Experimental assessment on potential for processiblity of carbon nanotubes/epoxy system used as nanocomposites

In this study, carboxylic acid functionalized carbon nanotubes (CNTs) were used to modify epoxy with intent to develop a nanocomposite matrix for hybrid multiscale composites combining benefits of nanoscale reinforcement with well‐established fibrous composites. CNTs were dispersed in epoxy by using high energy sonication, followed by the fabrication of epoxy/CNTs composites. The processibility of CNTs/epoxy systems was explored with respect to their dispersion state and viscosity. The dependences of viscosity, mechanical and thermomechanical properties of nanocomposite system on CNTs content were investigated. The dispersion quality and reagglomeration behavior of CNTs in epoxy and the capillary infiltration of continuous fiber with the epoxy/CNTs dispersion were characterized using optical microscope and capillary experiment. As compared with neat epoxy sample, the CNTs nanocomposites exhibit flexural strength of 126.5 MPa for 1 wt% CNTs content and impact strength of 28.9 kJ m^?2 for 0.1 wt% CNTs content, respectively. A CNTs loading of 0.1 wt% significantly improved the glass transition temperatures, T_g, of the nanocomposites. Scanning electron microscopy (SEM) was used to examine the fracture surface of the failed specimens. It is demonstrated that the properties of CNTs/epoxy system are dispersion‐dominated and interface sensitive. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

The role of multi‐walled carbon nanotubes in epoxy nanocomposites and resin transfer molded glass fiber hybrid composites: Dispersion,local distribution,thermal, and fracture/mechanical properties

Hybrid composites containing endless glass fiber reinforcement and surface‐functionalized carbon nanotubes (CNTs) dispersed in the matrix phase were produced by resin transfer molding (RTM). An efficient surface modification of the nanotubes enhances the compatibility with the matrix system and the dispersion quality, enabling the impregnation process via liquid composite molding. We assessed the quality of the RTM process by newly developed methodologies for the quantification of the filtering of CNTs. First, we established a method to analyze the CNT length distribution before and after injection for thermosetting composites to characterize length‐dependent withholding respectively the size distribution of nanotubes in the hybrid composites. Second, the resulting test laminates were locally examined by Raman spectroscopy and compared to reference (nanocomposite) samples of known CNT content to non‐destructively quantify the local CNT concentration along the resin flow path. Moreover, the thermal and mechanical properties of the modified composites were investigated. The nanocomposites containing 0.5 wt% surface‐functionalized CNTs exhibited superior ductility and increased fracture toughness. Glass fiber hybrid composites containing 0.5 wt% functionalized CNTs in the resin phase exhibited increased fracture toughness in mode I and a slight deterioration in mode II due to the constrained formation of hackles. POLYM. COMPOS., 38:1849–1863, 2017. © 2015 Society of Plastics Engineers     

Preparation of a functional reduced graphene oxide and carbon nanotube hybrid and its reinforcement effects on the properties of polyimide composites

The homogeneous dispersion and strong interfacial interactions of carbon nanomaterials are vital factors on enhancing the properties of polymer composites. Two‐dimensional reduced graphene oxide (rGO) and one‐dimensional carbon nanotubes (CNTs) were first grafted by 4,4′‐oxydianiline (ODA). The successful grafting of ODA onto the rGO and CNTs were confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and X‐ray photoelectron spectroscopy. The hybrid carbon nanomaterials of the functionalized CNTs and rGO with different ratios were prepared via a solution‐mixing method, and their dispersion state was investigated. The hybrid carbon nanomaterials with good stability were introduced to polyimide (PI) via in situ polymerization. The morphology and properties of the polymer composites were studied. The results show that much better mechanical and electrical properties of the composites could be achieved in comparison with those of the neat PI. An improvement of 100.7% on the tensile strength and eight orders for the electrical conductivity were achieved at only a 1.0 wt % hybrid content. A significant enhancement effect was attributed to the homogeneous dispersion of the filler, filler–matrix strong interfacial interactions, and unique structure of the hybrid carbon nanomaterials in the composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44575.     

Mechanical properties of hybrid structural composites reinforced with nanosilica

Epoxy‐based hybrid structural composites reinforced with 14 nm spherical silica particles were investigated for mechanical properties as a function of nanosilica loading fractions. Composites were fabricated using continuous glass or carbon fiber of unidirectional architecture and nanosilica dispersed epoxy, through resin film infusion process. Uniform dispersion of nanoparticles in resin matrix was ensured by an optimized ultrasound‐assisted process. Although resin viscosity marginally reduces in the presence of nanosilica enabling a better control in composite manufacturing process, glass transition temperature of epoxy remained unaffected at low weight fractions. Compressive strength of hybrid glass or carbon fiber/epoxy composites showed more than 30–35% increase with nanosilica at a concentration as low as 0.2 wt%. Tensile and compressive properties of hybrid composites in transverse direction to the reinforcement remained unaffected. POLYM. COMPOS. 37:1216–1222, 2016. © 2014 Society of Plastics Engineers     

Enhancement of flexural strength of glass fiber reinforced polymer laminates using multiwall carbon nanotubes

In this work, advance/multiscale nanocomposite were made by adding different amount (0, 0.5, 1.25, and 2 wt%) of multiwall carbon nanotubes (MWCNTs) to glass fiber reinforced polymer (GFRP) composites by hand lay‐up and vacuum bagging technique. Flexural strength and interlaminar shear strength (ILSS) of composites were performed on unfilled and MWCNTs‐filled glass fiber/epoxy nanocomposite to identify the effect of adding nanotubes on the mechanical properties. For understanding the structure and morphology of advance nanocomposite, the dispersion states were studied using field emission scanning electron microscopy (FE‐SEM). Mechanics of fracture behavior in different test were also discussed in details. POLYM. ENG. SCI., 59:E248–E261, 2019. © 2018 Society of Plastics Engineers     

Mechanical and thermal enhancements of benzoxazine‐based GF composite laminated by in situ reaction with carboxyl functionalized CNTs

An easy and efficient approach by using carboxyl functionalized CNTs (CNT‐COOH) as nano reinforcement was reported to develop advanced thermosetting composite laminates. Benzoxazine containing cyano groups (BA‐ph) grafted with CNTs (CNT‐g‐BA‐ph), obtained from the in situ reaction of BA‐ph and CNT‐COOH, was used as polymer matrix and processed into glass fiber (GF)‐reinforced laminates through hot‐pressed technology. FTIR study confirmed that CNT‐COOH was bonded to BA‐ph matrices. The flexural strength and modulus increased from 450 MPa and 26.4 GPa in BA‐ph laminate to 650 MPa and 28.4 GPa in CNT‐g‐BA‐ph/GF composite, leading to 44 and 7.5% increase, respectively. The SEM image observation indicated that the CNT‐COOH was distributed homogeneously in the matrix, and thus significantly eliminated the resin‐rich regions and free volumes. Besides, the obtained composite laminates showed excellent thermal and thermal‐oxidative stabilities with the onset degradation temperature up to 624°C in N₂ and 522°C in air. This study demonstrated that CNT‐COOH grafted on thermosetting matrices through in situ reaction can lead to obvious mechanical and thermal increments, which provided a new and effective way to design and improve the properties of composite laminates. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Hybrid ZnAl‐LDH/CNTs nanocomposites: Noncovalent assembly and enhanced photodegradation performance

In this article, we reported a facile and effective strategy for assembling hybrid ZnAl‐layered double hydroxide/carbon nanotubes (ZnAl‐LDH/CNTs) nanocomposites through noncovalent bonds, for the first time, in the presence of L ‐cysteine molecules. The materials have been characterized by powder X‐ray diffraction (XRD), energy dispersive X‐ray spectroscopy (EDS), transmission electron microscopy (TEM), thermogravimetry and differential scanning calorimetry (TG‐DSC), X‐ray photoelectron spectra (XPS) and specific surface area measurement. The results indicate that L ‐cysteine as bridging linker plays a key role for enhancing both adhesion and dispersion of LDH nanocrystallites onto the surface of CNTs matrix through the interfacial interaction, and effectively inhibits the in situ growth of LDH crystallites, thus resulting in remarkably reduced LDH crystallite sizes; the Eu(III) fluorescence quenching in intercalated‐Eu(III)complex LDH/CNTs nanocomposite can occur because of the interaction between LDH crystallites and CNTs matrix. Furthermore, it is found that as‐assembled hybrid LDH/CNTs nanocomposites exhibit excellent performance for photodegradation of methyl orange molecules under UV irradiation, which is closely related to the unique hybrid nanostructure and composition of composites. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Influence of multiwalled carbon nanotubes on the processing behavior of epoxy powder compositions and on the mechanical properties of their fiber reinforced composites

This study reports the preparation of advanced carbon fiber composites with a nanocomposite matrix prepared by dispersing multiwall carbon nanotubes (CNTs) in a powder type epoxy oligomer with two different processing techniques (1) master batch dilution technique and (2) direct mixing (with the help of twin‐screw extruder in both cases). The master batch technique shows a better efficiency for the dispersion of the CNTs aggregates. The rheological results demonstrate that the incorporation of the CNTs into the epoxy oligomer leads, as expected, to a marked increase in the viscosity and of the presence of a yield stress point that also depends on the processing technique adopted. Carbon fiber (CFRP) and glass fiber (GFRP) composite materials were produced by electrostatic spraying of the epoxy matrix formulations on the carbon and glass fabric, respectively, followed by calendering and mold pressing. The mechanical properties of the obtained epoxy/CNT‐matrix composite materials, such as interlaminar fracture toughness, flexural strength, shear storage and loss moduli are discussed in terms of the processing techniques and fabric material. The incorporation of 1 wt% CNTs in the epoxy matrix results in a relevant increase of the fracture toughness, flexural strength and modulus of both CFRP and GFRP. POLYM. COMPOS., 37:2377–2383, 2016. © 2015 Society of Plastics Engineers     

Influence of nano‐organomontmorillonite on the viscoelasticity of the poly(trimethylene terephthalate)/glass fiber/organomontmorillonite hybrid nanocomposites materials

The influences of organically modified montmorillonite (OMMT) on the viscoelasticity of poly(trimethylene terephthalate)/glass fiber/OMMT (PTT/GF/OMMT) hybrid nanocomposite materials at liquid, elastic and glassy states, respectively, were investigated by using the rotational rheometer and dynamic mechanical analyzer (DMA). The viscoelasticity results suggest that OMMT has many important influences on the structure, modulus and toughness of the hybrid nanocomposite materials. At melton state, the shear‐thinning phenomena of the hybrid composite melts become remarkable with increasing OMMT content. At low frequency, the shear storage modulus (G′) and shear loss modulus (G″) of the melts increase with increasing OMMT content. The melt's elastic response increases by OMMT, and OMMT improves the creep resistance of the melts; in addition, the stress relaxation of the hybrid composite melts become slow with increasing OMMT content, and the stress leavings becomes much higher with increasing OMMT content. At glassy state, the storage modulus of the hybrid nanocomposites increases with increasing OMMT content, while the materials' loss modulus increases first and then decreases with increasing OMMT content; therefore, OMMT nanosheets have reinforcement effect on the composites, and it also has definite toughening effect on the hybrid composite when the OMMT content is no >2 wt%. At rubbery state, the hybrid composites show lower decreasing storage modulus but have lower cold‐crystallization ability than that of pure PTT and PTT/GF composite. POLYM. COMPOS., 35:795–805, 2014. © 2013 Society of Plastics Engineers     

Structure and properties of aeronautical composites using carbon nanotubes/epoxy dispersion as nanocomposite matrix

The structure and properties of hybrid multiscale composites containing carbon nanotubes (CNTs) was reported. CNTs were dispersed in epoxy by using high energy ultrasonication, followed by the fabrication of CNT hybrid composites via resin transfer molding (RTM) processing. The processability of CNTs/epoxy systems was explored by a capillary experiment. The dependences of mechanical and electrical properties of the hybrid composites on CNT content were investigated. Microscopic observation confirms the formation of CNTs percolation network. The different roles of CNT networks in mechanical reinforcement and electrical amelioration were analyzed. One explanation based on the dispersion and distribution of CNTs is proposed. It is found that the variations of the hybrid composites with respect to mechanical and electrical properties are attributed to the hierarchical structure in the hybrid composites. As far as the hybrid multiscale composites produced via RTM process is concerned, the formation of CNT percolation network, subjected to dynamic impregnation, is hindered by the presence of continuous fibrous reinforcement. The hierarchical structure influenced by several competing factors reveals great potential in being able to tailor the structural and functional performance of the CNT hybrid composites. The effects of CNTs on the dimensional stability of polymer based composites are also assessed. POLYM. COMPOS., 34:1690–1697, 2013. © 2013 Society of Plastics Engineers     

Injection‐molded short hemp fiber/glass fiber‐reinforced polypropylene hybrid composites—Mechanical,water absorption and thermal properties

Natural fiber‐based thermoplastic composites are generally lower in strength performance compared to thermoset composites. However, they have the advantage of design flexibility and recycling possibilities. Hybridization with small amounts of synthetic fibers makes these natural fiber composites more suitable for technical applications such as automotive interior parts. Hemp fiber is one of the important lignocellulosic bast fiber and has been used as reinforcement for industrial applications. This study focused on the performance of injection‐molded short hemp fiber and hemp/glass fiber hybrid polypropylene composites. Results showed that hybridization with glass fiber enhanced the performance properties. A value of 101 MPa for flexural strength and 5.5 GPa for the flexural modulus is achieved from a hybrid composite containing 25 wt % of hemp and 15 wt % of glass. Notched Izod impact strength of the hybrid composites exhibited great enhancement (34%). Analysis of fiber length distribution in the composite and fracture surface was performed to study the fiber breakage and fracture mechanism. Thermal properties and resistance to water absorption properties of the hemp fiber composites were improved by hybridization with glass fibers. Overall studies indicated that the short hemp/glass fiber hybrid polypropylene composites are promising candidates for structural applications where high stiffness and thermal resistance is required. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2432–2441, 2007     

Dynamic mechanical properties of oil palm fiber/phenol formaldehyde and oil palm fiber/glass hybrid phenol formaldehyde composites

The dynamic mechanical properties of oil palm fiber reinforced phenol formaldehyde (PF) composites and oil palm/glass hybrid fiber reinforced PF composites were investigated as a function of fiber content and hybrid fiber ratio. The dynamic modulus of the neat PF sample decreases with decrease in frequency. Glass transition attributed with the α relaxation of the neat PF sample was observed around 140°C. Tanδ values and storage modulus show great enhancement upon fiber addition. The value increases with increase in fiber content. The loss modulus shows a reverse trend with increase in fiber loading. Incorporation of oil palm fiber shifts the glass transition towards lower temperature value. The glass transition temperature of the hybrid composites is lower than that of the unhybridized composites. The highest value of mechanical damping is observed in hybrid composites. Storage modulus of the hybrid composites is lower than unhybridized oil palm fiber/PF composite. A similar trend is observed for loss modulus. Activation energies for the relaxation processes in different composites were calculated. Activation energy is increased upon fibrous reinforcement. Complex modulus variations and phase behavior of the composites were studied from Cole‐Cole plots. Finally, master curves for the viscoelastic properties of the composites were constructed on the basis of time‐temperature superposition principle. POLYM. COMPOS., 26:388–400, 2005. © 2005 Society of Plastics Engineers     

Long jute fiber‐reinforced polypropylene composite: Effects of jute fiber bundle and glass fiber hybridization

Two types of long jute fiber pellet consisting of twisted‐jute yarn (LFT‐JF/PP) and untwisted‐jute yarn (UT‐JF/PP) pellets are used to prepare jute fiber–reinforced polypropylene (JF/PP) composites. The mechanical properties of both long fiber composites are compared with that of re‐pelletized pellet (RP‐JF/PP) of LFT‐JF/PP pellet, which is re‐compounded by extrusion compounding. High stiffness and high impact strength of JF/PP composites are as a result of using long fiber. However, the longer fiber bundle consequently affects the distribution of jute fiber. The incorporation of 10 wt % glass fibers is found to improve mechanical properties of JF/PP composites. Increasing mechanical properties of hybrid composites is dependent on the type of JF/PP pellets, which directly affect the fiber length and fiber orientation of glass fiber within hybrid composites. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41819.     

Temperature effect on graphene‐filled interface between glass–carbon hybrid fibers and epoxy resin characterized by fiber‐bundle pull‐out test

The overall mechanical performance of glass–carbon hybrid fibers reinforced epoxy composites depends heavily upon fiber–matrix interfacial properties and the service temperatures. Fiber‐bundle pull‐out tests of glass (GF) and/or carbon fiber (CF) reinforced epoxy composites were carried out at room and elevated temperatures. Graphene nanoplatelets were added in the interfacial region to investigate their influence on the interfacial shear strength (IFSS). Results show that IFSS of specimens with fiber‐bundle number ratio of GF:CF = 1:2 is the largest among the hybrid composites, and a positive hybridization effect is found at elevated temperatures. IFSS of all the specimens decreases with the increasing of test temperatures, while the toughness shows a contrary tendency. As verified by scanning electron microscopy observations, graphene nanoplatelets on fiber surface could enhance the IFSS of pure glass/carbon and hybrid fibers reinforced epoxy composites at higher temperatures significantly. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46263.     

Preparation and mechanical properties of waterborne polyurethane/carbon nanotube composites

Waterborne polyurethane (WBPU) and multiwalled carbon nanotubes (CNTs) composite films with 0–4.0 wt% CNTs were prepared by ultrasonic dispersion of carboxylic acid‐functionalized CNTs in WBPU followed by emulsion casting process. The elongations at break of the WBPU/CNTs composites increase with the incorporation of CNTs. The tensile strength and crystallinity of the nanocomposite films with lower CNTs contents (<2 wt%) increase obviously; while the tensile strengths of the composites with more CNTs (≥2 wt%) decrease, in contrast to the pure PU film. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations indicated that the CNTs are uniformly dispersed in the composites incorporated with lower CNTs contents (≤1.5 wt%). However, aggregation of CNTs increased with increasing CNTs content in the WBPU/CNTs composites, causing the macrophase separation. The dispersion state of the CNTs affects the crystallinity of the PU matrix and the phase separation of the composites, which are two key factors to influence the mechanical properties of the WBPU/CNTs composites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Highly conductive polymer composites based on controlled agglomeration of carbon nanotubes

This paper reports an innovative approach to enhance electrical conductivity of fiber composites based on non-conductive fiber and polymer matrix. The dispersion of carbon nanotubes (CNTs) is carried out using a fiber sizing agent which contains uniformly distributed CNTs. The infusion of the sizing agent into the fiber preform prior to resin infusion gives rise to high agglomeration of CNTs on the fiber surface and results in electrical conductivities of 2-3 orders of magnitude higher than those of specimens prepared by a calendering approach.     

Preparation and characterization of the modulus intermediate layer in carbon fiber/epoxy composites by depositing sepiolites

An important aspect in development of multi‐scale reinforced composites is their mass production which can be easily realized. In this article, the sepiolites (Si12O30Mg8(OH)4(OH2)4·8H2O) are directly deposited onto the surface of JH‐T800 carbon fibers for the first time with no need for removal of the commercial sizing agent. The sepiolites adhering to the carbon fibers are uniformly distributed with random orientation, and participated in the formation of high modulus intermediate layer encompassing the carbon fiber. After the deposition of sepiolites, the interfacial shear strengths (IFSS) of the carbon fiber/epoxy composites are significantly improved as shown in single‐fiber composite fragmentation tests. Compared to the commercial carbon fiber composites, the sepiolite‐deposited fiber composites also exhibit obvious improvement in the interlaminar shear strength and flexural strength. As a new kind of multi‐scale reinforcement with industrial application value, the sepiolite‐deposited carbon fibers can further raise the level of mechanical properties of the existing carbon fiber reinforced composites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43955.     

Electrophoretic deposition of different carbon nanoscale reinforcements on carbon fiber fabrics and mechanical properties of the resulting hybrid multi‐scale epoxy composites

Three types of carbon nanoscale reinforcements (CNRs) including the shortened electrospun carbon nanofibers (ECNFs, with diameters and lengths of ∼200 nm and ∼15 µm, respectively), carbon nanofibers (CNFs), and graphite nanofibers (GNFs) were electrophoretically deposited on carbon fiber (CF) fabrics for the fabrication of hybrid multi‐scale epoxy composites. The results indicated that the electrophoretic deposition (EPD) of CNRs onto CF fabrics led to substantial improvements on mechanical properties of hybrid multi‐scale epoxy composites; in particular, the hybrid multi‐scale epoxy composite containing surface‐functionalized ECNFs (with amino groups) exhibited the highest mechanical properties. The study also indicated that some agglomerates of CNRs (particularly GNFs) could form during the EPD process, which would decrease mechanical properties of the resulting composites. Additionally, the reinforcement mechanisms were investigated, and the results suggested that continuous (or long) ECNFs would outperform short ECNFs on the reinforcement of resin‐rich interlaminar regions in the composites. POLYM. COMPOS., 35:1229–1237, 2014. © 2013 Society of Plastics Engineers     

The viscoelastic properties of modified thermoplastic impregnated multiaxial aramid fabrics

This study reports the manufacture of new fabric forms from the preparation of hybrid laminated multiaxial composites with enhanced thermo‐mechanical properties. Thermal and dynamic mechanical analysis of polymer matrix films and fabricated hybrid composites were used to determine the optimal material composition and reinforcement content for composites with improved viscoelastic properties. The introduction of 5 wt% silica nanoparticles in a composite of p‐aramid–poly(vinyl butyral) led to significant improvements in the mechanical properties, and the addition of silane coupling agents yielded maximal values of the storage modulus for hybrid nanocomposites. The introduction of silane led to a better dispersion and deagglomeration of SiO₂ particles, and to the formation of chemical bonds between organic and inorganic constituents, or p‐aramid–poly(vinyl butyral) composites. In this way, the mobility of macromolecules was reduced, which can be seen from the decreasing value of damping factor for the p‐aramid–poly(vinyl butyral) composite. Analysis of the glass transition temperature of the composite with amino‐functionalized silica nanoparticles revealed improved thermal stability in addition to the aforementioned mechanical properties of the tested materials. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Comparison of two different carbon nanotubes-based hybrid multiscale composites with respect to mechanical and electrical properties

Pristine and carboxylic acid functionalised carbon nanotubes (CNTs-P and CNTs-COOH) hybrid composites based on ultrasonically processed nanocomposite epoxy matrix have been prepared. The thermodynamic interactions between CNTs and epoxy components are evaluated through solution experiment. The measurements of mechanical properties and volume electrical resistivity are performed to characterise the structure-property interplay of CNTs hybrid composites. A 0.3?wt-% CNTs-COOH loading significantly enhances the glass transition temperatures (Tg) of the resultant hybrid composites. The re-agglomeration of CNTs-P has been ascribed to the thermodynamic and kinetic factors, which determine the morphological characteristics of CNTs within the overall composites. CNTs-P network enables a continuous conductive path to be present in the composites at lower CNTs-P concentration. An analysis of the effects of the functionalisation of CNTs on the structure and properties of their hybrid composites has been carried out.