Effects of Nylon 6,6 nanofibrous mats on thermal properties and delamination behavior of high performance CFRP laminates

Nylon 6,6 electrospun nanofibrous membranes interleaved in “high performance” Carbon Fiber Reinforced Polymer (CFRP) laminates have been proposed as a means to provide a high threshold value to delamination on structural sites where composites are more prone to develop such failure. A model, highly crosslinked, thus inherently brittle, epoxy matrix was selected for its high Young's modulus and glass transition temperature exceeding 250°C. The influence of the Nylon 6,6 nanofibers on the curing behavior of the matrix and on the thermal and dynamic mechanical properties of the cured resin was investigated. These properties were related to the features of the epoxy resin and of the resin impregnated nanofibrous mat. Finally, the delamination behavior of the composite laminates interleaved with Nylon interleaves with different thicknesses was studied through Mode I delamination tests on Double Cantilever Beam (DCB) samples. The results show that the initial Mode I fracture toughness was increased up to about 50% by the presence of the thin mat interleaf. POLYM. COMPOS., 36:1303–1313, 2015. © 2014 Society of Plastics Engineers     

Delamination toughness of fiber-reinforced composites containing a carbon nanotube/polyamide-12 epoxy thin film interlayer

We present a simple, out-of-autoclave approach to improve the delamination toughness of fiber-reinforced composites using epoxy interlayers containing 20 wt.% polyamide-12 (PA) particles and 1 wt.% multi-walled carbon nanotubes (MWCNTs). Composites were prepared by integrating partially cured thin films at the laminate mid-plane using vacuum-assisted resin transfer molding. The introduction of epoxy/PA interlayers increased fracture toughness due to the ductile deformation and crack bridging of PA particles within an interlaminar damage zone with uniform thickness of about 20 μm. Composites interlayered with epoxy/PA/MWCNT exhibited nearly 2.5 and 1.5 times higher fracture toughness than composites containing neat epoxy and epoxy/PA interlayers, respectively, without an observable increase in interlaminar thickness. The fracture surface was analyzed to identify failure modes responsible for the fracture toughness improvement. The MWCNTs are proposed to inhibit critical loading of defects by minimizing stress concentration within the interlaminar region, thereby enabling greater deformation of the PA particles during fracture.     

Interlaminar fracture toughness of woven fabric composite laminates with carbon nanotube/epoxy interleaf films

The Mode I interlaminar fracture behavior of woven carbon fiber/epoxy composite laminates incorporating partially cured carbon nanotube/epoxy composite films has been investigated. Laminates with films containing carbon nanotubes (CNTs) in the as‐received state and functionalized with polyamidoamine were evaluated, as well as laminates with neat epoxy films. Double‐cantilever beam (DCB) specimens were used to measure G_Ic, the critical strain energy release rate (fracture toughness) versus crack length. Post‐fracture microscopic inspection of the fracture surfaces was performed. Results show that initial fracture toughness was improved with the amino‐functionalized CNT/epoxy interleaf films, but the important factor appears to be the polyamidoamine functionalization, not the CNTs. The initial fracture toughness remained relatively unaffected with the incorporation of neat epoxy and as‐received CNT/epoxy interleaf films. Plateau fracture toughness was unchanged with the use of functionalized CNT/epoxy interleaf films, and was reduced with the use of neat epoxy and as‐received CNT/epoxy interleaf films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effects of molecular weight and polymorphism on the fracture and thermo-mechanical properties of a carbon-fibre composite modified by electrospun poly (vinylidene fluoride) membranes

The interlaminar toughening of a carbon-fibre reinforced composite by incorporation of electrospun polyvinylidene fluoride (PVDF) nanofibrous membranes was explored in this work. The electrospinning process of low and high molecular weight PVDF was optimised to form nanofibres free of defects with diameters averaging several hundred nanometres. The nanofibres were electrospun directly onto commercial pre-impregnated carbon fibre materials and under these optimised conditions, PVDF primarily crystallised in its β phase polymorphic form but significant variations were observed between samples. There is strong evidence from DMTA analysis to suggest that a partial miscibility between the amorphous phases of the PVDF nanofibres and the epoxy exists. The improved plastic deformation at the crack tip after inclusion of the nanofibres was directly translated to a 57% increase in the mode II interlaminar fracture toughness (in-plane shear failure). Conversely, the fracture toughness in mode I (opening failure) was slightly lower than the reference by approximately 20%, and the results were interpreted from the complex micromechanisms of failure arising from the changes in polymorphism and molecular weight of the PVDF.     

Enhancement of interlaminar fracture toughness of carbon fiber–epoxy composites using polyamide‐6,6 electrospun nanofibers

In this study, carbon fiber–epoxy composites are interleaved with electrospun polyamide‐6,6 (PA 66) nanofibers to improve their Mode‐I fracture toughness. These nanofibers are directly deposited onto carbon fabrics before composite manufacturing via vacuum infusion. Three‐point bending, tensile, compression, interlaminar shear strength, Charpy impact, and double cantilever beam tests are performed on the reference and PA 66 interleaved specimens to evaluate the effects of PA 66 nanofibers on the mechanical properties of composites. To investigate the effect of nanofiber areal weight density (AWD), nanointerlayers with various AWD are prepared by changing the electrospinning duration. It is found that the electrospun PA 66 nanofibers are very effective in improving Mode‐I toughness and impact resistance, compressive strength, flexural modulus, and strength of the composites. However, these nanofibers cause a decrease in the tensile strength of the composites. The glass‐transition temperature of the composites is not affected by the addition of PA 66 nanofibers. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45244.     

Effects of carbon nanofiller functionalization and distribution on interlaminar fracture toughness of multi-scale reinforced polymer composites

Carbon nanofillers with different surface functional groups and aspect ratios, including carboxyl carbon nanotubes, un-functionalized carbon nanofibers (CNFs), glycidyloxypropyl-trimethoxysilane carbon nanotubes (GPS-CNTs) and nanofibers were evaluated for their potential for increasing the interlaminar fracture toughness of an S2-glass fiber/epoxy composite. The fillers were added in the matrix of the fiber reinforced plies, in the resin interlayer between plies, or in both regions. Comparisons were made based on mode I and mode II interlaminar fracture toughness. For composites made with CNTs dispersed in the matrix, fracture toughness was largely unaffected except for a slight increase seen with long GPS-CNTs. However, adding a CNF or CNT modified resin interlayer significantly increased the fracture toughness, with the highest improvement over the baseline material achieved by adding long GPS-CNTs in the interlayer (79% and 91% for mode I and mode II onset toughness, respectively). Important material parameters identified for improving interlaminar fracture toughness are the nanofiller aspect ratio and concentration at the fracture plane. Based on microscopic evaluations of the fracture surfaces, a high density of high aspect ratio nanofillers causes the best entanglement between the filler and glass fibers and effectively obstructs interlaminar crack propagation.     

Mode II interlaminar fracture behavior of carbon bead‐filled epoxy/glass fiber hybrid composite

To investigate the effect of including carbon beads on the mechanical properties of epoxy resin, the fracture toughness of carbon bead‐filled epoxy was earlier evaluated using a CT (compact tension) specimens and Mode I fracture toughness was observed. Based on those results, in this study, the Mode II interlaminar fracture toughness of carbon bead filled epoxy/glass fiber hybrid composites was evaluated using end notch flexure (ENF) specimens. The hybrid composites showed increased Mode II interlaminar fracture toughness. The optimal bead volume fraction was around 15%.     

Mechanical properties of carbon woven reinforced epoxy matrix composites. A study on the influence of matrix modification with polysulfone

An experimental investigation has been carried out to study the influence of thermoplastic addition on the mechanical properties of woven carbon fiber/epoxy matrix composites. As toughening agent bisphenol‐A polysulfone, PSu, has been added to the epoxy matrix. Flexural tests haved been performed to characterize the mechanical behavior of unmodified and PSu‐modified bulk tetra‐ and bifunctional epoxy matrices and also for the corresponding woven carbon fiber, CF, composite materials. Three‐point notched flexural tests been used to investigate the influence of polysulfone addition in the mode‐I fracture properties of the bulk epoxy matrices, relating them to their microstructural features investigated by atomic force microscopy (AFM). The double‐cantilever bea (DCB) and the end‐notched flexural (ENF) tests have been applied to characterize the interlaminar fracture toughness of the corresponding composites. For composites, the flexural properties were simmilar independent of the funcetionality of the epoxy matrix and of the thermoplastic content. Nevertheless, PSu addition to the epoxy matrix celarly enhanced the ode‐I and II interlaminar fracture toughness of the corresponding composites, the immprovement being higher for the composites manufactured with the bifunctional epoxy matrix at every thermoplastic content because of the lower crosslink density of the epoxy matrix.     

Interlaminar mechanical properties of carbon fiber reinforced plastic laminates modified with graphene oxide interleaf

By taking the advantage of the excellent mechanical properties and high specific surface area of graphene oxide (GO) sheets, we develop a simple and effective strategy to improve the interlaminar mechanical properties of carbon fiber reinforced plastic (CFRP) laminates. With the incorporation of graphene oxide reinforced epoxy interleaf into the interface of CFRP laminates, the Mode-I fracture toughness and resistance were greatly increased. The experimental results of double cantilever beam (DCB) tests demonstrated that, with 2 g/m² addition of GO, the Mode-I fracture toughness and resistance of the specimen increase by 170.8% and 108.0%, respectively, compared to those of the plain specimen. The improvement mechanisms were investigated by the observation of fracture surface with scanning electron microscopies. Moreover, finite element analyses were performed based on the cohesive zone model to verify the experimental fracture toughness and to predict the interfacial tensile strength of CFRP laminates.     

Enhancement of Interlaminar Fracture Toughness of Carbon Fiber/Epoxy Composites Using Silk Fibroin Electrospun Nanofibers

In this article, the effect of silk fibroin nanofibers as a toughening agent of carbon fiber/fabric-reinforced epoxy composites is experimentally investigated. The composites showed up to 30% improvement in Mode II fracture toughness at 0.1 wt% of silk fibroin nanofibers content. The scanning electron microscopy observation revealed that the fracture surface of silk fibroin nanofibers modified carbon fiber/fabric-reinforced epoxy composites appearance of the broken fiber and the ductile-like matrix cracks showed a good adhesion between matrix resin and carbon fibers, which are reasons for the enhanced mode II interlaminar fracture toughness.     

The effect of silicon carbide whiskers on the Mode I interlaminar fracture of carbon fiber composites

This paper reports on the Mode I interlaminar fracture toughness improvement of carbon fiber-epoxy composites as a result of incorporating SiC whiskers in the epoxy matrix. Five laminates of unidirectional carbon fiber-epoxy composites at different weight fractions of SiC whiskers were manufactured using hand layup vacuum bagging process. Optical and scanning electron microscopic analysis were conducted to give an insight into the fracture morphogoloy, failure mechanisms, and the energy dissipation mechanisms created by the presence of the whiskers in the composite. Experimental results showed that composites containing 5 wt% whiskers exhibited 67% increase in the crack initiation interlaminar fracture toughness G_IC, whereas it exhibited 55% increase in the maximum G_IC compared to pristine composite. The optical and SEM fractographs revealed a strong relation between the microstructure of the fractured surfaces and the energy release rate trend of the composites.     

The effect of silica nanoparticles and carbon nanotubes on the toughness of a thermosetting epoxy polymer

Silica nanoparticles and multiwalled carbon nanotubes (MWCNTs) have been incorporated into an anhydride‐cured epoxy resin to form “hybrid” nanocomposites. A good dispersion of the silica nanoparticles was found to occur, even at relatively high concentrations of the nanoparticles. However, in contrast, the MWCNTs were not so well dispersed but relatively agglomerated. The glass transition temperature of the epoxy polymer was 145°C and was not significantly affected by the addition of the silica nanoparticles or the MWCNTs. The Young's modulus was increased by the addition of the silica nanoparticles, but the addition of up to 0.18 wt % MWCNTs had no further significant effect. The addition of both MWCNTs and silica nanoparticles led to a significant improvement in the fracture toughness of these polymeric nanocomposites. For example, the fracture toughness was increased from 0.69 MPam^1/2 for the unmodified epoxy polymer to 1.03 MPam^1/2 for the hybrid nanocomposite containing both 0.18 wt % MWCNTs and 6.0 wt % silica nanoparticles; the fracture energy was also increased from 133 to 204 J/m². The mechanisms responsible for the enhancements in the measured toughness were identified by observing the fracture surfaces using field‐emission gun scanning electron microscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Imidazole and chromium acetylacetonate as additives for the cure and fracture toughness of epoxy resins and their composites

The effects of additives such as 2-undecyl-imidazole (C₁₁Z) and chromium acetylacetonate (Cr(acac)₃) were examined on the curing behavior and fracture toughness of tetraglycidyldiaminodiphenyl methane/diaminodiphenyl sulphone (TGDDM/DDS) epoxy resins and their composites. The C₁₁Z additive alone reacted with TGDDM epoxy resins at about 127°C and increased the resin viscosity, resulting in an acceptable resin content for composite processing. Further addition of Cr(acac)₃ to TGDDM/DDS/C₁₁Z formulation increased the fracture toughness 5.7 times compared to the typical TGDDM/DDS/BF₃MEA epoxy formulation used for the preparation of laminates. The interlaminar fracture toughness of the laminates prepared by TGDDM/DDS/C₁₁Z/Cr(acac)₃ formulation was only twice as much as that prepared by typical TGDDM/DDS/BF₃MEA. This was due to the fiber bridging contribution to the interlaminar fracture toughness. Based on the experiment, this fiber bridging contribution was only dependent on the fiber content. Thus, the interlaminar fracture toughness is approximated by the sum of the fracture toughness of epoxy matrix and the estimated fiber bridging contribution.     

Preparation and properties of environmental friendly nonhalogen flame retardant melamine cyanurate/nylon 66 composites

Melamine cyanurate (MCA) was utilized as an environmental friendly additive to prepare the nonhalogen flame retardant MCA/Nylon 66 composites by melt blending technique. Because of the strong hydrogen bond interactions and fine interfacial compatibility between MCA and Nylon 66, the resultant even dispersion of MCA filler in polymer matrix leads to the better toughness and strength of MCA/Nylon 66 composites than those of neat Nylon 66. Both Nylon 66 and MCA/Nylon 66 composites exhibit similar α‐crystalline structure, but the presence of MCA influences the distribution of α1 and α2 crystalline phases in Nylon 66 by inducing its hydrogen‐bonded sheet separation. Moreover, the blending of MCA and Nylon 66 increases the crystallization temperature and exothermicity but decreases the thermal stability of Nylon 66 and accelerates the degradation of MCA. The MCA/Nylon 66 composites show better flame retardancy at intermediate MCA contents of 10 and 15 wt %. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface morphology,thermomechanical and barrier properties of poly(ether sulfone)‐toughened epoxy clay ternary nanocomposites

Poly(ether sulfone) (PES)‐toughened epoxy clay ternary nanocomposites were prepared by melt blending of PES with diglycidyl ether of bisphenol A epoxy resin along with Cloisite 30B followed by curing with 4,4′‐diaminodiphenylsulfone. The effect of organoclay and thermoplastic on the fracture toughness, permeability, viscoelasticity and thermomechanical properties of the epoxy system was investigated. A significant improvement in fracture toughness and modulus with reduced coefficient of thermal expansion (CTE) and gas permeability were observed with the addition of thermoplastic and clay to the epoxy system. Scanning electron microscopy of fracture‐failed specimens revealed crack path deflection and ductile fracture without phase separation. Oxygen gas permeability was reduced by 57% and fracture toughness was increased by 66% with the incorporation of 5 phr clay and 5 phr thermoplastic into the epoxy system. Optical transparency was retained even with high clay content. The addition of thermoplastic and organoclay to the epoxy system had a synergic effect on fracture toughness, modulus, CTE and barrier properties. Planetary ball‐milled samples gave exfoliated morphology with better thermomechanical properties compared to ultrasonicated samples with intercalated morphology. Copyright © 2010 Society of Chemical Industry     

Mode II interlaminar delamination of composite laminates incorporating with polymer ultrathin fibers

This study makes use of electrospinning to produce epoxy polymer ultrathin fibers. Those fibers were collected as nonwoven sheets with various thicknesses. The collected ultrathin fibrous sheets (UFS) were incorporated into ply interfaces of a glass/epoxy composite laminate. End‐notch flexure (ENF) specimens were employed to measure the mode II interlaminar fracture toughness (G_IIC) of the resulting laminate. Scanning electron microscopy (SEM) was carried out to investigate the fracture surface and fracture mechanism of tested samples. Results indicate that there were some reinforcing effects of the UFS on the G_IIC when the thickness of the sheets was not more than 0.13 mm for a single sheet and 0.06 mm for multi‐sheets incorporated. The mechanical properties were quickly decreased and became poorer when a higher thickness of the sheets was used. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Experimental investigation on the enhancement of Mode I fracture toughness of adhesive bonded joints by electrospun nanofibers

ABSTRACT

The use of an electrospun nylon nanofibrous mat at the interface between adjacent plies of a composite laminate is a promising mean to improve the delamination strength, as the nanomat acts a reinforcing web enabling a ply-to-ply bridging. This kind of reinforcement can be potentially used in other applications, such as adhesive bonding, where it may also work as adhesive carrier. The present work is therefore aimed at analysing the potential of an electrospun polymeric nanomat as adhesive carrier and reinforcing web in adhesive bonding. The adhesive is used to pre-impregnate a nylon nanofibrous mat that is then placed at the interface between two metal pieces and cured. The effectiveness of this procedure is evaluated by comparing of the mode-I fracture toughness measured 2024-T3 aluminum alloy DCB (Double Cantilever Beam) specimen bonded using a two-part epoxy resin with and without the nanomat.     

Mechanical characterization of woven carbon fiber composites with poly(methyl methacrylate)–modified epoxy matrices

The influence of the modification of epoxy matrices with poly(methyl methacrylate) (PMMA) on the fracture behavior of composite laminates based on woven carbon fibers has been investigated. Three‐point flexural, short beam shear (SBS) and end‐notched flexural tests (ENF) have been carried out. Microstructural features have been investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). Dynamic mechanical thermal analysis of the different epoxy matrices and their corresponding composites shows the power of this technique for microstructural studies. Fracture behavior is compared with that shown by similar bifunctional (DGEBA) epoxy matrix composites. In spite of the two‐phase structure obtained in tetrafunctional (TGDDM) epoxy matrix‐based systems for all PMMA contents, only a small improvement in fracture toughness and interlaminar shear strength properties was obtained. In contrast, for DGEBA bulk matrices and composites, a higher enhancement of fracture toughness was obtained, as a consequence of the lower crosslink densities of bifunctional matrices.     

Electrophoretic deposition of carbon nanotubes onto carbon-fiber fabric for production of carbon/epoxy composites with improved mechanical properties

Carbon nanotubes (CNTs) have been deposited onto carbon-fiber fabric using electrophoretic deposition (EPD) prior to the infusion of epoxy resin for the production of carbon/epoxy composites. The carbon-fiber fabric employed for EPD was used in the as-received condition, in which the proprietary epoxy sizing-agent was present. CNTs were functionalized prior to EPD using ozone treatment for oxidation, followed by chemical reaction with polyethyleneimine. The CNT oxidation used a novel recirculating system which enabled ozonolysis to be conducted on large-volume solutions of CNTs in the presence of high-powered sonication, facilitating preparation of stable dispersions suitable for EPD. Significant increases in the shear strength and fracture toughness of the carbon/epoxy composites with the CNT treatment have been measured relative to composites without the CNT treatment. Analysis of fracture surfaces revealed interlaminar regions with high levels of CNTs and evidence of good adhesion between the carbon nanotubes and sized carbon-fiber, which is believed to have contributed to the measured improvement in mechanical properties.     

Fracture and toughening behavior of aramid fiber/epoxy composites

The effect of short Aramid fibers on the fracture and toughening behavior of epoxy with high glass transition temperature has been studied. Fine dispersion of the fibers throughout the matrix is evidenced by optical microscopy. Compared with neat epoxy resin, the fracture toughness (K_IC) of the composites steadily increases with increasing fiber loading, indicating that addition of Aramid fibers has an effective toughening effect to the intrinsically brittle epoxy matrix. Scanning electron microscopy (SEM) indicates that formation of numerous step structures for fiber‐filled epoxy systems is responsible for the significant toughness improvement. SEM and transmitted optical microscopy show that fiber pullout and fiber breakage are the main toughening mechanisms for the Aramid fiber/epoxy composites. POLYM. COMPOS. 26:333–342, 2005. © 2005 Society of Plastics Engineers.