Silane coupling agent modification on interlaminar shear strength of carbon fiber/epoxy/nano‐CaCo3 composites

Four different types of composites were prepared based on unmodified and modified epoxy matrices: (A) unmodified epoxy/carbon fiber composites, (B) modified epoxy/carbon fiber composites by silane coupling agent/nano‐CaCO₃ master batch, (C) modified epoxy/carbon fiber composites by nano‐CaCO₃ particles directly, and (D) modified epoxy/carbon fiber composites by nano‐CaCO₃ particles and silane coupling agent together. The interlaminar shear strength (ILSS) of the carbon fiber‐reinforced composites was investigated. The results show that the silane coupling agent/nano‐CaCO₃ master batch can increase the ILSS to the highest degree. Nevertheless, Sample D, i.e., modified by nano‐CaCO₃ particles and silane coupling agent together, even presents a decrease of the ILSS. The integration effect of silane coupling agent/nano‐CaCO₃ master batch was concluded. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Viscoelastic behavior of epoxy/carbon fiber/Zno nano‐rods hybrid composites

The insufficient viscoelastic resistance of fiber reinforced plastics can be retrofitted by the addition of more rigid nano fillers to the polymer matrix. In this study, carbon fibers plies were grafted with zinc oxide (ZnO) nano‐rods and the hybridized reinforcement was utilized in laminated composites. Flexural creep tests were carried out using dynamic mechanical analysis (DMA) and the time/temperature superposition principle was employed for accelerated testing. To verify the applicability of TTPS, prolonged stress relaxation tests were also carried out in flexural mode. Data from the DMA flexural creep tests revealed that the whiskerization of carbon fibers with ZnO nano rods reduced the creep compliance by 23% at elevated temperatures and prolonged durations. Also, the relaxation data confirmed the applicability of TTPS to these hybrid composites. The stress relaxation modulus improved by 65% in comparison to composites based on neat carbon fibers. POLYM. COMPOS., 36:1967–1972, 2015. © 2014 Society of Plastics Engineer     

Plasticization of nano‐CaCO3 in polystyrene/nano‐CaCO3 composites

The shear rheological properties of polystyrene (PS)/nano‐CaCO₃ composites were studied to determine the plasticization of nano‐CaCO₃ to PS. The composites were prepared by melt extrusion. A poly(styrene–butadiene–styrene) triblock copolymer (SBS), a poly(styrene–isoprene–styrene) triblock copolymer (SIS), SBS‐grafted maleic anhydride (SBS–MAH), and SIS‐grafted maleic anhydride were used as modifiers or compatibilizers. Because of the weak interaction between CaCO₃ and the PS matrix, the composites with 1 and 3 phr CaCO₃ loadings exhibited apparently higher melt shear rates under the same shear stress with respect to the matrix polymer. The storage moduli for the composites increased with low CaCO₃ concentrations. The results showed that CaCO₃ had some effects on the compatibility of PS/SBS (or SBS–MAH)/CaCO₃ composites, in which SBS could effectively retard the movement of PS chain segments. The improvement of compatibility, due to the chemical interaction between CaCO₃ and the grafted maleic anhydride, had obvious effects on the rheological behavior of the composites, the melt shear rate of the composites decreased greatly, and the results showed that nano‐CaCO₃ could plasticize the PS matrix to some extent. Rheological methods provided an indirect but useful characterization of the composite structure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Fracture behavior of PVC/Blendex/nano‐CaCO3 composites

PVC/Blendex/Nano‐CaCO₃ composites were prepared by melt‐blending method. The Blendex (BLENDEX® 338) (GE Specialty Chemicals Co., Ltd., Shanghai, China) was an acrylonitrile‐butadiene‐styrene copolymer with high butadiene content. The fracture behavior of PVC/Blendex/nano‐CaCO₃ composites was studied using a modified essential work of fracture model, U/A = u₀ + u_dl, where u₀ is the limiting specific fracture energy and u_d is the dissipative energy density. The u₀ of PVC/Blendex blend could be greatly increased by the addition of nano‐CaCO₃, while the u_d was decreased. Nano‐CaCO₃ with particle size of 38 nm increased the u₀ of PVC/Blendex blend more effectively than that with particle size of 64 nm, when nano‐CaCO₃ content was below 10 phr. Both the u₀ and u_d of PVC/Blendex/nano‐CaCO₃ composites were not much affected by increasing specimen thickness from 3 mm to 5 mm, while the two fracture parameters were increased with increasing loading rate from 2 mm/min to 10 mm/min, and u_d was found to be more sensitive to the loading rate than u₀. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 953–961, 2005     

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%.     

Morphology and mechanical properties of PP/POE/nano‐CaCO3 composites

The mechanical properties including tensile, flexural, and impact of the nanometer on calcium carbonate (nano‐CaCO₃) filled polypropylene (PP)/poly (ethylene‐co‐octene) (POE) composites were measured at room temperature to identify the effects of the POE content on the mechanical properties. It was found that the Young's modulus, tensile strength, and tensile elongation at break decreased nonlinearly while the tensile fracture strength varied slightly with increasing the POE weight fraction; the V‐notched and unnotched Izod impact fracture strength increased nonlinearly with an increase of the POE weight fraction; the flexural modulus and strength decreased roughly linearly with increasing the POE weight fraction. Furthermore, the impact fracture surface of the specimens was observed by means of a scanning electronic microscope to discuss the toughening mechanisms. POLYM. COMPOS., 37:539–546, 2016. © 2014 Society of Plastics Engineers     

Polystyrene/CaCO3 composites with different CaCO3 radius and different nano‐CaCO3 content—structure and properties

The Archimedes' principle and physical theory are attempted to analysis the densification and structure of the polystyrene (PS) composites by melt compounding with CaCO₃ having different particle size. The difference between the measured specific volume (ν) andthe theoretically calculated specific volume (ν_mix), Δν = ν−ν_mix, can reflect the densification of the composites. It is clearly demonstrated that the PS composites become more condensed with the reduction of the CaCO₃ particle size. Especially, when the content for nano‐CaCO₃ achieves 2 wt%, the Δν value of the composites reaches the least, which shows the best densification. Meanwhile, the glass transition temperature (T_g) reaches the maximum value of about 100°C by differential scanning calorimetry (DSC) and thermal mechanical analysis (TMA), which indirectly reveals the composites microstructure more condensed. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) reveal that 2 wt% nano‐CaCO₃ uniformly disperses in PS composites. The CaCO₃ selected in this experiment has certain toughening effect on PS. The impact and tensile strength increase with addition of nano‐CaCO₃, but the elongation at break decreases. When nano‐CaCO₃ content achieved 2 wt%, the impact and tensile strength present the maximum value of 1.63 KJ/m² and 44.5 MPa, which is higher than the pure PS and the composites filled with the same content of micro‐CaCO₃. POLYM. COMPOS., 31:1258–1264, 2010. © 2009 Society of Plastics Engineers     

Selective particle distribution and mechanical properties of nano‐CaCO3/ethylene‐propylene‐diene terpolymer/polypropylene composites with high content of nano‐CaCO3

T ernary composite of nano‐CaCO₃/ethylene‐propylene‐diene terpolymer (EPDM)/polypropylene (PP) with high content of nano‐CaCO₃ was prepared by two step compounding route, in which EPDM and nano‐CaCO₃ were mixed first, and then melt compounding with PP matrix. The influence of mixing time during the second compounding on distribution of nano‐CaCO₃ particles and the impact strength of the ternary composite have been investigated. It was found that the Izod impact strength of composite decreased with increasing mixing time. The observation of transmission electron microscopy obviously showed that nano‐CaCO₃ particles transported from EPDM to PP matrix firstly and then from PP to the vicinity of EPDM dispersed phase with the increase of mixing time. This phenomenon can be well explained by the minimization of the dissipative energy and the Young's equation. The scanning electron microscope images show that lots of nano fibrils exist at the interface between nano‐CaCO₃ agglomerates and matrix, which can dissipate lots of energy. The toughening mechanism has been interpreted in terms of three‐stage‐mechanism: stress concentration, void and shear band formation, and induced shear yielding. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and properties of nano‐CaCO3/acrylonitrile‐butadiene‐styrene composites

CaCO₃/acrylonitrile‐butadiene‐styrene (ABS) and CaCO₃/ethylene‐vinyl acetate copolymer (EVA)/ABS nanocomposites were prepared by melting‐blend with a single‐screw extruder. Mechanical properties of the nanocomposites and the dispersion state of CaCO₃ particles in ABS matrix were investigated. The results showed that in CaCO₃/EVA/ABS nanocomposites, CaCO₃ nanoparticles could increase flexural modulus of the composites and maintain or increase their impact strength for a certain nano‐CaCO₃ loading range. The tensile strength of the nanocomposites, however, was appreciably decreased by adding CaCO₃ nanoparticles. The microstructure of neat ABS, CaCO₃/ABS nanocomposites, and CaCO₃/EVA/ABS nanocomposites was observed by scanning electron microscopy. It can be found that CaCO₃ nanoparticles were well‐dispersed in ABS matrix at nanoscale. The morphology of the fracture surfaces of the nanocomposites revealed that when CaCO₃/EVA/ABS nanocomposites were exposed to external force, nano‐CaCO₃ particles initiated and terminated crazing (silver streak), which can absorb more impact energy than neat ABS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of graphene oxide on the interlaminar fracture toughness of carbon fiber/epoxy composites

Graphene oxide (GO) nanoparticles were introduced in the interlaminar region of carbon fiber–epoxy composites by dispersing it in a thermoplastic polymer carrier such as polyvinylpyrrolidone (PVP). Mode‐I fracture toughness (G_IC) was investigated using double cantilever beam testing to evaluate the effect of the GO on the delamination behavior of the composite. The GO content was varied from 0% to 7% by weight as a function of the PVP content. Improvement of ～100% in the Mode I fracture toughness (G_IC) was observed compared to composites with no GO. The optimum amount of nanoparticles for improving the interlaminar fracture toughness was found to be ～0.007% by weight of the composite. The increase in the value of flexural strength value was also observed. Scanning electron microscopy of fracture surfaces, X‐ray diffraction, and transmission electron microscopy, and reflectance Fourier transform infrared spectra, as well as Raman spectroscopy results, are presented to support the conclusions. POLYM. ENG. SCI., 59:1199–1208 2019. © 2019 Society of Plastics Engineers     

Chemical modification and adhesion in carbon fiber/epoxy micro‐composites; coupling and surface coverage

Four compounds were used to improve adhesion between carbon fibers and an epoxy matrix. Triglycidyl isocyanurate (TGIC) and 3‐glycidoxy‐propyl‐triethoxysilane (EPS) contained reactive epoxy groups, while N‐(3‐trimethoxysilane‐propyl)ethylene diamine (AMS) a primary and a secondary amino group. The fourth coupling agent was 4,4' diphenylmethane‐diisocianate (MDI). The interaction of the fiber and the coupling agents was studied by dissolution experiments. Chemical reactions taking place on the surface of the fiber were followed by FTIR spectroscopy. Interfacial shear stress determined by fragmentation was used for the characterization of matrix/fiber adhesion. Beside coupling to the surface, EPS, AMS and MDI formed a polymer layer on the surface, but TGIC also entered into secondary reactions during the treatment. Both the type and the amount of the coupling agent affects strongly interfacial adhesion, which is determined by the thickness and properties of the formed coupling agent layer. The combination of dissolution experiments with the fragmentation test yields valuable information about the processes taking place on the surface of the fiber, facilitate the selection of the best coupling agent, as well as the development of surface treatment technology.     

Improving the interlaminar shear strength and thermal conductivity of carbon fiber/epoxy laminates by utilizing the graphene-coated carbon fiber

The poor interlaminar properties restrict the application of carbon fiber reinforced polymer (CFRP) composites. In this work, a novel method for fabricating a graded interface structure is developed to improve the through-thickness thermal conductivity of CFRP composites. High-strength graphene nano-plates (GnP) and phenolic resin (PF) were selected to deposit on the surface of carbon fiber to design a novel CF/Epoxy laminates, where a simultaneous improvement of interlaminar shear strength (ILSS) and through-thickness thermal conductivity was observed. With addition of 1 wt % of GnP-PF in CF, 37.04% increase of the ILSS, and 16.67% enhancement of thermal conductivity compared to the original CFRP. The mechanism for improvement of both ILSS and thermal conductivity was studied by scanning electron microscopy and nano-indentation, where a better interface formed by GnP-PF has been clearly observed. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47061.     

Enhanced interlaminar shear and impact performance of woven carbon/epoxy composites interleaved with needle punched high performance polyethylene fiber nonwoven

In this study, high-performance polyethylene (HPPE) fiber-based needle punched nonwovens were interleaved in cross-plied woven carbon fabric/epoxy composite laminates to enhance their interlaminar and impact properties. The placement of needle punched nonwoven interleaves exhibited considerable enhancement in interlaminar shear strength (ILSS), impact damage tolerance, and compression after impact (CAI) strength of laminates as evidenced by higher interlaminar strength, less absorbed energy, higher elastic energy, reduced damage degree, reduced out-of-plane deformation, higher load-bearing capacity, and higher residual compressive strength as compared to control sample. In particular, the composite laminate with placement of interleaves in alternating sequence between carbon plies resulted in 205.76% increase in ILSS and 129, 103 and 85% increase in CAI at 10, 25, and 40 J impact energy, respectively. Moreover, damaged surface area and out-of-plane deformation reduced to 38.75% and 62.5%, respectively for the same specimen impacted at 40 J energy. These results suggest that the HPPE fiber-based needle punched nonwoven interleaving can be adopted as a simple and low-cost approach compared with other interleaving techniques, to enhance the resistance to delamination, impact performance, and damage tolerance of traditional structural laminates.     

Microstructure and rheologic development of polypropylene/nano‐CaCO3 composites along twin‐screw extruder

Polypropylene/nano‐calcium carbonate (PP/nano‐CaCO₃) composites were prepared by using an intermeshing, co‐rotating twin‐screw extruder. Two different screw configurations, denoted by screws A and B, respectively, were employed. The former provided high dispersive mixing and the later provided high dispersive and distributive mixing. Effect of mixing type on microstructure and rheologic development of nanocomposites was investigated by taking samples from four locations along screws A and B. Transmission electron microscopy results show that in the sample at the exit of extruder, the percentage of nano‐CaCO₃ particles with the equivalent diameter lower than 100 nm along screws A and B is 66.5 and 79.0%. respectively. Moreover, for screw B, the number‐averaged diameter at four sampling locations is smaller than that for screw A. This means that the distributive mixing, provided by screw B, favors the size decrease of nano‐CaCO₃ in the PP matrix. In addition, rheologic results show that the decrease of complex viscosity for the nanocomposites is deeply related to turbine mixing elements, which provides distributive mixing. The online melt shear viscosity of the nanocomposite at the exit of extruder prepared by screw B is lower than that of pure PP. This is related to the dispersion of nano‐CaCO₃ in PP matrix. Finally, the relationship between rheologic properties and microstructure was analyzed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermophysical properties of anhydride‐cured epoxy/nano‐clay composites

Polymer nano‐composites made with a matrix of anhydride‐cured diglycidyl ether of bisphenol A (DGEBA) and reinforced with organo‐montmorillonite clay were investigated. A sonication technique was used to process the epoxy/clay nano‐composites. The thermal properties of the nano‐composites were measured with dynamic mechanical analysis (DMA). The glass transition temperature T_g of the anhydride‐cured epoxy was higher than the room temperature (RT). For samples with 6.25 wt% (4.0 vol%) of clay, the storage modulus at 30°C and at (T_g + 15)°C was observed to increase 43% and 230%, respectively, relative to the value of unfilled epoxy. The clay reinforcing effect was evaluated using the Tandon‐Weng model for randomly oriented particulate filled composites. Transmission electron microscopy (TEM) examination of the nano‐composites prepared by sonication of clays in acetone showed well‐dispersed platelets in the nano‐composites. The clay nano‐platelets were observed to be well‐intercalated/expanded in the anhydride‐cured epoxy resin system. POLYM. COMPOS., 26:42–51, 2005. © 2004 Society of Plastics Engineers.     

Effects of novolac resin modification on mechanical properties of carbon fiber/epoxy composites

The epoxy resin matrix of carbon fiber (CF)‐reinforced epoxy composites was modified with novolac resin (NR) to improve the matrix‐dominated mechanical properties of composites. Flexural strength, interlaminar shear strength (ILSS), and impact strength were measured with unfilled, 7 wt% NR, 13 wt% NR, and 18 wt% NR filled to epoxy to identify the effect of adding NR on the mechanical properties of composites. The results showed that both interfacial and impact properties of composites were improved except for flexural property. The largest improvement in ILSS and impact strength were obtained with 13 wt% loading of NR. ILSS and impact strength were improved by 7.3% and 38.6%, respectively, compared with the composite without NR. The fracture and surface morphologies of the composite specimens were characterized by scanning electron microscopy. Intimate bonding of the fibers and the matrix was evident with the content of 7–13 wt% NR range. Decrease of crosslinking density and formation of NR transition layer were deduced with adding NR. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Investigation on preparation and property of nano‐CaCO3/PP masterbatch modified by reactive monomers

Nano‐CaCO₃/polypropylene (PP) masterbatch containing above 80 wt % nano‐CaCO₃ was prepared by nano‐CaCO₃ coated PP modified by reactive monomers. The chemical interaction, crystallization and melting behavior, thermal stability, morphology, and surface contact angle of masterbatch were investigated with IR, DSC, TEM, TGA, ESCA, and surface contact angle. The results indicated that nano‐CaCO₃ was coated by PP graft copolymers in the masterbatch modified by reactive monomers. The graft ratio and crystallization and melting behavior of PP in the masterbatch depended on the type and content of reactive monomer. The crystallization temperatures of masterbatch modified by reactive monomer is methyl methacrylate > butyl acrylate > methyl acrylate ≈ mixture of acrylic acid and styrene > unmodified ≈ maleic anhydride ≈ acrylic acid > styrene. Modification by reactive monomer increased the thermal stability and surface contact angle of masterbatch. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3907–3914, 2006     

Preparation and properties of multi‐walled carbon nanotubes/carbon fiber/epoxy composites

Multi‐walled carbon nanotubes/carbon fiber (MWCNTs/CF) hybrid fillers are employed to prepare MWCNTs/CF/epoxy composites. Results reveal that a great improvement of the thermal conductivities of the epoxy composites with the addition of MWCNTs/CF hybrid fillers, and the thermal conductivity of the MWCNTs/CF/epoxy composites is 1.426 W/mK with 8 vol% treated MWCNTs/CF hybrid fillers (5 vol% MWCNTs + 3 vol% CF). Both the flexural and impact strength of the MWCNTs/CF/epoxy composites are increased firstly, but decreased with the excessive addition of MWCNTs. The flexural and impact strength of the MWCNTs/epoxy composites are optimal with 2 vol% MWCNTs. For a given MWCNTs/CF hybrid fillers loading, the surface treatment of MWCNTs/CF hybrid fillers can further increase the thermal conductivities and mechanical properties of the MWCNTs/CF/epoxy composites. POLYM. COMPOS., 35:2150–2153, 2014. © 2014 Society of Plastics Engineers     

Characterization of interlaminar shear strength of laminated woven E‐glass/epoxy composites by four point bend shear test

An experimental and numerical investigation was performed to study the interlaminar shear response of laminated woven E‐glass/epoxy composites. The interlaminar shear strength results obtained from four point bend shear tests were compared with the results obtained from American Society for Testing and Materials (ASTM) test standards D2344 (short beam strength). The test results reveal that the four point bend interlaminar shear test results at a span to thickness ratio of 8 is higher than the short beam shear test results at a span to thickness ratio of 4. Numerical simulations were performed with ANSYS® software. The experimental results and the corresponding numerical results are in good agreement. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers