Functionalization of carbon nanotubes with (3‐glycidyloxypropyl)‐trimethoxysilane: Effect of wrapping on epoxy matrix nanocomposites

In this work, multiwalled carbon nanotubes (MWCNT), after previous oxidation, are functionalized with excess (3‐glycidyloxypropyl)trimethoxysilane (GLYMO) and used as reinforcement in epoxy matrix nanocomposites. Infrared, Raman, and energy‐dispersive X‐ray spectroscopies confirm the silanization of the MWCNT, while transmission electron microscopy images show that oxidized nanotubes presented less entanglement than pristine and silanized MWCNT. Thickening of the nanotubes is also observed after silanization, suggesting that the MWCNT are wrapped by siloxane chains. Field‐emission scanning electron microscopy reveals that oxidized nanotubes are better dispersed in the matrix, providing nanocomposites with better mechanical properties than those reinforced with pristine and silanized MWCNT. On the other hand, the glass transition temperature of the nanocomposite with 0.05 wt % MWCNT‐GLYMO increased by 14 °C compared to the neat epoxy resin, suggesting a strong matrix–nanotube adhesion. The functionalization of nanotubes using an excess amount of silane can thus favor the formation of an organosiloxane coating on the MWCNT, preventing its dispersion and contributing to poor mechanical properties of epoxy nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44245.     

Curing kinetics of epoxy resin–imidazole–organic montmorillonite nanocomposites determined by differential scanning calorimetry

The curing kinetics of epoxy resin–imidazole–organic montmorillonite nanocomposites were investigated by differential scanning calorimetry (DSC) in the isothermal mode. X‐ray diffraction (XRD) analysis indicated the formation of a layered silicate–epoxy nanocomposite. The cure rates for the epoxy resin–imidazole–organic montmorillonite nanocomposite were lower than the values for the neat system at higher temperature (120 and 130°C), as indicated by the relation between the cure conversion and time. These results revealed that the autocatalytic model and the modified Avrami equation are both valid for describing the cure behaviors of epoxy resin–imidazole–organic montmorillonite systems. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2932–2941, 2003     

Solvent-Free One-Pot Synthesis of high performance silica/epoxy nanocomposites

High performance silanized silica/epoxy nanocomposites were prepared through mixing epoxy, tetraethyl orthosilicate (TEOS), (3-aminopropyl)trimethoxysilane (APTMS) and ammonia solution at 50 °C. This all-in-one “Solvent-Free One-Pot Synthesis” results in nanocomposites with uniform dispersion of oval shaped silica nanoparticles and strong adhesion between silica and epoxy matrix. The influence of the synthesis conditions, such as molar ratio of NH₃:TEOS, aging time, curing process and silica content on the thermal mechanical properties of nanocomposites were studied. The silanized silica/epoxy nanocomposite prepared in this study exhibits better thermal mechanical property in comparison with neat epoxy, non-functionalized silica/epoxy and commercialized silica/epoxy systems. The prepared nanocomposite with 3 wt% silanized silica exhibits 20%, 17% and 6% improvements on flexural, tensile and storage modulus over those of neat epoxy, respectively.     

The effect of graphene oxide on UV curing kinetics and properties of SU8 nanocomposites

In the present study SU8 nanocomposites were prepared by incorporating graphene oxide (GO ), and its effect on the UV curing kinetics, morphology, electrical, hardness and thermal properties of the nanocomposites were investigated at different loading levels of GO (0.1 ? 3 wt%). Studying the reaction kinetics of the UV curing process by means of real‐time infrared spectroscopy showed that the polymerization rate and the final conversion of epoxy groups was related to the loading level of GO in the nanocomposites. An autocatalytic kinetics model of the curing reaction confirmed the effect of GO nanoparticles on the curing rate constant (k ), the order of the initiation reaction (m ) and the ultimate conversion of the UV ‐cured nanocomposites. Appropriate experimental observations indicated that dispersion of GO within the resin plays a critical role on the cure kinetics and final conversion. The results of the kinetics modeling and morphological observations showed that the curing rate constant of the nanocomposites is highly dependent on the GO content and its dispersion state, indicating that GO prevents epoxy resin crosslinking by photoinitator deactivation. Moreover, oxygen functionalities, such as hydroxyl and carboxyl groups, on the surface of GO facilitate interfacial interactions between epoxy groups from the matrix and GO . Electrical conductivity measurements demonstrated that the UV ‐induced photo‐cured GO filled resins are conductive SU8 nanocomposites. It was observed that the thermal stability of the nanocomposites is enhanced due to the dispersion of GO in the matrix. Moreover, the microhardness analysis showed that addition of GO to neat SU8 increases the mechanical hardness of the nanocomposite. © 2016 Society of Chemical Industry     

Effects of carbon nanotube fillers on the curing processes of epoxy resin‐based composites

The effects of different grades of carbon nanotubes on the curing of a typical epoxy resin (EPIKOTE? resin 862 and EPIKURE? curing agent W) were examined via differential scanning calorimetry. It was found that nanotubes could initiate cure at lower temperatures, while the overall curing process was slowed as evidenced by lower total heat of reaction and lower glass transition temperatures of the cured nanocomposites compared to neat epoxy. This finding is practically important as it is essential to have a consistent degree of cure when the properties of thermosets with nanoinclusions are compared to neat resins. It was also found that the inclusion of carbon nanotubes might induce the thermal degradation of epoxy composites at lower temperatures. Morphological analysis done with scanning electron microscopy revealed good dispersion of nanotubes within the epoxy matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5248–5254, 2006     

Supercritical carbon dioxide-assisted silanization of multi-walled carbon nanotubes and their effect on the thermo-mechanical properties of epoxy nanocomposites

Supercritical carbon dioxide was employed as the solvent for the functionalization of multi-walled carbon nanotubes (MWCNTs) with an epoxy-capped silane. The silanization protocol was found to be a suitable green alternative to traditional routes that rely on organic solvents for grafting nearly monolayers of silane molecules onto the nanotube surfaces. The addition of silanized MWCNTs to a model epoxy markedly increased its T_g, and measurements of the network cooperativity length scale linked this change to a reduction in polymer segment mobility. Composites filled with low loading levels of both pristine and silanized MWCNTs exhibited significantly higher strain at break and toughness than the neat epoxy, and the greatest improvements were observed at low loading levels. SEM analysis of the composite fracture surfaces revealed that nanotube pullout was the primary failure mechanism in epoxy loaded with pristine MWCNTs while crack bridging predominated in composites containing silanized MWCNTs as the result of strong interfacial bonding with the matrix. The elevated T_g and toughness achieved with small additions of silanized MWCNTs promise to extend the engineering applications of the epoxy resin.     

Analysis of the cure of epoxy based layered silicate nanocomposites: Reaction kinetics and nanostructure development

The cure reaction kinetics of epoxy resin, with organically modified montmorillonite loadings of up to 20 wt % and with stoichiometric conditions, has been studied by differential scanning calorimetry with a view to understanding further the fabrication of epoxy‐based polymer layered silicate nanocomposites. The kinetic analysis of isothermal and nonisothermal cure shows that the autocatalytic model is the more appropriate to describe the kinetics of these reactions, and it is observed that a dominant effect of the montmorillonite is to catalyze the curing reaction. However, it was not possible to model the reactions over the whole range of degrees of conversion, in particular for nonisothermal cure. This attributed to the complexity of the reactions, and especially to the occurrence of etherification by cationic homopolymerization catalyzed by the onium ion of the organically modified montmorillonite. The homopolymerization reaction results in an excess of diamine in the system, and hence in practice the reaction is off stoichiometric, which leads to a reduction in both the heat of cure and the glass transition temperature as the montmorillonite content increases. Small angle X‐ray scattering of the cured nanocomposites shows that an exfoliated nanostructure is obtained in nonisothermal cure at slow heating rates, whereas for nonisothermal cure at faster heating rates, as well as for isothermal cure at 70°C and 100°C, a certain amount of exfoliation is accompanied by the growth of d‐spacings of 1.4 nm and 1.8 nm for dynamic and isothermal cure, respectively, smaller than the d‐spacings of the modified clay before intercalation of the resin. A similar nanostructure, consisting of extensive exfoliation accompanied by a strong scattering at distances less than the d‐spacing of the modified clay, is also found for resin/clay mixtures, before the addition of any crosslinking agent, which have been preconditioned by storage for long times at room temperature. The development of these nanostructures is attributed to the presence of clay agglomerations in the original resin/clay mixtures and highlights the importance of the quality of the dispersion of the clay in the resin in respect of achieving a homogeneous exfoliated nanostructure in the cured nanocomposite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Enhancement of dynamic mechanical properties and flame resistance of nanocomposites based on epoxy and nanosilica modified with KR-12 coupling agent

The epoxy/silica nanocomposites containing a wide range of isopropyltri[di(octyl) phosphate] titanate coupling agent (KR-12) modified nanosilica (m-nanosilica) loading (0–7 wt%) cured with tetrabutyl titanate hardener were prepared. Their morphology, thermal stability, thermal expansion, and mechanical properties including hardness, abrasion resistance were investigated. The wetting ability of epoxy-nanosilica systems on glass surface was assessed based on static contact angle. The obtained results showed that the contact angle of the nanocomposites containing m-nanosilica is slightly changed as compared to the contact angle of pure epoxy resin and lower than that of the nanocomposite containing unmodified nanosilica. The data of dynamic mechanical analysis of the nanocomposites using different nanosilica content indicated that the presence of m-nanosilica lowered the recovery energy of the nanocomposites to 41.62% as compared to neat epoxy. The limiting oxygen index (LOI) of the nanocomposites confirmed that the m-nanosilica increased the flame retardance of epoxy matrix. When using 7 wt% of m-nanosilca, the LOI value of the nanocomposite was 27.4 while this index of neat epoxy was 21.6. The scanning electron microscopic images of residual char combustion of the nanocompsites indicated a formation of nanosilica layer contributed to restrain combustion of the material.     

Curing behavior of epoxy resin/tung oil anhydride exfoliated nanocomposite by differential scanning calorimetry

The nanocomposite of epoxy resin/tung oil anhydride/organic montmorillonite was prepared by casting and curing. The distance of the clay gallery rose and the exfoliated nanocomposite was formed. The exfoliation behaviors of the nanocomposite had been investigated by X‐ray diffraction (XRD). The curing mechanism and kinetics of epoxy resin with the different amounts of organic montmorillonite were studied using isothermal and dynamic methods by differential scanning calorimetry (DSC). Some parameters, the activation energy and reaction orders, were calculated by the modified Avrami equation in analysis of the isothermal experiment. The total curing mechanism and kinetics of curing reaction were also analyzed by the Flynn–Wall–Ozawa method. It was noted that the instantaneous activity energy during the curing process could be obtained by the Flynn–Wall–Ozawa method and the trend of the results was in agreement with those obtained from the modified Avrami equation. These results show that the activity energy decreases with the addition of organic montmorillonite. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3822–3829, 2004     

Cure kinetics of neat and graphite-fiber-reinforced epoxy formulations

An investigation was carried out into the cure kinetics of neat and graphite fiber-reinforced epoxy formulation, composed of tetraglycidyl 4,4′-diaminodiphenyl methane (TGDDM) resin and diaminodiphenyl sulfone (DDS) curing agent. Two experimental techniques were employed: isothermal differential scanning calorimetry (IDSC) and dynamic differential scanning calorimetry (DDSC). An autocatalytic mechanism with the overall reaction rate order of 2 was found to describe adequately the cure kinetics, of the neat resin and the composite. All kinetic parameters, including reaction rate constants, activation energies and preexponential factors, were calculated and reported. The presence of graphite fibers in the composite had only a very small initial effect on the kinetics of cure.     

Ternary nanocomposites based on epoxy,modified silica,and tetrabutyl titanate: Morphology,characteristics, and kinetics of the curing process

In this study, the effects of unmodified nanosilica and nanosilica modified by an isopropyl tri[di(octyl) phosphate] titanate coupling agent (KR-12; m-nanosilica) on the structure, morphology, thermomechanical properties, and kinetics of the curing process of epoxy–tetrabutyl titanate (TBuT) nanocomposites were investigated. The viscosity, tensile strength, and flexural strength of the cured epoxy and cured epoxy–m-silica–TBuT nanocomposites were determined with a Brookfield viscometer and an Instron 5582-100KN universal machine. The morphology and gel fraction content of the nanocomposites were analyzed with transmission electron microscopy and scanning electron microscopy methods and Soxhlet extraction. The viscosity, mechanical properties, gel fraction content, and morphology results of the cured epoxy–m-silica–TBuT nanocomposites confirm that 5 wt % m-nanosilica was the most suitable for improving the dispersion of m-nanosilica in the epoxy matrix and the properties of these materials. The thermal behavior of the nanocomposites was determined by thermogravimetric analysis and differential scanning calorimetry (DSC) methods. On the basis of DSC data, the average value of the activation energy of the cured epoxy–TBuT system, calculated according to Flynn–Wall–Ozawa and Kissinger equations, was 67.893 kJ/mol. The calculation according to the Crane equation showed that the first-order kinetics complied with the curing reaction for the neat epoxy. When we introduced the unmodified nanosilica and modified nanosilica into the epoxy matrix, the order kinetics of the curing reaction for the nanocomposites also followed first-order kinetics, but the activation energy of their curing reaction decreased significantly. Some other properties were also investigated with dynamic mechanical analysis and Fourier transform infrared analysis and are discussed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47412.     

Preparation and properties of silanized vapor‐grown carbon nanofibers/epoxy shape memory nanocomposites

Silanized vapor‐grown carbon nanofiber/epoxy (silanized‐VGCNF/EP) shape memory polymer (SMP) nanocomposites are successfully fabricated by using a composite molding technology. The surface functionalization of VGCNF is performed using an acid treatment followed by a reaction with silane. The oxidation as well as silanization of VGCNF and silanized‐VGCNF/EP nanocomposites are systematically and explicitly characterized using various analytical methods. The influence of the silane‐functionalized VGCNF on the properties of VGCNF/EP nanocomposites is investigated using field emission scanning electronic microscopy (FE‐SEM) and a dynamic mechanical analysis (DMA). The shape memory properties of the silanized‐VGCNF/EP nanocomposites are evaluated by a fold‐deploy shape memory test. The results reveal that the silanized‐VGCNF is preferably dispersed in the epoxy resin matrix. Furthermore, the glass transition temperature of silanized‐VGCNF/EP nanocomposites is enhanced, and the shape memory properties of the silanized‐VGCNF/EP nanocomposites are significantly improved. POLYM. COMPOS., 35:412–417, 2014. © 2013 Society of Plastics Engineers     

Abrasion and nanoscratch in nanostructured epoxy coatings

A series of epoxy nanostructured coatings based on diglycidyl ether of bisphenol A (DGEBA) and an isophorone diamine crosslinker was prepared. Top‐down nanocomposites (3% nanofiller) were obtained by the mechanical dispersion of nanoalumina, silanized nanoalumina, and organomodified clays. Bottom‐up hybrids were instead achieved after the silanization of the DGEBA resin and after cocrosslinking with tetraethylorthosilicate through a self‐catalyzed sol–gel process. The curing process of the nanocomposites was studied by differential scanning calorimetry and suggested an overall increase in the crosslinking kinetics in the presence of nanoparticles. Other characterization included dynamic mechanical analysis, Buchholtz indentation hardness testing, and Taber abrasion testing. Finally, atomic force microscopy (AFM) techniques were used to study the surface morphology of the coatings and to produce nanoscratches. We concluded that, in the top‐down nanocomposites, there were minor changes in the surface hardness and a slight improvement in the abrasion resistance, whereas the nanoscratch resistance assessed by AFM tests showed significantly better performances in the hybrid coatings obtained through sol–gel chemistry. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

环氧树脂插层纳米复合材料固化动力学研究

运用自制的有机蒙脱土，采用浇模固化成型法制备环氧树脂／二乙烯三胺／有机蒙脱土纳米复合材料，对固化产物利用XRD（X射线衍射）分析有机蒙脱土的层间距变化，确定产物为插层型的纳米复合材料，并用DSC（差示扫描量热法）跟踪环氧树脂固化行为。运用Kissinger,Flynn-Wall-Ozawa,Crane方法对环氧树脂的固化反应过程进行分析，求出活化能和反应级数等动力学以在数。结果发现，加入有机化蒙脱土后使固化反应活化能和频率下降，从而有利于固化工艺的实现，便于纳米复合材料实际应用。     

SiAlON nanoparticles effect on the behaviour of epoxy coating

In this work, the influence of SiAlON nanoparticles loading level (0?C12?wt%) was investigated on the mechanical and chemical properties of epoxy resin-based nanocomposites coatings. The samples were characterized by fracture toughness, chemical, pull off, hardness and abrasion tests, followed by scanning electron microscopy of the fracture surfaces and sample surface after performing a chemical test. Nanoparticles were also characterized by transmission electron microscopy and linear light scattering analysis techniques. Epoxy resin coating based on bisphenol A was treated with polyamine hardener as a curing agent. Fracture toughness measurements were carried out using a single edge notched bend specimens within a three-point bending test at room temperature. Effect of SiAlON nanoparticles on the chemical resistance of epoxy resin was investigated by immersion of samples in 3.5?wt% NaCl solution at 85?°C for 60?days. Results indicated the enhancements in the mechanical properties and chemical resistance of epoxy nanocomposite due to the addition of small parts of SiAlON nanoparticles. The contents of samples with 3 and 5?wt% of SiAlON nanopowders have been considered as optimum contents compared to the other samples. They showed improvement in the crack propagation resistance in chemical solution and fracture toughness tests, both. Enhancment in abrasion resistance was found at either of 3 and 5?wt% SiAlON epoxy nanocomposite samples where they showed 59 and 34% abrasion resistance more than that of the neat resin, respectively.     

Development of high‐performance epoxy/clay nanocomposites by incorporating novel phosphonium modified montmorillonite

Novel organoclays were synthesized by several kinds of phosphonium cations to improve the dispersibility in matrix resin of composites and accelerate the curing of matrix resin. The possibility of the application for epoxy/clay nanocomposites and the thermal, mechanical, and adhesive properties were investigated. Furthermore, the structures and morphologies of the epoxy/clay nanocomposites were evaluated by transmission electron microscopy. Consequently, the corporation of organoclays with different types of phosphonium cations into the epoxy matrix led to different morphologies of the organoclay particles, and then the distribution changes of silicate layers in the epoxy resin influenced the physical properties of the nanocomposites. When high‐reactive phosphonium cations with epoxy groups were adopted, the clay particles were well exfoliated and dispersed. The epoxy/clay nanocomposite realized the high glass‐transition temperature (T_g) and low coefficient of thermal expansion (CTE) in comparison with those of neat epoxy resin. On the other hand, in the case of low‐reactive phoshonium cations, the dispersion states of clay particles were intercalated but not exfoliated. The intercalated clay did not influence the T_g and CTE of the nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermomechanical and barrier properties of UV‐cured epoxy/O‐montmorillonite nanocomposites

Mixtures of an epoxy resin and organophilic montmorillonites were subjected to ultraviolet (UV)‐induced photopolymerization. Two types of commercially available nanoclays, namely Cloisite 30B and Cloisite Na⁺, were modified through interaction with organic compatibilizers (dodecylsuccinic anhydride, octadecylamine, octadecyl alcohol, and octadecanoic acid). The modified nanoclays, dispersed in the liquid epoxy resin at 5 wt%, were photopolymerized to get nanocomposite films. The kinetics of the photopolymerization was evaluated by means of real‐time Fourier transform infrared spectroscopy. The modified nanoclays and their nanocomposites were characterized through X‐ray diffractometry; transmission electron microscopy showed the presence of intercalated and partially exfoliated morphologies in the nanocomposites. Thermogravimetric and dynamic‐mechanical analyses showed an increase of the thermal properties and an increase of the glass transition temperatures of the nanocomposites compared with that of the neat UV‐cured resin. Finally, the oxygen barrier properties of nanocomposite films, coated on a polyethyleneterephtalate substrate, were evaluated; the decrease of permeability was correlated with the degree of exfoliation of the nanocomposites. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Curing of epoxy resin with poly(m‐phenylene methylphosphonate)

The mechanism and kinetics of curing of epoxy resin with poly(m‐phenylene methylphosphonate) (PMP) was studied by extraction and swelling experiments, DSC, ³¹P NMR, and FTIR. It was shown that at linear heating of 20°C/min PMP cures bisphenol A type epoxy resin at 230–300°C, whereas in the presence of catalytic amount of 2‐methyl imidazole the curing occurs at 200–230°C. Under isothermal conditions, epoxy resin was cured with PMP after 40–70 min at 150°C. An unusual mechanism of curing due to opening and insertion of epoxy into the phosphonate bond was suggested. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4011–4022, 2006     

Curing kinetics of a novolac resin modified with oxidized multi‐walled carbon nanotubes

The influence of oxidized multi‐walled carbon nanotubes (o‐MWCNTs) on the curing kinetics of a novolac resin was studied by means of non‐isothermal differential scanning calorimetry. Regarding the kinetics issues, the high concentration of hydroxyl groups on the o‐MWCNTs slightly modified the curing reaction of the novolac resin, shifting the differential scanning calorimetry exothermic peak to higher temperatures. The effective activation energy of the curing reaction was calculated by the isoconversional Kissinger‐Akahira‐Sunose method and increased by the presence of o‐MWCNTs with respect to neat novolac. This change was attributed to the increase of the material viscosity. In addition, thermogravimetric analysis revealed that nanocomposites samples containing 0.4 and 1.0 wt% o‐MWCNTs presented increased char yield values, indicating an improvement of flame retardancy.     

Sepiolite‐reinforced epoxy nanocomposites: Thermal,mechanical, and morphological behavior

A bisphenol A‐based epoxy resin was modified with pristine sepiolite and an organically surface‐modified sepiolite and thermally cured using two different curing agents: an aliphatic and a cycloaromatic diamine. The nanocomposites were characterized by dynamic mechanical analysis (DMA), rheology, thermogravimetric analysis (TGA), and electron microscopy. The initial sepiolite–epoxy mixtures show a better dispersion for the sepiolite‐modified system that forms a percolation network structure. Mechanical properties have also been determined. The flexural modulus of the epoxy matrix slightly increases by the incorporation of the organophilic sepiolite. The flexural strength of the sepiolite‐modified resin cured with the aliphatic diamine increased by 10%, while the sepiolite‐modified resin cured with the cycloaromatic diamine resulted in a lower flexural strength, as compared with the unmodified resin. Electron micrographs revealed a better nanodispersion of the sepiolite in the epoxy matrix for the organophilic modified sepiolite nanocomposite. The initial thermal decomposition temperature did not change significantly with the addition of sepiolite, whereas mechanical properties were affected. The reduced flexural strength was attributed to the stress concentrations caused by the sepiolite modifier. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011