Improvements in mechanical properties of a carbon fiber epoxy composite using nanotube science and technology

Carbon fiber reinforced epoxy composite laminates, with strategically incorporated fluorine functionalized carbon nanotubes (f-CNTs) at 0.2, 0.3 and 0.5 weight percent (wt.%), are studied for improvements in tensile strength and stiffness and durability under both tension–tension (R = +0.1) and tension–compression (R = −0.1) cyclic loadings, and then compared to the neat (0.0 wt.% CNTs) composite laminate material. To develop the nanocomposite laminates, a spraying technology was used to deposit nanotubes on both sides of each four-harness satin weave carbon fiber fabric piece for the 12 ply laminate lay up. For these experimental studies the carbon fiber reinforced epoxy laminates were fabricated using a heated vacuum assisted resin transfer molding (H-VARTM®) method followed by a 2 soak curing cycle. The f-CNTs toughened the epoxy resin-fiber interfaces to mitigate the evolution of fiber/fabric-matrix interfacial cracking and delamination under both static and cyclic loadings. As a consequence, significant improvements in the mechanical properties of tensile strength, stiffness and resistance to failure due to cyclic loadings resulted for this carbon fiber reinforced epoxy composite laminate.     

Hybrid nanoreinforced carbon/epoxy composites for enhanced damage tolerance and fatigue life

Hybrid nano/microcomposites with a nanoparticle reinforced matrix were developed, manufactured, and tested showing significant enhancements in damage tolerance properties. A woven carbon fiber reinforced polymer composite, with the polymer (epoxy) matrix reinforced with well dispersed carbon nanotubes, was produced using dispersant-and-sonication based methods and a wet lay-up process. Various interlaminar damage tolerance properties of this composite, including static strength, fracture toughness, fatigue life, and crack growth rates were examined experimentally and compared with similarly-processed reference material produced without nanoreinforcement. Significant improvements were obtained in interlaminar shear strength (20%), fracture toughness (180%), shear fatigue life (order of magnitude), and fatigue crack growth rate (factor of 2). Observations by scanning electron microscopy of failed specimens showed significant differences in fracture surface morphology between the two materials, related to the differences in properties and providing context for understanding of the enhancement mechanisms.     

Probing deformation of double-walled carbon nanotube (DWNT)/epoxy composites using FTIR and Raman techniques

Two of the limitations of carbon nanotube (CNT) polymer composites have been the low volume fraction of nanotubes and inadequate load transfer from the polymer to the stiff CNT. Here, we have utilized functionalized mats of double-walled nanotubes (DWNT) to obtain 10 wt.% DWNT in an epoxy matrix, with strength approaching those of quasi-isotropic carbon fiber composites. We used the transmission FTIR technique with in situ loaded specimens to monitor spectral shift per unit applied stress for understanding load transfer behavior at the nanotube–epoxy interface. Tests show that in most cases a tensile stress causes negative FTIR peak shift in the neat epoxy, but this behavior is not always observed for the epoxy matrix in the composite. The FTIR data can be used successfully to estimate the average matrix stress in the composite and thereby the average stress in the nanotubes. In situ Raman studies using the G′ peak are also conducted to obtain complementary information on average tensile stress in the DWNT in the loading direction. The shift response is found to be ∼37 cm⁻¹/GPa.     

The tensile fatigue behaviour of a silica nanoparticle-modified glass fibre reinforced epoxy composite

An anhydride-cured thermosetting epoxy polymer was modified by incorporating 10 wt.% of well-dispersed silica nanoparticles. The stress-controlled tensile fatigue behaviour at a stress ratio of R = 0.1 was investigated for bulk specimens of the neat and the nanoparticle-modified epoxy. The addition of the silica nanoparticles increased the fatigue life by about three to four times. The neat and the nanoparticle-modified epoxy resins were used to fabricate glass fibre reinforced plastic (GFRP) composite laminates by resin infusion under flexible tooling (RIFT) technique. Tensile fatigue tests were performed on these composites, during which the matrix cracking and stiffness degradation was monitored. The fatigue life of the GFRP composite was increased by about three to four times due to the silica nanoparticles. Suppressed matrix cracking and reduced crack propagation rate in the nanoparticle-modified matrix were observed to contribute towards the enhanced fatigue life of the GFRP composite employing silica nanoparticle-modified epoxy matrix.     

Reinforcing epoxy nanocomposites with functionalized carbon nanotubes via biotin–streptavidin interactions

We report on the preparation of nanocomposites consisting of biofunctionalized single-walled carbon nanotubes (BF-SWCNTs) reinforcing an ultraviolet curable epoxy polymer by means of biotin–streptavidin interactions. The as-produced laser ablation SWCNTs are biofunctionalized via acid oxidization based purification process and non-covalent functionalization using surfactant, followed by grafting the resulting nanotubes with biomolecules. The biotin-grafted nanotubes are capable of interacting with epoxy groups in presence of streptavidin molecules by which chemical bridges between BF-SWCNTs and epoxy matrix are formed. The biomolecules grafted to the nanotubes surface not only facilitate the load transfer, but also improve the nanotube dispersion into the epoxy matrix, as observed by optical imaging and scanning electron microscopy. Mechanical characterization on the nanocomposite microfibers demonstrates considerable enhancement in both strength (by 76%) and modulus (by 93%) with the addition of only 1 wt.% of BF-SWCNTs. The electrical measurements reveal a clear change in electrical conductivity of nanocomposite microfibers reinforced with 1 wt.% of BF-SWCNTs in comparison to the microfibers containing solely purified carbon nanotubes. These multifunctional nanocomposite materials could be used to fabricate macro and microstructures for a wide variety of applications such as high strength polymer nanocomposite and potential easily-manipulated biosensors.     

Interfacial load transfer in carbon nanotube/ceramic microfiber hybrid polymer composites

Growing carbon nanotubes (CNTs) on the surface of fibers has the potential to modify fiber–matrix interfacial adhesion, enhance the composite delamination resistance, and possibly improve its toughness and any matrix-dominated elastic property as well. In the present work aligned CNTs were grown upon ceramic fibers (silica and alumina) by chemical vapor deposition (CVD) at temperatures of 650 °C and 750 °C. Continuously-monitored single fiber composite (SFC) fragmentation tests were performed on pristine as well as on CNT-grown fibers embedded in epoxy. The critical fragment length, fiber tensile strength at critical length, and interfacial shear strength were evaluated. Significant increases (up to 50%) are observed in the fiber tensile strength and in the interfacial adhesion (which was sometimes doubled) with all fiber types upon which CNTs are CVD-grown at 750 °C. We discuss the likely sources of these improvements as well as their implications.     

Carbon nanofibers enhance the fracture toughness and fatigue performance of a structural epoxy system

This study investigates the monotonic and dynamic fracture characteristics of a discontinuous fiber reinforced polymer matrix. Specifically, small amounts (0-1 wt.%) of a helical-ribbon carbon nanofiber (CNF) were added to an amine cured epoxy system. The resulting nanocomposites were tested to failure in two modes of testing; Mode I fracture toughness and constant amplitude of stress tension-tension fatigue. Fracture toughness testing revealed that adding 0.5 and 1.0 wt.% CNFs to the epoxy matrix enhanced the resistance to fracture by 66% and 78%, respectively. Fatigue testing at 20 MPa peak stress showed a median increase in fatigue life of 180% and 365% over the control by the addition of 0.5 and 1.0 wt.% CNF, respectively. These results clearly demonstrate the addition of small weight fractions of CNFs to significantly enhance the monotonic fracture behavior and long-term fatigue performance of this polymer. A discussion is presented linking the two behaviors indicating their interdependence and reliance upon the stress intensity factor, K.     

Dynamic compressive behavior of unidirectional IM7/5250-4 laminate after thermal oxidation

Fiber reinforced high temperature polymer matrix composites are currently gaining wide usage in aircraft structures, especially in airframe and engine inlet casing. The failure of composites in worst-case operational conditions mandates the extensive investigation of the mechanical behavior, and the durability in long-term performance and service life under thermal oxidation. In this work, unidirectional IM7 carbon fiber reinforced high-temperature BMI resin composite (IM7/5250-4) were isothermally aged in air for 2 months at 195 °C and 245 °C, respectively. The dynamic behavior of thermally aged composites was investigated on a split Hopkinson pressure bar (SHPB) in three principal directions. The results indicate that thermal oxidation leads to significant reduction in both stiffness and strength of the composites. Optical micrographs of fracture surface and failure pattern of composite after SHPB impact reveals oxidation induced debonding along the fiber–matrix interface due to oxygen diffusion under long-term exposure to elevated temperatures.     

Fatigue life evaluation for carbon/epoxy laminate composites under constant and variable block loading

This paper presents the results of current research on the fatigue life prediction of carbon/epoxy laminate composites involving twelve balanced woven bidirectional layers of carbon fibres and epoxy resin manufactured by a vacuum moulding method. The plates were produced with 3 mm thickness and 0.66 fibre weight fraction. The dog bone shape specimens were cut from these plates with the load line aligned with one of the fibre directions. The fatigue tests were performed using load control with a frequency of 10 Hz and at room temperature. The fatigue behaviour was studied for different stress ratios and for variable amplitude block loadings. The damage process was monitored in terms of the stiffness loss. The fatigue life of specimens submitted to block loading tests was modelled using Palmgren–Miner’s law and taking in to account the stress ratio effect. The estimated and experimental fatigue lives were compared and good agreement was observed.     

Enhancement of mechanical performance of epoxy/carbon fiber laminate composites using single-walled carbon nanotubes

Carbon nanotubes (CNT) in their various forms have great potential for use in the development of multifunctional multiscale laminated composites due to their unique geometry and properties. Recent advancements in the development of CNT hierarchical composites have mostly focused on multi-walled carbon nanotubes (MWCNT). In this work, single-walled carbon nanotubes (SWCNT) were used to develop nano-modified carbon fiber/epoxy laminates. A functionalization technique based on reduced SWCNT was employed to improve dispersion and epoxy resin-nanotube interaction. A commercial prepregging unit was then used to impregnate unidirectional carbon fiber tape with a modified epoxy system containing 0.1 wt% functionalized SWCNT. Impact and compression-after-impact (CAI) tests, Mode I interlaminar fracture toughness and Mode II interlaminar fracture toughness tests were performed on laminates with and without SWCNT. It was found that incorporation of 0.1 wt% of SWCNT resulted in a 5% reduction of the area of impact damage, a 3.5% increase in CAI strength, a 13% increase in Mode I fracture toughness, and 28% increase in Mode II interlaminar fracture toughness. A comparison between the results of this work and literature results on MWCNT-modified laminated composites suggests that SWCNT, at similar loadings, are more effective in enhancing the mechanical performance of traditional laminated composites.     

Comparison of the thermal properties between composites reinforced by raw and amino-functionalized carbon materials

Carbon materials, such as graphite oxides, carbon nanotubes and graphenes, have exceptional thermal conductivity, which render them excellent candidates as fillers in advanced thermal interface materials for high density electronics. In this paper, these carbon materials were functionalized with 4,4′-diaminodiphenyl sulphone (DDS), to enhance the bonding between the carbon materials and the resin matrix. Their visibly different properties were investigated. It seems that DDS-functionalization can obviously improve the interfacial heat transfer between the carbon materials and the epoxy matrix. The thermal conductivity enhancement of D-Graphene composites (0.493 W/m K) was about 30% higher than that of D-MWNTs composites (0.387 W/m K) at 0.5 vol.% loading. The different effects among EGO, D-EGO, MWNTs, D-MWNTs and D-Graphene in polymer composites were also discussed. It was demonstrated that DDS-functionalized carbon materials had an obvious effect on the thermal performances of composite materials and were more effective in thermal conductivity enhancement.     

Improved mechanical properties of an epoxy glass–fiber composite reinforced with surface organomodified nanoclays

An organomodified surface nanoclay reinforced epoxy glass-fiber composite is evaluated for properties of mechanical strength, stiffness, ductility and fatigue life, and compared with the pristine or epoxy glass-fiber composite material not reinforced with nanoclays. The results from monotonic tensile tests of the nanoclay reinforced composite material at 60 °C in air showed an average 11.7% improvement in the ultimate tensile strength, 10.6% improvement in tensile modulus, and 10.5% improvement in tensile ductility vs. these mechanical properties obtained for the pristine material. From tension–tension fatigue tests at a stress-ratio = +0.9 and at 60 °C in air, the nanoclay reinforced composite had a 7.9% greater fatigue strength and a fatigue life over a decade longer or 1000% greater than the pristine composite when extrapolated to 10⁹ cycles or a simulated 10-year cyclic life. Electron microscopy and Raman spectroscopy of the fracture and failure modes of the test specimens were used to support the results and conclusions. This nanocomposite could be used as a new and improved material for repair or rehabilitation of external surface wall corrosion or physical damage on piping and vessels found in petrochemical process plants and facilities to extend their operational life.     

Role of matrix modification on interlaminar shear strength of glass fibre/epoxy composites

Interlaminar shear properties of fibre reinforced polymer composites are important in many structural applications. Matrix modification is an effective way to improve the composite interlaminar shear properties. In this paper, diglycidyl ether of bisphenol-F/diethyl toluene diamine system is used as the starting epoxy matrix. Multi-walled carbon nanotubes (MWCNTs) and reactive aliphatic diluent named n-butyl glycidyl ether (BGE) are employed to modify the epoxy matrix. Unmodified and modified epoxy resins are used for fabricating glass fibre reinforced composites by a hot-press process. The interlaminar shear strength (ILSS) of the glass fibre reinforced composites is investigated and the results indicate that introduction of MWCNT and BGE obviously enhances the ILSS. In particular, the simultaneous addition of 0.5 wt.% MWCNTs and 10 phr BGE leads to the 25.4% increase in the ILSS for the glass fibre reinforced composite. The fracture surfaces of the fibre reinforced composites are examined by scanning electron microscopy and the micrographs are employed to explain the ILSS results.     

Cryogenic mechanical behaviors of carbon nanotube reinforced composites based on modified epoxy by poly(ethersulfone)

Cryogenic mechanical properties are important parameters for epoxy resins used in cryogenic engineering areas. In this study, multi-walled carbon nanotubes (MWCNTs) were employed to reinforce diglycidyl ether of bisphenol F (DGBEF)/diethyl toluene diamine (DETD) epoxy system modified by poly(ethersulfone) (PES) for enhancing the cryogenic mechanical properties. The epoxy system was properly modified by PES in our previous work and the optimized formulation of the epoxy system was reinforced by MWCNTs in the present work. The results show that the tensile strength and Young’s modulus at 77 K were enhanced by 57.9% and 10.1%, respectively. The reported decrease in the previous work of the Young’s modulus of the modified epoxy system due to the introduction of flexible PES is offset by the increase of the modulus due to the introduction of MWCNTs. Meanwhile, the fracture toughness (K_IC) at 77 K was improved by about 13.5% compared to that of the PES modified epoxy matrix when the 0.5 wt.% MWCNT content was introduced. These interesting results imply that the simultaneous usage of PES and MWCNTs in a brittle epoxy resin is a promising approach for efficiently modifying and reinforcing epoxy resins for cryogenic engineering applications.     

Adhesive bonding of carbon fiber reinforced composite using UV-curing epoxy resin

Carbon fiber reinforced materials are widely used in a variety of products due to their stiffness, high strength and light weight. However, the strength of fiber reinforced composites will dramatically decrease when they have suffered damage from impact. Therefore, repair is necessary to maintain integrity. In many cases, speed of this repair is paramount. In this work, UV resins adhered to a damaged panel to form a hard patch are considered for fast repair. The challenge in using UV curing resins on carbon fiber reinforced materials is the non-UV transparency of the composite. In this work, a cationic UV epoxy resin is used due to its characteristic of dark polymerization after UV exposure. ASTM lap shear testing showed the shear stress was above 1000 psi. However, the large scale testing failed due to partial curing of adhesive before repair indicating that control in dosing and resin delivery is critical, yet problematic.     

Dynamic fracture of carbon nanotube/epoxy composites under high strain-rate loading

We investigate dynamic fracture of three types of multiwalled carbon nanotube (MWCNT)/epoxy composites and neat epoxy under high strain-rate loading (${10}^5''–''{10}^6$ s⁻¹). The composites include randomly dispersed, 1 wt%, functionalized and pristine CNT/epoxy composites, as well as laminated, ∼50 wt% CNT buckypaper/epoxy composites. The pristine and functionalized CNT composites demonstrate spall strength and fracture toughness slightly higher and lower than that of neat epoxy, respectively, and the spall strength of laminated CNT buckypaper/epoxy composites is considerably lower; both types of CNTs reduce the extent of damage. Pullout, sliding and immediate fracture modes are observed; the fracture mechanisms depend on the CNT–epoxy interface strength and fiber strength, and other microstructures such as the interface between CNT laminates. Compared to the functionalized CNT composites, weaker CNT–epoxy interface strength and higher fiber strength lead to a higher probability of sliding fracture and higher tensile strength in the pristine CNT composites at high strain rates. On the contrary, sliding fracture is more pronounced in the functionalized CNT composites under quasistatic loading, a manifestation of a loading-rate effect on fracture modes. Despite their helpful sliding fracture mode and large CNT content, the weak laminate–laminate interfaces play a detrimental role in fracture of the laminated CNT buckypaper/epoxy composites. Regardless of materials, increasing strain rates leads to pronounced rise in tensile strength and fracture toughness.     

Anisomorphic constant fatigue life diagrams for a woven fabric carbon/epoxy laminate at different temperatures

The effect of temperature on the constant fatigue life (CFL) diagram for a woven fabric carbon/epoxy quasi-isotropic laminate has been examined. Constant amplitude fatigue tests are first performed at different stress ratios on coupon specimens at room temperature (RT), 100 and 150 °C, respectively. The experimental results show that the CFL diagram for the woven CFRP laminate, which is plotted in the plane of mean and alternating stresses, becomes asymmetric about the alternating stress axis, regardless of test temperature, and shrinks as temperature increases. The CFL envelopes for given constant values of life are nonlinear over the range of fatigue cycles, regardless of test temperature, and they take peaks approximately at a particular stress ratio “critical stress ratio” that is given by the ratio of compressive strength to tensile strength. Then, the experimental CFL diagram for each temperature is compared with prediction using the anisomorphic CFL diagram approach that allows constructing the asymmetric and nonlinear CFL diagram for a given composite on the basis of the static strengths in tension and compression and the reference S-N relationship for the critical stress ratio. It is demonstrated that the anisomorphic CFL diagram approach can successfully be employed for predicting the CFL diagram and thus for predicting the S-N relationships for the woven CFRP laminate at any stress ratios, regardless of test temperature.     

CF/EP composite laminates with carbon black and copper chloride for improved electrical conductivity and interlaminar fracture toughness

An experimental study was conducted to improve the electrical conductivity of continuous carbon fibre/epoxy (CF/EP) composite laminate, with simultaneous improvement in mechanical performance, by incorporating nano-scale carbon black (CB) particles and copper chloride (CC) electrolyte into the epoxy matrix. CF/EP laminates of 65 vol.% of carbon fibres were manufactured using a vacuum-assisted resin infusion (VARI) technique. The effects of CB and the synergy of CB/CC on electrical resistivity, tensile strength and elastic modulus and fracture toughness (K_IC) of the epoxy matrix were experimentally characterised, as well as the transverse tensile modulus and strength, Mode I and Mode II interlaminar fracture toughness of the CF/EP laminates. The results showed that the addition of up to 3.0 wt.% CB in the epoxy matrix, with the assistance of CC, noticeably improved the electrical conductivity of the epoxy and the CF/EP laminates, with mechanical performance also enhanced to a certain extent.     

Influence of dry grinding in a ball mill on the length of multiwalled carbon nanotubes and their dispersion and percolation behaviour in melt mixed polycarbonate composites

Ball milling of carbon nanotubes (CNTs) in the dry state is a common way to produce tailored CNT materials for composite applications, especially to adjust nanotube lengths. For Nanocyl^TM NC7000 nanotube material before and after milling for 5 and 10 h the length distributions were quantified using TEM analysis, showing decreases of the mean length to 54% and 35%, respectively. With increasing ball milling time in addition a decrease of agglomerate size and an increase of packing density took place resulting in a worse dispersability in aqueous surfactant solutions. In melt mixed CNT/polycarbonate composites produced using masterbatch dilution step, the electrical properties, the nanotube length distribution after processing, and the nano- and macrodispersion of the nanotubes were studied. The slight increase in the electrical percolation threshold in the melt mixed composites with ball milling time of CNTs can be assigned to lower nanotube lengths as well as the worse dispersability of the ball milled nanotubes. After melt compounding, the mean CNT lengths were shortened to 31%, 50%, and 66% of the initial lengths of NC7000, NC7000-5 h, and NC7000-10 h, respectively.     

Mechanical properties of aligned multi-walled carbon nanotube/epoxy composites processed using a hot-melt prepreg method

This study examined the mechanical properties of aligned multi-walled carbon nanotube (CNT)/epoxy composites processed using a hot-melt prepreg method. Vertically aligned ultra-long CNT arrays (forest) were synthesized using chemical vapor deposition, and were converted to horizontally aligned CNT sheets by pulling them out. An aligned CNT/epoxy prepreg was fabricated using hot-melting with B-stage cured epoxy resin film. The resin content in prepreg was well controlled. The prepreg sheets showed good drapability and tackiness. Composite film specimens of 24-33 μm thickness were produced, and tensile tests were conducted to evaluate the mechanical properties. The resultant composites exhibit higher Young’s modulus and tensile strength than those of composites produced using conventional CNT/epoxy mixing methods. For example, the maximum elastic modulus and ultimate tensile strength (UTS) of a CNT (21.4 vol.%)/epoxy composite were 50.6 GPa and 183 MPa. These values were, respectively, 19 and 2.9 times those of the epoxy resin.