Interfacial studies on the surface modified aramid fiber reinforced epoxy composites

In this work, solutions of rare earth modifier (RES) and epoxy chloropropane (ECP) grafting modification method were used for the surface treatment of aramid fiber. The effect of chemical treatment on aramid fiber has been studied in a composite system. The surface characteristics of aramid fibers were characterized by Fourier transform infrared spectroscopy (FTIR). The interfacial properties of aramid/epoxy composites were investigated by means of the single fiber pull‐out tests. The mechanical properties of the aramid/epoxy composites were studied by interlaminar shear strength (ILSS). As a result, it was found that RES surface treatment is superior to ECP grafting treatment in promoting the interfacial adhesion between aramid fiber and epoxy matrix, resulting in the improved mechanical properties of the composites. Meanwhile, the tensile strengths of single fibers were almost not affected by RES treatment. This was probably due to the presence of reactive functional groups on the aramid fiber surface, leading to an increment of interfacial binding force between fibers and matrix in a composite system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:4165–4170, 2006     

UV photo‐stabilization of tetrabutyl titanate for aramid fibers via sol–gel surface modification

Tetrabutyl titanate was used as sol–gel precursor of a nanosized TiO₂ coating to improve the photo‐stability of aramid fibers. The nanosized TiO₂ coating was characterized by XRD and XPS. The influence of the TiO₂ coating on photo‐stability of aramid fibers was investigated by an accelerated photo‐ageing method. The photo‐stability of aramid fiber showed obvious improvement after coating. After 156 h of UV exposure, the coated fibers showed less deterioration in mechanical properties with the retained tensile strength and elongation at break greater than 36 and 50% of the original values, respectively, whereas the uncoated fibers degraded completely and became powdery. SEM analysis showed no significant surface morphological change on the coated fiber after the exposure, while some latitudinal crack fractures appeared on the uncoated aramid fiber. The effect of the nanosized TiO₂ coating was also well demonstrated by examining the difference of distributions of C1s in XPS deconvolution analysis on the surface of uncoated/coated fibers with increasing UV exposure time. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3113–3119, 2007     

Enzyme‐mediated surface modification of jute and its influence on the properties of jute/epoxy composites

Surface modification of jute fibers is necessary to improve the adhesion and interfacial compatibility between fibers and resin matrix before using fibers in polymer composites. In this study, dodecyl gallate (DG) was enzymatically grafted onto the jute fiber by laccase to endow the fiber with hydrophobicity. A hand lay‐up technique was then adopted to prepare jute/epoxy composites. Contact angle and wetting time measurements showed that the surface hydrophobicity of the jute fabric was increased after the enzymatic graft modification. The water absorption and thickness swelling of the DG‐grafted jute fabric/epoxy composite were lower than those of the other composites. The tensile and dynamic mechanical properties of the jute/epoxy composites were enhanced by the surface modification. Scanning electron microscopy images revealed stronger fiber–matrix adhesion in composites with modified fibers. Therefore, the enzymatic graft modification increased the fiber–matrix interface area. The fiber–matrix adhesion was enhanced, and the mechanical properties of the composites were improved. POLYM. COMPOS., 38:1327–1334, 2017. © 2015 Society of Plastics Engineers     

Improvement of adhesion of Kevlar fiber to epoxy by chemical modification

Kevlar 149 fibers were surface-modified by chlorosulfonation and subsequent reaction of -SO₂O with some reagents (e.g. glycine, water, ethylenediamine, and 2-butanol) to improve the adhesion to epoxy resin. The mechanical properties and surface topography of the modified fibers were investigated at different reaction times and reagent concentrations. The surface functional groups introduced into the surface of the fibers were identified by X-ray photoelectron spectroscopy (XPS) and static secondary ion mass spectroscopy (SIMS). The interfacial shear strength (IFSS) between the fibers and epoxy resin was measured by the microbond test. The results showed that the IFSS was markedly improved (by a factor of 2.25) by the chlorosulfonation/glycine treatment and that the fiber strength was not affected. Scanning electron microscopy (SEM) was also used to study the surface topography of fibers pulled from the epoxy resin. Furthermore, energy dispersive X-ray (EDX) spectroscopy was used to qualitatively examine the amount of sulfur in the fiber surfaces and in the fracture surfaces of fibers from microbond pull-out specimens. The results of EDX examination were consistent with a change of the fracture mode from the interface between the fiber and the epoxy resin to a location within the fiber and/or epoxy resin as observed by SEM.     

Influences of liquid elastomer additive on the behavior of short glass fiber reinforced epoxy

In this study, improvements in mechanical and thermal behavior of short glass fiber (GF) reinforced diglycidyl ether of bisphenol-A (DGEBA) based epoxy with hydroxyl terminated polybutadiene (HTPB) modification have been studied. A silane coupling agent (SCA) with a rubber reactive group was also used to improve the interfacial adhesion between glass fibers and an epoxy matrix. 10, 20, and 30 wt% GF reinforced composite specimens were prepared with and without silane coupling agent treatment of fibers and also HTPB modification of epoxy mixture. In the ruber modified specimens, hardener and HTPB were premixed and left at room temperature for 1 hr before epoxy addition. In order to observe the effects of short glass fiber reinforcement of epoxy matrix, silane treatment of fiber surfaces, and also rubber modification of epoxy on the mechanical behavior of specimens, tension and impact tests were performed. The fracture surfaces and thermal behavior of all specimens were examined by scanning electron microscope (SEM), and dynamic mechanical analysis (DMA), respectively. It can be concluded that increasing the short GF content increased the tensile and impact strengths of the specimens. Moreover, the surface treatment of GFs with SCA and HTPB modification of epoxy improved the mechanical properties because of the strong interaction between fibers, epoxy, and rubber. SEM studies showed that use of SCA improved interfacial bonding between the glass fibers and the epoxy matrix. Moreover, it was found that HTPB domains having relatively round shapes formed in the matrix. These rubber domains led to improved strength and toughness, due mainly to the “rubber toughening” effect in the brittle epoxy matrix.     

Effect of rare earth elements surface treatment on tensile properties of aramid fiber‐reinforced epoxy composites

Solutions of rare earth modifier (RES) and epoxy chloropropane (ECP) grafting modification method were used for the surface treatment of aramid fiber. Tensile properties of both the aramid/epoxy composites and single fibers were tested. The effects of RES concentration on tensile properties of aramid/epoxy composites were investigated in detail to explore an optimum amount of rare earth elements in solution for modifying aramid fiber. The fracture surface morphologies of tensile specimens were observed and analyzed with the aid of SEM. The experimental results show that rare earth treatment is superior to ECP grafting treatment in promoting interfacial adhesion between the aramid fiber and epoxy matrix. Meanwhile, the tensile strengths of single fibers were almost not affected by RES treatment. The optimum performance is obtained when the content of rare earth elements is 0.5 wt %. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1037–1041, 2004     

Analysis of the tensile modulus of poly(p‐hydroxybenzoate)/poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) ternary polyester composite fibers

Liquid crystalline polymer reinforced plastics were prepared by compounding (PHB/PEN/PET) blends. A fibrillar PHB structure was formed in situ in the PEN/PET matrix under a high elongational flow field during melt‐spinning of the composite fibers. The formation of PHB microfibrils in the composite fiber with different PHB contents and winding speeds was observed. The PHB microfibril reinforced PEN/PET composite fibers exhibited an unexpectedly low tensile modulus. We have evaluated the tensile modulus of the fibers using the non‐modified 22 and a modified 23 Halpin–Tsai model. From the analysis of both models, large differences were found between the theoretical and experimental values of the tensile modulus, and the low value of the tensile modulus of the composite fiber could not adequately be explained by either model. Thus, we analyzed the observed modulus values using the Takayanagi model, 24 which describes the concept of mechanical discontinuities in semi‐crystalline polymers. Using the Takayanagi model, the effective fraction of continuous or discontinuous microfibrils was evaluated. Consequently, we could successfully explain the very low modulus of the PHB/PEN/PET composite fiber, having a large number of PHB microfibrils, using the Takayanagi model. Copyright © 2003 Society of Chemical Industry     

Improvement of the mechanical properties of an ultrahigh molecular weight polyethylene fiber/epoxy composite by corona‐discharge treatment

The interfacial shear strength of an ultrahigh molecular weight (UHMW) polyethylene (PE) fiber/epoxy‐resin system was greatly improved by the corona‐discharge treatment of the fiber. The UHMW PE‐fiber/epoxy‐resin composite was prepared with corona‐discharge‐treated UHMW PE fiber. The mechanical properties of the composite sheet were determined by tensile testing. The tensile strength of the composite was also very much improved. However, the tensile strength of the composite was about one‐half of the theoretical strength. This result was due to the molecular degradation of the PE‐fiber surface caused by surface modification. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1162–1168, 2001     

PET as a support material for TiO2 in advanced oxidation processes

The use of polyethylene terephthalate (PET) as a support material for TiO₂ films in advanced oxidation processes (AOPs) for water treatment was investigated. A green, low‐cost immobilization procedure was developed and the amount of deposited photocatalyst ranged from 0.036 to 0.202 mg per cm² PET. Photocatalytic activity of the films was evidenced by degrading paracetamol solutions under UV radiation. The highest kinetic constants were observed for at least 0.09 mg TiO₂ per cm² PET. Scan electron microscopy (SEM) and energy‐dispersive X‐ray (EDX) analyses indicated 0.15 mg TiO₂ per cm² PET as enough to provide complete covering of the PET support. Characterization analyses were also performed with a film after 30 h of use in a UV/TiO₂/O₃ reactor. According to SEM analyses, the photocatalyst was not detached from the PET support, while EDX and gravimetric data indicated the possibility of the TiO₂ to have been contaminated by compounds present in the solution during the treatment. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40175.     

Mechanical and morphological properties of carbon fiber reinforced–modified epoxy composites

Epoxy, prepared through aminomethyl 3,5,5‐trimethylcyclohexylamine hardening of diglycidylether of bisphenol‐A (DGEBA) prepolymer, toughened with polycarbonate (PC) in different proportions, and reinforced with carbon fiber, was investigated by differential scanning calorimetry, tensile and interlaminar shear strength testing, and scanning electron microscopy (SEM). A single glass transition temperature was found in all compositions of the epoxy/PC blend system. The tensile properties of the blend were found to be better than that of the pure epoxy matrix. They increased with PC content up to 10%, beyond which they decreased. The influence of carbon fiber orientation on the mechanical properties of the composites was studied, where the fiber content was kept constant at 68 wt %. Composites with 45° fiber orientation were found to have very weak mechanical properties, and the mechanical properties of the blend matrix composites were found to be better than those of the pure epoxy matrix composites. The fracture and surface morphologies of the composite samples were characterized by SEM. Good bonding was observed between the fiber and matrix for the blend matrix composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3529–3536, 2006     

RETRACTED ARTICLE: Surface modification of aramid fibers with novel chemical approach

Friedel–Crafts Reaction as a simple and convenient approach to the surface modification of aramid fiber was introduced in this paper. Epoxy chloropropane was chosen as the treatment reagent to modify aramid fibers surface via Graft reaction. After the modification, the interfacial properties of aramid/epoxy composites were investigated by the single fiber pull-out test (SFP), and the mechanical properties of aramid fibers were investigated by the tensile strength test. The results showed that the interfacial shear strength (IFSS) value of aramid/epoxy composites was enhanced by about 50%, and the tensile strength of aramid fibers had no obvious damage. The crystalline state of aramid fibers was determined by X-ray diffraction instrument (XRD), and the results showed that there were not any distinct crystal type varieties. The surface elements of aramid fibers were determined by X-ray photoelectron spectroscopy (XPS), the analysis of which showed that the oxygen/carbon ratio of aramid fiber surface increased obviously. The possible changes of the chemical structure of aramid fibers were investigated via Fourier transform infrared spectrum (FTIR), and the analysis of which showed that the epoxy functional groups were grafted into the molecule structure of aramid fibers. The surface morphology of aramid fibers was analyzed by Scanning electron microscope (SEM), and the SEM results showed that the physical structure of aramid fibers was not etched or damaged obviously. The surface energy of aramid fibers was investigated via the dynamic capillary method, and the results showed that the surface energy was enhanced by 31.5%, and then the wettability degree of aramid fiber surface was enhanced obviously too. All of the results indicated that this novel chemical modification approach not only can improve the interfacial bonding strength of aramid/epoxy composites remarkably, but also have no negative influence on the intrinsic tensile strength of aramid fibers.     

Removing Hydroxypropyl Methylcellulose Sizing from Sapphire Fibers by Ultraviolet/Ozone Cleaning

Ceramic-fiber-reinforced metallic and intermetallic matrix composites require well-characterized fiber/matrix interfaces. These interfaces require that the fiber surface be clean prior to the formation of a composite or application of a fiber coating. This work investigates the effectiveness of ultraviolet (UV)/ozone exposure at removing hydroxypropyl methylcellulose sizing from sapphire plates and fibers. The surface cleanliness was characterized using X-ray photoelectron spectroscopy (XPS). It was found that UV/ozone exposure removed the hydroxypropyl methyl-cellulose sizing from the plates and fibers but did not remove inorganic species contained in the coating or on the sapphire surface. These inorganic species were readily removed with a water/methanol rinse, providing a clean sapphire surface for incorporation into a composite.     

Accelerated ultraviolet aging study of the Vectran fiber

Aging behavior of Vectran fiber exposed to ultraviolet (UV) radiation was investigated. Vectran fiber was subjected to UV‐accelerated degradation environment. Tensile strength of Vectran fiber was determined at room temperature using a two‐parameter Weibull distribution. The average tensile strength loss was 42.75% when the irradiation time reached 186 h. The surface morphology of the degraded fiber was examined using scanning electron microscopy (SEM) and atomic force microscopy (AFM). X‐ray photoelectron spectroscopy (XPS) and ¹³C‐NMR were used to provide a molecular characterization of fibers. SEM and AFM showed that UV exposure result in microvoids on the surface of fibers. The results of the XPS and ¹³C‐NMR indicated that the UV radiation could lead to chain scission of fiber surface layer. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Solvent‐crazed PET fibers imparting antibacterial activity by release of Zn2+

Poly(ethylene terephthalate) fibers containing zinc chloride in the fiber bulk were prepared by solvent crazing. Fibers containing 6 g/Kg and 13 g/Kg Zn²⁺ were investigated. SEM‐EDX analyses and the formation of the pink bis(1,5‐dithiocarbazonato‐N,S) complex inside the fibers confirm the presence of zinc. UV‐Vis spectroscopy indicates a slow release of zinc ions into the aqueous media and, thus, the fibers serve as a release system to inhibit the growth of Escherichia coli during the first exposure. Thermal annealing of the freshly prepared fibers above T_g was shown to modify the release profile so that bacterial growth was also inhibited during repetitive and prolonged exposures. The washing fastness is fair and after 10 washing cycles, ～ 30% of the original zinc content still remains in the fiber. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Surface modification of UHMWPE fibers by means of polyethylene wax grafted maleic anhydride treatment

A novel surface modification method for ultrahigh molecular weight polyethylene (UHMWPE) fibers to improve the adhesion with epoxy matrix was demonstrated. Polyethylene wax grafted maleic anhydride (PEW‐g‐MAH) was deposited on the UHMWPE fibers surface by coating method. The changes of surface chemical composition, crystalline structure, mechanical properties of fiber and composite, wettability, surface topography of fibers and adhesion between fiber and epoxy resin before and after finishing were studied, respectively. The Fourier transform infrared spectroscopy spectra proved that some polar groups (MAH) were introduced onto the fiber surface after finishing. The X‐ray diffraction spectra indicated that crystallinity of the fiber was the same before and after finishing. Tensile testing results showed that mechanical properties of the fiber did not change significantly and the tensile strength of 9 wt % PEW‐g‐MAH treated fiber reinforced composite showed about 10.75% enhancement. The water contact angle of the fibers decreased after finishing. A single‐fiber pull out test was applied to evaluate the adhesion of UHMWPE fibers with the epoxy matrix. After treatment with 9 wt % PEW‐g‐MAH, a pull‐out force of 1.304 MPa which is 53.59% higher than that of pristine UNMWPE fibers was achieved. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46555.     

Properties of poly(ethylene terephthalate) containing epoxy‐functionalized polyhedral oligomeric silsesquioxane

Poly(ethylene terephthalate) (PET) containing epoxy‐functionalized polyhedral oligomeric silsesquioxane (POSS) was prepared by melt‐mixing and in situ polymerization methods. The melt‐mixed composite showed phase separation while the in situ polymerized composite did not, based on SEM characterization. During melt mixing, the reaction between the epoxy groups of POSS and hydroxyl groups of PET occurred, based on DSC results. DSC results on the in situ polymerization product showed formation of a lower‐melting component compared with PET. The tensile strength and modulus of the melt‐mixed composite fiber decreased compared with those properties of PET, whereas those of the in situ polymerized composite showed slightly higher values than PET despite the relatively small amounts (1 wt%) of POSS used. Dynamic mechanical analysis results showed an increase in storage modulus for the in situ polymerized composite of POSS and PET compared with PET over the temperature range of 40 °C to 140 °C. Copyright © 2004 Society of Chemical Industry     

Carbon fiber reinforced melamine‐formaldehyde

New composites based on carbon fiber (cf) and melamine‐formaldehyde (MF) are presented. Composites were manufactured by pressing stacked planar random veils (webs) or unidirectionally (UD) arranged fibers, and MF impregnated thin cellulose sheets. Non‐vented pressing for 60 s was used. Also, planar random, UD and bidirectional fiber composites with or without alumina trihydrate (ATH) were manufactured by conventional compression molding using much longer times (up to 20 min). Tensile strength of about 500 MPa and stiffness of 60 GPa was obtained for the UD composite containing 23 vol% fiber, and no ATH. Practically the same strength was measured for the bidirectional composite containing 46 vol% fiber and no ATH. Tensile strength and modulus of 130 MPa and 28 GPa, respectively, was obtained for the random fiber composite containing 16 vol% fiber. Measurements showed that replacement of ATH with cellulose in a composite containing 6 vol% carbon fibers increased the strength (2.5 times) without any penalty on stiffness, and increased strain at break. Cf‐MF interfacial strength is low. This was estimated for clean fibers by means of transverse tensile testing and in‐situ scanning electron microscopy (SEM), and for fibers with an epoxy compatible coating by using the interlaminar shear strength (ILSS) test. The cf/MF/cellulose composite performed well up to 200°C. Within this temperature range it retained 80% of its stiffness compared to about 60% in the case of a representative epoxy with a higher content of carbon fibers.     

Preparation and characterization of chemically modified Jute–Coir hybrid fiber reinforced epoxy novolac composites

In this study, the effects of fiber surface modification and hybrid fiber composition on the properties of the composites is presented. Jute fibers are cellulose rich (>65%) modified by alkali treatment, while the lignin rich (>40%) coconut coir fibers consist in creating quinones by oxidation with sodium chlorite in the lignin portions of fiber and react them with furfuryl alcohol (FA) to create a coating around the fiber more compatible with the epoxy resins used to prepare polymer composites. The maximum improvement on the properties was achieved for the hybrid composite containing the jute–coir content of 50 : 50. The tensile and flexural strength are recorded as 25 and 63 MPa at modified coir fiber content of 50 vol %, respectively, which are 78% and 61% higher than those obtained for unmodified fiber reinforced composites, i.e., tensile and flexural strength are 14 and 39 MPa, respectively. The reinforcement of the modified fiber was significantly enhanced the thermal stability of the composites. SEM features correlated satisfactorily with the mechanical properties of modified fiber reinforced hybrid composites. SEM analysis and water absorption measurements have confirmed the FA-grafting and shown a better compatibility at the interface between chemically modified fiber bundles and epoxy novolac resin. Hailwood–Horrobin model was used to predict the moisture sorption behavior of the hybrid composite systems. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and EMI shielding properties of nickel‐coated PET fiber filled epoxy composites

Electrically conductive composites were prepared using epoxy resin (EP) as matrix and nickel‐coated polyethylene teraphthalate (PET) fibers as filler. The fibers were coated with nickel by plating and ultrasonic electroless deposition techniques. The coaxial transmission line method was used to measure the electromagnetic interference (EMI) shielding effectiveness of the nickel‐coated PET fiber/EP composites. The contents of nickel and phosphorus in the coating were determined by X‐ray photoelectron spectroscopy (XPS). As a result, the ultrasonic electroless nickel‐coated PET fiber/EP composites showed excellent electrical conductive capability and better EMI shielding effectiveness due to higher content of nickel and lower content of phosphorus in the coating than conventional plated nickel‐coated PET fiber/EP composites. POLYM. COMPOS., 27:24–29, 2006. © 2005 Society of Plastics Engineers     

Surface modification and physical properties of various UHMWPE‐fiber‐reinforced modified epoxy composites

Two surface modification methods—plasma surface treatment and chemical agent treatment—were used to investigate their effects on the surface properties of ultrahigh‐molecular‐weight polyethylene (UHMWPE) fibers. In the analyses, performed using electron spectroscopy for chemical analysis, changes in weight, and scanning electron microscope observations, demonstrated that the two fiber‐surface‐modified composites formed between UHMWPE fiber and epoxy matrix exhibited improved interfacial adhesion and slight improvements in tensile strengths, but notable decreases in elongation, relative to those properties of the composites reinforced with the untreated UHMWPE fibers. In addition, three kinds of epoxy resins—neat DGEBA, polyurethane‐crosslinked DGEBA, and BHHBP‐DGEBA—were used as resin matrices to examine the tensile and elongation properties of their UHMWPE fiber‐reinforced composites. From stress/strain measurements and scanning electron microscope observations, the resin matrix improved the tensile strength apparently, but did not affect the elongation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 655–665, 2007