, the penetration rates of probe liquids into thin porous layers of the celluloses deposited onto horizontal glass plates were measured. It was found that the wicking was a reproducible process and that the thin-layer wicking technique could be used for the determination of the celluloses' surface free energy components. The size of the cellulose particles was characterized with the Galai CIS-100 system and their crystallinity was measured by X-ray diffraction. The three celluloses have high apolar (y^LWS = 50-56 mJ/m²) and electron donor (γs = 42-45 mJ/m²) components, while the electron acceptor component (γS⁺ ) is practically zero. The free energy interactions of cellulose/water/cellulose calculated from the components are positive, regardless of the cellulose crystallinity. This would mean that the cellulose surfaces have a hydrophilic character. However, the work of spreading of water has a small negative value (3-9 mJ/m²), indicating that the surfaces are slightly hydrophobic. It is believed that the work of spreading characterizes better the hydrophobicity of the surface than the free energy of particle/water/particle interaction, because in the latter case, no electrostatic repulsion is taken into account in the calculations.     

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     

Surface energy mapping of Kevlar® fibers by inverse gas chromatography

The surface energy characteristics of three Kevlar® fibers have been systematically studied using two inverse gas chromatography (IGC) techniques, i.e., at an infinite probe dilution and at a finite probe concentration, with the latter allowing a unique mapping of the surface energy levels, which complements greatly the more traditional characterization of the highest energy sites. The standard thermodynamic parameters, such as the free energy −Δ , and the adsorption enthalpy and entropy (Δ and −Δ ), as well as the dispersive and the specific component ( and ΔG^sp/I^sp) of the fiber surface energy, were determined from the retention behavior at zero coverage of selected molecules of various polarity. The values are between 49–58 mJ m⁻² for the three fibers at 50°C. The polar components, ΔG^sp or I^sp, calculated by three different methods, reveal the polar feature of the fiber surface. It is interesting to note that the adsorption enthalpies Δ for the short chain alkane probes are nearly the same as their liquefaction energies. Using the second IGC approach, i.e., at finite concentration, the isotherms for the adsorption of n-octane and n-hexylamine on the three selected Kevlar® fibers were constructed by the one-peak method. These are shown to be instrumental to establish the corresponding energy distribution functions. The results may indicate that, unlike the alkane probes, the polar molecules interact strongly with the Kevlar® fiber surfaces, which appear, in this case, energetically heterogeneous. The resulting energy distribution mapping opens new avenues towards the surface characterization of the global surface without the restriction of the averaging imposed by other bulk analysis techniques. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 487–500, 1998     

Inverse gas chromatography for determining the dispersive surface free energy and acid–base interactions of sheet molding compound—Part II 14 Ligno‐cellulosic fiber types for possible composite reinforcement

Composites reinforced with natural plant fibers are currently actively researched. Inverse gas chromatography (IGC) is a technique that is used to characterize the surface energy and polar characteristics of materials. The theoretical approaches used with IGC are reviewed and applied to the study of 14 ligno‐cellulosic fiber types including grass fibers, bast fibers, leaf fibers, seed fibers, and fruit fibers. This was done to provide insight into the impact of fiber composition on the surface characteristics of the different fiber types and explore possible correlations among the data. The dispersive surface energy, and K_a, K_b constants are reported for the 14 fiber types and compared with values reported in the literature. The dispersive energies ranged from 35.5 mJ/m² to 44.2 mJ/m² at 20°C with K_a from 0.01 to 0.38 and K_b from 0 to 1.05. A correlation was found at 40°C for surface energy related to fiber composition and fiber type where the surface energy decreases with increasing lignin and hemicellulose composition but increased with increasing cellulose concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Tailoring intrinsic hydrophobicity and surface energy on rough surface via low-T Cassie–Wenzel wetting transition method

Wettability is an important parameter of micro/nanostructured composites. The measurement of apparent contact angle is strongly affected by surface roughness, which induces some challenges to study the intrinsic hydrophobicity correlating to the nature of chemistry. Carbon-Nafion composites exhibited about 30° decrease in apparent contact angle from 30 to 10°C due to the condensation of water vapor into cavities, suggesting a significant Cassie–Wenzel wetting transition phenomenon. The focus of this work has been on the first-time use of a low-T Cassie–Wenzel wetting transition method to evaluate Young's (ideal) contact angle and surface free energy. A maximum Young's contact angle (113°) and minimum total surface energy (12 mJ/m²) were determined at Nafion content of 70 wt%, indicating the orientation effect that sulfonate groups in Nafion preferentially pointed toward polar carbon. This approach provided the reasonable prediction of intrinsic hydrophobicity, especially when a rough solid surface is not easily wetted by liquids.     

A novel positive photosensitive polybenzoxazole based on a tetrahydropyranyl (THP) protected polyhydroxyamide

Summary A new positive working, aqueous base developable photosensitive polybenzoxazole (PBO) precursor composition based on a partially tetrahydropyranyl (THP) protected PBO precursor and a Bisphenol A based 1,2-naphthoquinone diazide-4-sulfonate (DNQ-4) photosensitive compound has been developed. The polymer was prepared from a low temperature polymerization of 2 , 2'-bis-(3-amino-4-hydroxyphenyl) hexafluoropropane (BisAPAF) and isophthaloyl chloride (IC), followed by reacting with 3,4-Dihydro-2H-pyran in the presence of p-toluenesulfonic acid monohydrate as a catalyst. The photosensitive PBO precursor containing 20wt % DNQ-4 photosensitive compound showed a sensitivity of 221 mJ/cm² and a contrast of 1.44 in a 3 m film with a 0.6wt % tetramethylammonium hydroxide (TMAH) developer. A pattern with a resolution of 10 m was obtained from this composition. The novel PBO precursor photosensitive composition showed a significant improvement in dark film loss after development, which can and could be used to make a thick film resist.     

Structure–property correlations of foul release coatings based on low hard segment content poly(dimethylsiloxane–urethane–urea)

We report the foul release characteristics of model poly(dimethylsiloxane–urethane–urea) (PDMSPU)-based coatings with a relatively lower hard segment content of 9 to 13.7 wt%. The PDMSPUs were prepared by facile moisture curing of isophorone diisocyanate-capped hydroxyalkyl-terminated PDMS. The surface free energies of the coatings were tuned (20–25 mJ/m²) by varying the hard segment content to be in the minimum adhesive regime (20–30 mJ/m²) of Baier’s curve pertaining to the relative amount of biofouling vs the critical surface tension of various chemical substrates. A series of complimentary analytical tools, namely ¹H NMR spectroscopy, small-angle x-ray scattering (SAXS), FTIR-attenuated total reflectance spectroscopy (FTIR-ATR), contact angle goniometry, marine field tests, and quantitative biofouling adhesion in shear, have been employed to deduce several physicochemical parameters of importance to establish the structure property correlations. Further, the time-dependant changes in surface wettability and surface concentration of polar functional groups of the coatings (immersed in 3.5 wt% aqueous solution of NaCl) were investigated by FTIR-ATR and contact angle goniometry. The extent of surface restructuring was found to increase with increasing hard segment content of the PDMSPUs and consequently increasing attachment strengths of macrofoulants with the coatings, which were in the range 0.12–0.5 MPa.     

PBO纤维及其改性的研究进展

简述了聚对苯撑苯并双噁唑(PBO)纤维的结构与性能;详述了PBO纤维的改性研究进展。PBO纤维的改性主要是改善其抗压性能和表面粘结性能。提高微纤间相互作用或交联等方法可提高PBO纤维的压缩强度;通过酸处理、偶联剂处理、等离子体处理及电晕处理等方法可提高PBO纤维的表面粘结性能。指出表面改性仍将是PBO纤维改性研究的重点。     

Fluoroalkylation of polyester by end-capped fluoroalkyl-functional silanes

The surface modification of polyester was examined using both monomeric and oligomeric silanes having end-capped fluoroalkyl groups. From contact angle measurements, the surface free energies of polyester were reduced to 15-20 mJ/m² for the dispersive component and 1 -3 mJ/m² for the polar component, respectively, and all the surfaces were shown to be both highly water- and oil-repellent. By XPS (X-ray photoelectron spectroscopy) measurements, using the C l.s peak attributable to the C=O of polyester, the thickness of the siloxane layer on the surface was shown to be less than 5 nm. The solvent durability (resistance) of the modified surfaces was evaluated using contact angle and XPS measurements. Although all the modified surfaces showed durability against dodecane, xylene, ethyl acetate, tetrachloroethylene, and hydrochloric acid, long-time immersion in fluorine-containing solvents reduced the oil repellency of some of the surfaces modified with monomeric or oligomeric silanes having short fluoroalkyls. In particular, immersion in alkaline solution destroyed the siloxane network and thus reduced their water repellency, while interestingly their oil repellency remained unchanged. The modification mechanism is also discussed in terms of simultaneous thermal anchoring and polymerization of silanes.     

Effect of combined surface treatment on the adhesion performance of aluminium-lithium alloy

Herein we investigated the effect of various surface treatments, especially the combined surface treatment of grit-blasting and phosphoric acid anodization (PAA), on the surface characteristics and the adhesion performance of aluminium-lithium alloy sheets. For the combined surface treatment, rough surfaces were firstly created by grit-blasting to increase the surface area available for anodization. Next, porous structures were produced on the grit-blasted surfaces by PAA. The surface characteristics, surface wettability, fracture morphology, and shear strengths of samples subjected to different surface treatments were compared and analyzed. The effect of surface roughness on the bonding strength of aluminium-lithium alloys subjected to combined treatments was also investigated. The experimental results showed that combined treatment provided the best wettability and single-lap joint performances, with the highest surface free energy of 81.4?mJ/m² and shear strength of 40.8?MPa.     

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.     

Surface free energy of synthetic chalcocite from zeta potential and contact angle techniques

—The zeta potentials of synthetic chalcocite wetted with n-alkanes were determined in doubly-distilled water. Then the relationship between the coverage of the chalcocite surface with n-heptane or n-hexanol and the zeta potential in water was found. Using an empirical relation, the film pressure of n-heptane and n-hexane was determined. Next the dispersive and polar components of the surface free energy were calculated. The value of the dispersive component was also determined by contact angle measurements. The values obtained were 81.0 and 22.7 mJ/m², for the dispersive and the polar components of the surface free energy, respectively.     

Synthesis and interfacial properties of montmorillonite/polypyrrole nanocomposites

Montmorillonite/polypyrrole (MMT/PPy) nanocomposites were prepared by the in situ polymerization of pyrrole in the presence of MMT. The morphology of the MMT/PPy nanocomposites as examined by scanning electron microscopy differs slightly from that of the untreated MMT but markedly from that of polypyrrole. X-ray photoelectron spectroscopy (XPS) showed that the materials have MMT-rich surfaces, an indication that polypyrrole is essentially intercalated in the host clay galleries. The transmission electron microscopy showed, that the interlamellar spacing of the untreated MMT increased from 1.25 to 18.9 nm, when compared to nanocomposite MMT/10.8% PPy. Moreover, XPS highlighted the cation exchange of Na⁺ from montmorillonite by K⁺ (from the oxidant) and by the positively charged polypyrrole chains. Inverse gas chromatography indicated that the nanocomposites are high surface energy materials with a dispersive contribution to the surface energy reaching 200 mJ/m² at 150 °C, for a PPy loading of 21.4 wt%. The values of the MMT/PPy nanocomposites were correlated to the changes in the specific surface area of the MMT induced by the intercalation of polypyrrole.     

Recent developments in the technology of sulphur dioxide depolarized electrolysis

The use of sulphur dioxide as an anode depolarizer in the electrolytic production of hydrogen can considerably reduce the electrical energy input to the electrolyzer. The present work deals with developments in the technology of SO₂-depolarized electrolysis. Recent achievements in electrode fabrication techniques and optimization of cell configuration have resulted in substantial improvements in both cell potential and performance stability. While operating in 50 wt% sulphuric acid at 50° C and 1 atm, the measured cell potentials at 200 and 400mA cm^–2 were 0.77 and 1.05V (including ohmic losses), respectively. A cell endurance test, performed at a constant current density of 100mA cm^–2, indicated that a stabilized cell potential of 675 mV was achieved after 80 hours of continuous operation. The resulting gas from the test cell contained 98.7 vol% hydrogen. The effect of acid concentration in the range 10–60 wt% on the performance characteristics of an SO₂-depolarized electrolyzer was also investigated. Experimental results revealed that the optimum acid concentration for operating SO₂-depolarized electrolyzers is approximately 30 wt%. The observed cell potential was only 0.71 V at 200mA cm^–2.