Relation of interfacial adhesion in Kevlar®/epoxy systems to surface characterization and composite performance

A central problem in composite materials is the poorly understood relation between the nature of the surfaces at the fiber/matrix interface, the actual interfacial bond strength, and interface-sensitive composite properties, in this study on the Kevlar®/epoxy composite system, the interface was varied chemically by fiber sizings. The sized and unsized fiber surfaces and the cured matrix surface were characterized by contact angle measurements. The interfacial shear strength was directly measured by single-filament pull-out tests of sized and unsized fibers in epoxy matrix. The shear strengths of the composites made with sized and unsized fibers were measured. The results from surface analysis, interfacial shear tests, and composite shear tests were consitent. This suggests that surface-contact-angle analysis and single-filament pull-out tests may be helpful in screening strength of the composite.     

Influence of carbon fiber surface treatments on the structure and properties of conductive carbon fiber/polyethylene films

Effects of carbon fiber (CF) surface modification on the crystalline structure and both electrical and mechanical properties of conductive CF/high‐density polyethylene (HDPE) films were studied. Three different types of surface‐treated CF, epoxy‐sized, unsized, and sized but thermally treated, were considered. It was found that the uniformity of the transcrystalline zone around CF and the overall crystallinity of the polyethylene matrix decreased when epoxy‐sized CF was used. Epoxy‐sized CF caused a significant reduction not only in electrical resistivity and temperature coefficient of resistivity (TCR) but also tensile strength and coefficient of linear thermal expansion (CLTE) of composite films compared with that of unsized or sized CF that was thermally treated. We observed the systematic changes of TCR and CLTE values in accordance with CF surface modification and CF content in composite films. It was concluded that thermal expansion of the polymer matrix is the main reason for the positive TCR of CF/HDPE films. As the most probable reasons for decreased resistivity and strength of the CF/HDPE films with epoxy‐sized CF, the diffusion of epoxy sizing agent into the polyethylene matrix and the formation of loosened semiconductive interphase structure in the film are considered. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2040–2048, 2002; DOI 10.1002/app.10500     

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     

Temperature effect on interfacial bonding property of single‐carbon fiber/epoxy resin composite

The changes in interfacial fracture energy of three kinds of commercially sized carbon fiber (CF)/epoxy resin composites in the range from ambient temperature to 130°C were investigated using the single‐fiber fragmentation test to evaluate the heat resistance of the interphase. The effects of CF sizing on the interfacial bonding property were studied using desized CF/epoxy resin composites. Thermogravimetric analysis and differential scanning calorimetry of the combination of sizing and matrix were employed to investigate the role of sizing on the variations in the fiber/matrix interfacial property under elevated temperature. The interfacial fracture energy values of all the studied CF composites were found to decrease quickly during the initial stage of temperature rise and drop gradually at higher temperature. At elevated temperature, the desized CF composites had higher heat resistance than the corresponding sized fiber composites. The differences in the interfacial heat resistance among the three kinds of CF composites and the difference in the interfacial thermal stability between the sized and the desized fiber composites were related to different glass transition temperatures of the interphases. The interaction between sizing and the matrix and the chain motion of the crosslink structure of the interphase has been suggested to determine the interfacial heat resistance. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Characterization of a rigid silicone resin

Silicone resins have been used as binders for ceramic frit coatings and can withstand temperatures of 650°C to 1260°C. Conceptually, silicone resins can potentially be used as matrices for high temperature fiber‐reinforced composites. The mechanical and thermal properties of a commercially available silicone resin, Dow Corning® 6‐2230, were characterized. Neat 6‐2230 resin was found to have inferior room temperature mechanical properties such as flexural, tensile and fracture properties when compared to epoxy. The room temperature flexural properties and short beam shear strength of the silicone/glass composites were also found to be lower than those of epoxy/glass composite with similar glass content. However, the silicone resin had better elevated temperature properties. At an elevated temperature of 316°C, the retentions of flexural modulus and strength were 80% and 40% respectively of room temperature values; these were superior to those of phenolic/glass. Unlike the carbon‐based resins, the drop in flexural properties of the silicon/glass laminates with temperature leveled off with increase in temperature beyond 250°C. The resin weight loss at 316°C in 100 cm³/min of flowing air was small compared to other carbon‐based resins such as PMR‐15 and LaRC TPI. Only Avimid‐N appeared comparable to Dow Corning® 6‐2230.     

Influence of new thermoplastic sizing agents on the mechanical behavior of poly(ether ketone ketone)/carbon fiber composites

In this study, unidirectional poly(ether ether ketone)/carbon fiber (CF) composite sheets were elaborated with unsized, epoxy‐sized, and thermoplastic‐sized CFs by hot‐press molding. The thermoplastic sizings that we used were poly(ether imide) (PEI) and poly(ether ketone ketone) oligomer aqueous dispersions. Scanning electron microscopy observation of the composites freeze fractures showed that unlike unsized or epoxy‐sized CFs, the thermoplastic sizings improved the interaction between the fibers and the matrix. A comparative study of the mechanical relaxations by dynamic mechanical analysis was carried out on the different composites before and after immersion in kerosene. At low temperature, the PEI sizing had a significant influence on the β relaxation, particularly after kerosene immersion. The thermoplastic sizings did not modify the glass‐transition temperature but improved the kerosene resistance on the composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42550.     

Influence of epoxy sizing of carbon‐fiber on the properties of carbon fiber/cyanate ester composites

The high modulus carbon fiber (M40J) sized by epoxy resin E51 and E20 reinforced bisphenol A dicyanate (2,2′‐bis(4‐cyanatophenyl) isopropylidene resin composite was prepared in order to investigate the influence of epoxy sizing of the fiber on the properties of the composite. Differential scanning calorimetry (DSC) and fourier transforms infrared (FTIR) analysis showed that epoxy resin have catalytic effect on cure reaction of cyanate ester. Mechanical properties of the composite revealed that M40J fiber sized by epoxy resin could improve the flexural strength and interlaminar shear strength of M40J/bisphenol A dicyanate composites. The micro‐morphology of the composite fractures was studied by means of scanning electron microscopy (SEM). Reduced flaws were observed in the M40J‐bisphenol A dicyanate interface when the sized fiber was used. Water absorption of the composites was also investigated. It was found that the water absorption descended at the initial boiling stage (12 h). POLYM. COMPOS, 27: 591–598, 2006. © 2006 Society of Plastics Engineers     

Dynamic stress/strain response of the interphase in polymer matrix composites

The interphases of various sized E‐glass‐fiber/epoxy‐amine systems were tested at displacement rates in the range of 230 to 2450 fxm/sec using a new experimental technique (dynamic micro‐debonding technique). The fiber systems include unsized, epoxy‐amine compatible sized, and epoxy‐amine incompatible sized glass fibers. A data reduction scheme was developed to relate the force vs. displacement response obtained from the dynamic micro‐debonding technique to interphase shear stress/strain response. The stress/strain curves and interphase shear modulus values were obtained from these composite systems under average shear strain rates (ASSR) in the range of 215–3278 (1/s). The results showed that the magnitude of the interphase shear modulus was sizing and strain rate dependent. In all cases, the shear modulus was found to be more compliant than the bulk matrix. The two sized fiber systems exhibited the highest strain rate sensitivity, with modulus increasing about threefold over the range studied. In addition, the rate dependent behavior of the model interphase materials were determined using the dynamic mechanical analysis (DMA) technique. The model interphase materials closely resemble the interphase that forms on unsized and compatible sized fibers. Master curves relating the flexural storage modulus to strain rate were constructed based on the time‐temperature superposition principle from DMA frequency sweep measurements. The DMA measured results are consistent with the dynamic micro‐debonding test results, providing confidence in the test method as a reliable technique for characterizing the high strain rate properties of the interphase in composites.     

Determination of mechanical properties of glass‐epoxy composites in high temperatures

The objective of this study is to determine the tensile, compressive, and shear properties of unidirectional glass/epoxy composite plates under room (∼20°C) and high (40, 60, 80, and 100°C) temperatures. Mechanical properties were determined according to the ASTM standards. A hot lamination press was used for fabrication of composite plates. For curing process, laminated plates were retained at a constant pressure (250 kPa) and 120°C during 2 h. And then, composite plate is cooled to room temperature at the same pressure. The fiber volume fraction of laminated composite plate is measured as 65%. Experimental results show that the mechanical properties (except for the transverse tensile strength) of glass/epoxy composites are reduced by increasing temperature. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Interfacial stress transfer in nylon‐6/E‐Glass microcomposites: Effect of temperature and strain rate

In this study, the interfacial properties between E‐glass fibers with different commercial sizings have been investigated on model composites with a nylon‐6 matrix. In particular, the fiber critical length was measured by means of the single‐fiber fragmentation test over a wide range of temperatures (from 25 to 175°C) and strain rates (from 0.0008 to 4 min⁻¹). The general trend observed is that the fiber critical aspect ratio increases as the temperature increases and it decreases as strain rate is increased. The fiber critical aspect ratio for unsized fibers resulted to be reasonably well linearly related to the square root of the fiber to matrix modulus ratio. This results is in accordance with the Cox's shear‐lag theoretical model and the Termonia's numerical simulations. Sized fibers display an higher deviation from the theoretical prevision probably because of the presence of interphases whose properties are different from the bulk matrix. As a consequence, the interfacial shear strength values resulted to be dependent on the fiber sizing. In particular, the fibers coated with an epoxy sizing showed a superior thermal stability of the fiber matrix‐interface with respect to the unsized or nylon compatible sized fibers.     

Thermal degradation of epoxy resin reinforced with polypropylene fibers

The influence of polypropylene fibers on the thermal degradation of epoxy composites was investigated with thermogravimetric analysis. Three composites with 5, 10, or 15 wt % polypropylene fibers were prepared with epoxy as a matrix material. The polypropylene fibers, used as reinforcing materials, retarded the thermal decomposition, and increasing the weight percentage of the fiber material increased the thermal stability to a certain extent. Of the three composites, the 10 wt % polypropylene fiber/epoxy resin composite showed very good thermal stability, which was indicated by the increase in the resin decomposition temperature from 280°C for the 5 wt % polypropylene fiber/epoxy resin composite to 375°C for the 10 wt % polypropylene fiber/epoxy resin composite. The Horowitz–Metzger method was used to calculate the activation energies, and the results were tabulated. A morphological analysis was carried out with scanning electron microscopy to evaluate the dispersion of the fibers in the epoxy matrix. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 500–503, 2007     

Effect of polyurethane sizing on carbon fibers surface and interfacial adhesion of fiber/polyamide 6 composites

Commercial epoxy sized carbon fibers (CFs) or unsized CFs have poor interfacial adhesion with polyamide 6 (PA6). Here, CFs are coated with polyurethane (PU) and their surface properties in terms of surface chemistry, contact angle, roughness, and morphology, are investigated. The results of Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy demonstrate PU sizing evidently increases the quantity of polar functional groups on the CFs surface. The surface energy of the PU sized fiber is calculated according to the Owens–Wendt method. Compared with unsized fibers, the contact angle of PU sized fibers is decreased while their total surface energy is increased, indicating superior wettability. Moreover, transverse fiber bundle tests are performed to determine the interfacial adhesion between the CFs and PA6 matrix. The transverse fiber bundle strength of unsized CF is measured to be 12.57 MPa. For PU sized CFs processed with sizing concentration of 1.2%, this value is increased to 24.35 MPa, showing an increase of more than 90%. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46111.     

Effects of electrophoretically deposited carbon nanofibers on the interface of single carbon fibers embedded in epoxy matrix

Electrophoretic deposition (EPD) was used to deposit carboxylic acid-functionalized carbon nanofibers (O-CNFs) on the surface of single carbon fibers. Using the single fiber fragmentation technique and Weibull analysis, interfacial shear strength (IFSS) was estimated for different fiber surface treatments. Samples for sized, unsized, O-CNF deposited sized, and O-CNF deposited unsized carbon fibers were tested. Additionally, the effects of EPD were investigated by testing sized and unsized carbon fiber samples exposed to an electric field in water. Removal of the fiber sizing decreased IFSS by approximately 27%, but addition of O-CNFs to the unsized fiber surface led to an increase of 15% compared to the sized base fiber. The O-CNF deposited sized fibers provided IFSS increases of 207.6% and 66.9% for 1 and 5 min deposition durations, respectively. The surface morphology of all samples was characterized, and those containing homogeneous deposition of closely bound O-CNFs provided the highest IFSS values. Exposing sized fibers to the electric field for 1 min led to an IFSS increase of 79%, while unsized fibers undergoing the same treatment provided increases of 7.7% and 46% compared to the base sized fiber and unsized fiber samples, respectively.     

Synthesis and characterization of a new class of thermosetting resins: Allyl and propargyl substituted cyclopentadiene derivatives

A series of all-hydrocarbon resins were synthesized by reacting cyclopentadiene allyl chloride, propargyl chloride, or a mixture of allyl chloride and propargyl ide, under phase transfer conditions. Phase transfer reactions with and without added solvents, and with either quaternary ammonium or crown ether catalysts, yielded similar products consisting of a mixture of 1,1-disubstituted cyclopentadiene (minor amount) and 2-3 isomers each of tri-, tetra-, penta-, and hexa-substituted derivatives. No further reaction of each these components possible. The overall substitution pattern varied little with changes in reaction conditions although limiting the allyl chloride content led to still reactive, partially substituted products. Incorporation of all-propargyl and high propargyl-to-allyl mixed functionalities on cyclopentadiene yielded products whose stability was very hindering their thorough characterization. Preliminary evaluation was there-carried out for mixed resins with lower propargyl functionality. The allyl substituted resin (allylated cyclopentadiene, ACP) underwent thermal cure lout initiator at around 200°C while allyl/propargyl substituted resin (7:1 ratio, APCP) showed a faster, lower temperature cure at around 120°C. Cationic cure of ACP was also initiated by a novel sulfonium salt at around 100°C. Neat resin when cured at 200°C gave material with a flexural storage modulus 2 of about 300 MPa. Further cure at 250°C raised the modulus to 1.2 GPa. resin gave composites with excellent properties when used with glass and on fibers. Flexural modulus values (by DMA) of ∼ 66 GPa were obtained for ACP/carbon fiber composites compared with 42 GPa for epoxy/carbon composites made in our laboratories using commercially available materials. The modulus values at 300°C dropped to 10% of the room temperature value for the epoxy composites, while the ACP/carbon composite maintained 60% of its room temperature value at 300°C. When brought back to ambient temperature, the modulus of latter sample had increased to 80 GPa and that of the epoxy composite dropped to 23 GPa. Glass fiber ACP composites performed similar to an epoxy composite up to 200°C but maintained properties up to 300°C while those of the epoxy were drastically reduced. TGA analysis of both cured ACP resin and its composites showed decomposition beginning at 375°C. Three-point-bending tests indicated very high modulus with brittle failure for ACP composites. Scanning electron micrographs showed moderate bonding of the new resin to both carbon glass fiber surfaces. This new class of thermosetting resins offers excellent potential for application in low-cost glass and carbon composites with good thermal and physical properties.     

Thermal conductivity of pristine and brominated highly graphitized pitch based carbon fibers

The thermal conductivity of brominated and pristine Union Carbide P-100 graphite fibers in the 30–160°C temperature range was determined by measuring the thermal conductivities of graphite fiber epoxy composite samples and then excluding the epoxy contribution. A comparative thermal conductivity instrument was used to measure the thermal conductivity of the samples containing fibers. Results showed that the thermal conductivity values were 225–370 W/m-k and 215–340 W/m-K for pristine and brominated fibers respectively. Furthermore, the thermal conductivity ratio of brominated to pristine P-100 fibers was 0.89, 0.91 and 0.92 at 55–80°C, 108 and 130°C respectively. Such a decrease in thermal conductivity results almost entirely from the 10% increase in the fiber cross-sectional area due to bromination. This result suggested that bromination effects on P-100 fiber structure is small and that some structural changes (presumably the sharp-angled domain wall becomes less sharp) occurred in the 80–108°C temperature range.     

Effects of fiber size on short‐term creep behavior of wood fiber/HDPE composites

When natural fiber‐thermoplastic composites are used in long‐term loading applications, investigating creep behavior is essential. The creep behavior of high‐density polyethylene (HDPE)‐based composites reinforced with four sizes of wood fibers (WFs) (120–80, 80–40, 40–20, and 20–10 mesh) was investigated. The instantaneous deformation and creep strain of all WF/HDPE composites increased at a fixed loading level when the temperature was increased incrementally from 25 to 85°C. At a constant loading level, composites containing the larger‐sized WFs had better creep resistance than those containing smaller‐sized fibers at all measured temperatures. The creep properties of composites with smaller‐sized WFs were more temperature‐dependent than those with larger‐sized WFs. Two creep models (Burger's model and Findley's power law model) were used to fit the measured creep data. A time–temperature superposition principle calculation was attempted for long‐term creep prediction. The Findley model fitted the composite creep curves better than the four‐element Burger's model. From the predicted creep response of the WF/HDPE composites, two groups of small fibers (120–80 and 80–40 mesh) had the lowest creep resistance over long periods of time at the reference temperature of 25°C. The largest WFs (10–20 mesh) provided the best composite creep resistance. POLYM. ENG. SCI., 55:693–700, 2015. © 2014 Society of Plastics Engineers     

Incorporation of silicon dioxide nanoparticles at the carbon fiber‐epoxy matrix interphase and its effect on composite mechanical properties

Functionalized silicon dioxide nanoparticles (nano‐fSiO₂) were uniformly deposited on the surface of carbon fibers (CFs) using a coating process which consisted of immersing the fibers directly in a suspension of nano‐fSiO₂ particles and epoxy monomers in 1‐methyl‐2‐pyrrolidinone (NMP). The 0° flexural properties, 90° flexural properties, and Interlaminar shear strength (ILSS) mechanical properties of unidirectional epoxy composites made with nano‐fSiO₂+epoxy sized carbon fibers, with control fibers, and with epoxy‐only sized fibers were measured and compared. An obvious increase of the fiber/matrix adherence strength was obtained with the nano‐fSiO₂+epoxy coating. The nano‐fSiO₂+epoxy sized CF/epoxy composites showed a relative increase of 15%, 50%, and 22% in comparison to control fibers, for the Interlaminar shear strength, the 90^° flexural strength and the 90° flexural modulus, respectively, but little e difference was measured between the different systems for the 0° flexural properties. The observation of the fracture surfaces by scanning electron microscopy of composite fracture confirmed the improvement of the interfacially dependent mechanical properties. POLYM. COMPOS., 38:1474–1482, 2017. © 2015 Society of Plastics Engineers     

Concentration-dependent diffusion of dye in reactive dyeing systems

The cure of a tetrafunctional epoxy resin (largely tetraglycidyldiaminodiphenylmethane, TGDDM), cross-linked with diaminodiphenylsulphone (DDS) and boron trifluoride/ethylamine (BF₃EA) catalyst, is affected in a complex fashion by the presence of an oxidized carbon fiber surface. If the fiber is aged in a humid environment (25°C, 95% humidity) before coating with the matrix, the affinity of the oxidized fiber surface for water leads to destruction of the catalyst and retardation of the cure. This retardation is noticeable at lower humidities if the polymer content of the composite is reduced to > 20%. For oxidized fibers that are stored under ambient conditions (40% humidity), the retarding effect of water is overwhelmed by the catalytic effect of the acidic fiber surface. This activates the latent catalyst, increasing the rate of epoxy consumption and the proportion of the epoxy–epoxy reaction relative to the epoxy–amine reaction. For the low-humidity case, even though the rate of chemical reaction is increased, vitrification of the matrix is retarded, implying that there is less cross-linking and more extended epoxy–epoxy sequences in the network. The proposed chemical changes in epoxy/carbon fiber composites were confirmed by analysis of model reactions in solution. © 1992 John Wiley & Sons, Inc.     

CHARACTERIZATION, PROPERTIES, AND PROCESSING OF LARC PETI-5® AS A HIGH-TEMPERATURE SIZING MATERIAL: III. ADHESION ENHANCEMENT OF CARBON/BMI COMPOSITES

A phenylethynyl-terminated imide oligomer (LaRC PETI-5®) with a number average molecular weight of 2500 g/mol has been applied onto the surfaces of PAN-based carbon fiber tows and woven carbon fabrics as a sizing material to introduce an interphase between the fiber and matrix in carbon/BMI composites. The adhesion between the fiber and matrix was enhanced by the presence of a properly processed LaRC PETI-5® interphase. The results showed that when LaRC PETI-5® was sized and processed at 150°C, the interfacial shear strength (IFSS) of unidirectional IM7/BMI composite measured by using a microindentation technique and the interlaminar shear strength (ILSS) of a carbon/BMI composite measured by short beam shear test were markedly improved by about 35% and 66%, respectively, in comparison with the unsized counterparts. The adhesion enhancement strongly depends not only on the presence or absence of LaRC PETI-5® sizing interphase but also on the temperature profile applied to the sizing before composite fabrication. Both of these factors critically influence the physical and chemical state of the sizing material. Scanning electron microscopic observations of the composite fracture surfaces support the improved interfacial property of carbon/BMI composites.     

Effects of fiber surface grafting by functionalized carbon nanotubes on the interfacial durability during cryogenic testing and conditioning of CFRP composites

Carbon fiber reinforced epoxy (CE) composite is ideal for a cryogenic fuel storage tank in space applications due to its unmatched specific strength and modulus. In this article, inter-laminar shear strength (ILSS) of carbon fiber/epoxy (CE) composite is shown to be considerably improved by engineering the interface with carboxyl functionalized multi-walled carbon nanotube (FCNT) using electrophoretic deposition technique. FCNT deposited fibers from different bath concentrations (0.3, 0.5, and 1.0 g/L) were used to fabricate the laminates, which were then tested at room (30°C) and in-situ liquid nitrogen (LN) (−196°C) temperature as well as conditioning for different time durations (0.25, 0.5, 1, 6, and 12 h) followed by immediate RT testing to study the applicability of these engineered materials at the cryogenic environment. A maximum increment in ILSS was noticed at bath concentration of 0.5 g/L, which was ~21% and ~ 17% higher than neat composite at 30°C and − 196°C, respectively. Short-term LN conditioning was found to be detrimental due to developed cryogenic shock, which was further found to be compensated by cryogenic interfacial clamping upon long-term exposure.