One-pot synthesis of aminated multi-walled carbon nanotube using thiol-ene click chemistry for improvement of epoxy nanocomposites properties

A non-oxidative method based on thiol-ene click chemistry for functionalization of multi-walled carbon nanotube (CNT) was performed in order to improve the interfacial interactions between epoxy matrix and CNT. In this way, the CNT was aminated using 2-aminoethanethiol hydrochloride radicals thermally produced by a peroxide radical initiator. The aminated CNT (CNT-NH2) was characterized by FTIR, TGA, and solubility evaluations, confirming that thiol radicals are successfully grafted onto the CNT surface with a proper yield. Various percentages of pure CNT (p-CNT) and CNT-NH2 were then incorporated into epoxy matrix to evaluate the effect of the functionalization of CNT on thermal, mechanical, and morphological properties. The nanocomposites were characterized by DMA, tensile testing, and TGA. Results showed that glass transition temperature, tensile properties and thermal stability of epoxy nanocomposites containing CNT-NH2 improves significantly compared to those containing unmodified CNT. These results prove the role of amino-functionalization in improving the interfacial adhesion between epoxy and CNT, which was further confirmed by morphological observations of fracture surfaces of the nanocomposites.

Improvement of coating durability, interfacial adhesion and compressive strength of UHMWPE fiber/epoxy composites through plasma pre-treatment and polypyrrole coating

Ultra-high-molecular-weight polyethylene (UHMWPE) fibers have exceptionally higher specific strength and stiffness compared with other high-performance fibers. However, the interfacial adhesion and compressive performance of UHMWPE fiber-reinforced polymer composites (FPCs) are extremely low. The challenges are to achieve load transfer at the interface between the fiber and matrix at a molecular level. Here, we show that plasma pre-treatment of UHMWPE fibers followed by coating with polypyrrole (PPy) results in an 848% improvement in the interfacial adhesion and 54% enhancement in compressive performance. This method takes advantage of a toughening mechanism observed in spider silk and collagen, which the hydrogen bond power the load transfer. The results showed that these improvements of interfacial adhesion and compressive strength were attributed to hydrogen-bonding interactions between the plasma pre-treated UHMWPE and PPy, which improves the fiber-matrix-fiber load transfer process. In addition, the hydrogen-bonded PPy coatings also endowed durability electrical conductivity properties of the UHMWPE fiber.

One-step amino-functionalization of milled carbon fibre for enhancement of thermo-physical properties of epoxy composites

Development of new chemical approaches for preparation of engineered carbon-based fillers is critical for high-performance applications. Herein, an efficient method for covalent functionalization of polyacrylonitrile-based carbon fibre through azo radical addition under mild condition is demonstrated. In this way, isobutyronitrile radicals in situ produced from thermal decomposition of 2,2′-azobisisobutyronitrile (AIBN), were covalently grafted on milled carbon fibre (MCF) surface, assisted by microwave irradiation, as evidenced by FTIR, Raman, and TGA analysis. The grafted isobutyronitriles on MCF surface (n-MCF) were applied for further MCF amino-functionalization (a-MCF) via nucleophilic reaction of an amine-rich compound. Then, both pure MCF and a-MCF were incorporated into epoxy matrix; and its curing process and thermo-physical properties were investigated using DSC, rheometry, DMA, TGA, and flexural analysis. The Tg and flexural strength of epoxy/a-MCF composites, compared to epoxy/MCF, increased by ∼3.5% and ∼10.2%, resulting from good adhesion between a-MCF and epoxy matrix which confirmed by SEM observations.

Rapidly cured epoxy/anhydride composites: effect of residual stress on laminate shear strength

The drive towards rapid cure thermosetting composites requires a better understanding of the residual stresses that develop during curing. This study investigates the impact of residual stresses on the interlaminar shear strength of resin-infused epoxy/anhydride carbon-fibre laminates. The magnitude of the residual stress was varied by changing the initial injection cure temperature between 75 °C and 145 °C. The corresponding cycle times and the final glass transition temperature of the resin were also measured. The experimentally measured chemical shrinkage and thermal expansion properties of the resin after vitrification were used as inputs to a finite element analysis to calculate the peak residual stresses in the composite. An increase in the initial cure temperature from 85 to 135 °C resulted in an increase of 25% in the residual stress, which led to an experimentally measured reduction in the composite's short beam shear strength of approximately 16% (8 MPa), in good agreement with model prediction.

An experimental study of low velocity impact response in 2/2 twill weave composite laminates manufactured by a novel fabrication process

A novel fabrication process for advanced composite components—the QuicktepTM process was described. 2/2 twill weave MTM56/CF0300 carbon epoxy composite laminates were manufactured by the Quickstep and the autoclave processes. The response of these laminates to drop-weight low velocity impact at energy levels ranging from 5 to 30 J was investigated. It was found that the laminates fabricated by the Quickstep had better impact damage tolerance than those fabricated by the autoclave. Optical microscopy revealed extensive matrix fracture in the center of the backside of the autoclave laminates indicating the more brittle property of the epoxy matrix cured by the autoclave process. Interfacial shear strength (IFSS) for two composite systems were measured by micro–debond experiments. The MTM56/CF0300 material cured by the Quickstep showed stronger fibre matrix adhesion. Since the thickness and density of the impact targets produced by two processes were different, finite element analysis (FEA) was performed to study the effect of these factors on the impact response. The simulation results showed that the difference in thickness and density affects the stress distribution under impact loading. Higher thickness and lower density caused by processing lead to less endurance to drop weight impact loading. Therefore the better performance of Quickstep laminates under impact loading was not due to the thickness and density change, but resulted from stronger mechanical properties.

Nanostructures, semicrystalline morphology, and nanoscale confinement effect on the crystallization kinetics in self-organized block copolymer/thermoset blends

This work reports the first instance of self-organized thermoset blends containing diblock copolymers with a crystallizable thermoset-immiscible block. Nanostructured thermoset blends of bisphenol A-type epoxy resin (ER) and a low-molecular-weight (Mn = 1400) amphiphilic polyethylene-block-poly(ethylene oxide) (EEO) symmetric diblock copolymer were prepared using 4,4'-methylenedianiline (MDA) as curing agent and were characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), and differential scanning calorimetry (DSC). All the MDA-cured ER/EEO blends do not show macroscopic phase separation but exhibit microstructures. The ER selectively mixes with the epoxy-miscible PEO block in the EEO diblock copolymer whereas the crystallizable PE blocks that are immiscible with ER form separate microdomains at nanoscales in the blends. The PE crystals with size on nanoscales are formed and restricted within the individual spherical micelles in the nanostructured ER/EEO blends with EEO content up to 30 wt %. The spherical micelles are highly aggregated in the blends containing 40 and 50 wt % EEO. The PE dentritic crystallites exist in the blend containing 50 wt % EEO whereas the blends with even higher EEO content are completely volume-filled with PE spherulites. The semicrystalline microphase-separated lamellae in the symmetric EEO diblock copolymer are swollen in the blend with decreasing EEO content, followed by a structural transition to aggregated spherical micellar phase morphology and, eventually, spherical micellar phase morphology at the lowest EEO contents. Three morphological regimes are identified, corresponding precisely to the three regimes of crystallization kinetics of the PE blocks. The nanoscale confinement effect on the crystallization kinetics in nanostructured thermoset blends is revealed for the first time. This new phenomenon is explained on the basis of homogeneous nucleation controlled crystallization within nanoscale confined environments in the block copolymer/thermoset blends.

Strain rate effects on the energy absorption of rapidly manufactured composite tubes

As a result of recent increases in fuel prices and the growing number of accident fatalities, the two major concerns of the automotive industry and their customers are now occupant safety and fuel economy {1, 2]. Increasing the amount of energy and optimizing the manner in which energy is absorbed within vehicle crush zones can improve occupant survivability in the event of a crash, while fuel economy is improved through a reduction in weight.  Axial crush tests were conducted on tubular specimens of Carbon/Epoxy (Toray T700/G83C) and Glass/Polypropylene (Twintex). This paper presents results from the tests conducted at quasi-static rates at Deakin Unniversity, Victoria Australia, and intermediate rate tests performed at the Oak Ridge National Laboratory, Tennessee  USA.   The quasi-static tests were conducted at 10mm/min (1.67x10-4m/s) using 5 different forms of initiation. Tests at intermediate rates were performed at speeds of 0.25m/s, 0.5m/s, 0.75m/s 1m/s, 2m/s and 4m/s. Quasi-static tests of tubular specimens showed high specific energy absorption (SEA) values with 86 kJ/kg for Carbon/Epoxy specimens. The SEA of the Glass/Polypropylene specimens was measured to be 29 kJ/kg. Results from the intermediate test rates showed that SEA values did not fall below 55kJ/kg for carbon specimens or 35kJ/kg for the Glass/Polypropylene specimens. When compared with typical steel and aluminium, SEA values of 15 kJ/kg and 30kJ/kg respectively, the benefits of using composite materials in crash structures is apparent.                                                                     

Manufacturing process effects on the mode I interlaminar fracture toughness and nanocreep properties of CFRP

Quickstep ™ is a fluid filled floating mould technology which was recently developed by an Australian company of the same name. The Quickstep and conventional autoclave manufacture of composites were compared by investigating the mode I interlaminar fracture toughness and nanocreep propeties of HexPly914 carbon epoxy composites. It was found that composites cured using the Quickstep technology had significantly higher fracture toughness (1.8 times) than the composites cured via autoclave for this system. DMTA (dynamic mechanical thermal analysis) results showed a higher Tg (glass transition temperature) for the material manufactured by the Quickstep than that cured by the autoclave. FTIR (Fourier transform infrared spectroscopy) spectra did not indicate any difference in cure chemistry between the two processes. Nanocreep experiments were performed to explore the viscoelastic properties of the epoxy matrix of composites. The KelvinVoigt three-element model was applied to analyse the indentation creep behaviour of both composites.

Photochromic wool fabrics with enhanced durability and photochromic performance

In our previous work, we have produced a photochromic wool fabric by applying a thin layer of hybrid silica-photochromic dye onto the wool surface. The coating showed a very fast optical response, but had little influence on the fabric handle, however durability was low. In this context, we reported that durability of the hybrid layer can be improved by introducing epoxy groups into the silica matrix via co-hydrolysis and co-condensation of an alkyl trialkoxysilane (ATAS) and 3-glycidoxypropyltrimethoxysilane (GPTMS). The presence of epoxy groups in the silica enhanced both washing and abrasion durabilities. Also, the optical response speed was slightly increased as well. Effects of the type of alkyl silane and the GPTMS:alkyl silane ratio on the coating durability, fabric handle and optical response were examined.

固化条件对热塑增韧环氧树脂的固化动力学和相分离的影响

Thermoplastic toughened epoxy resins are widely used as matrices in modern prepreg systems.Different curing conditions play a great role in affecting the cure kinetics and phase behaviour of thermoplastic modified epoxies which further result in different mechanical properties of polymer matrix composites.Since the morphology of the cured thermoplastic/epoxy blends is directly related to the mechanical properties,it is essential to control processing conditions for obtaining desirable morphology.A polyethersulphone (PES) modified multifunctional epoxies,triglycidylaminophenol (TGAP) and tetraglycidyldiaminodiphenylmethane (TGDDM),was used for investigation.The cure kinetics and cured morphology of polymer blends heated at different heating rates and cured at different temperature were studied.It is shown that higher cure temperature and higher heating rate display similar effects in the epoxy conversion and the domain size of phase separated structure.

An evaluation of the performance of advanced melded composite joints

Melding is an efficient three step composite joining process that involves the selective cure of composite adherends before the final adhesive joint is created using the adherends own resin system. Melding does not require many of the processes and compromises associated with conventional techniques like adhesive bonding and mechanical fastening.

The Taguchi design of experiments technique was used to optimise three melded joint factors for a unidirectional epoxy prepreg material. The performance of the joint was evaluated using tensile and flexural strength as well as flexural modulus. It was found that not having a step for every ply in the joint was the most influential factor affecting joint performance. This was due to the differing failure modes induced by this factors various levels, which varied the amount of fibre breakage at failure.

Inspection of drop-weight impact damage in woven CFRP laminates fabricated by different processes

The influence of manufacturing process on the drop-weight impact damage in woven carbon/epoxy laminates was inspected by visual observation, dyepenetrant X-ray technique, and optical microscopy observation. The MTM56/ CF0300 woven quasi-isotropic laminates were fabricated by two processes: the autoclave and the Quickstep processes. Quickstep^TM is a novel composite manufacturing process, which was designed for the out-of-autoclave production of high-quality composite parts at lower cost. It utilizes higher heat conduction of fluid other than gas to transfer heat to components, which results in much shorter cure cycles. The laminates cured by this fast heating process showed different impact failure modes from those cured by the conventional autoclave process. The residual indentation in the top side of the Quickstep-cured laminates had a bigger diameter, but a smaller depth at the same impact energy level. Dye-penetrant X-ray revealed more intense and connected impact damage regions in the autoclave-cured laminates. Optical micrography as a supplementary method showed less severe matrix damage in the quickstep-cured laminates indicating a more ductile property of the resin matrix cured at a faster heating rate.

Study on thermoplastic-modified multifunctional epoxies : influence of heating rate on cure behaviour and phase separation

The effect of heating rate on the cure behaviour and phase separation of thermoplastic-modified epoxy systems was investigated. Polyethersulphone (PES) modified multifunctional epoxies, triglycidyl-aminophenol (TGAP) and tetraglycidyldiaminodiphenylmethane (TGDDM), as well T300/914 prepreg were used. It was shown that heating rate had a significant influence on the cure kinetics and phase structures of investigated systems. Greater heating rate causes higher epoxy conversion. The domain size of the macrophases formed from phase separation increases with the increase of heating rate. A more complete phase separation is achieved by fast heated thermoplastic-modified epoxy blends.

Strain rate effects on the energy absorption of rapidly manufactured composite tubes

Quasi-static and intermediate rate axial crush tests were conducted on tubular specimens of Carbon/Epoxy (Toray T700/G83C) and Glass/Polypropylene (Twintex). The quasi-static tests were conducted at 10 mm/min (1.67 x 10¯⁴ m/s); five different crush initiators were used. Tests at intermediate rates were performed at speeds of 0.25, 0.5, 0.75, 1, 2, and 4m/s. Modes of failure and specific energy absorption (SEA) values were studied. The highest SEA measured was 86 kJ/kg. This value was observed using Carbon/Epoxy samples at quasi static rates with a 45° chamfer initiator. The highest energy absorption for Twintex tubes was observed to be 57.56 kJ/kg during 45° chamfer initiated tests at 0.25 m/s. Compared with steel and aluminium, SEA values of 15 and 30 kJ/kg, respectively, the benefits of using composite materials in crash structures become apparent.

Mechanical characterizations of thick laminated composites before and after bonded repair

One set of composite laminates was manufactured from bi-directional carbon fibre woven cloth pre-impregnated with epoxy resin and used to establish experimental techniques. Another, similar set was used for extensive data collection. One other set of laminates, manufactured from uni-directional carbon fibre, was also subjected to extensive tests to represent a different material. The results give the pre and post characterizations of repaired composite materials; outlining at each stage the losses and gains of structural strength and stiffness and discusses the difficulties experienced.