Improved impact strength of epoxy by the addition of functionalized multiwalled carbon nanotubes and reactive diluent

Multiwalled carbon nanotubes (MWCNTs), both oxidized and amine functionalized (triethylenetetramine—TETA), have been used to improve the mechanical properties of nanocomposites based on epoxy resin. The TGA and XPS analysis allowed the evaluation of the degree of chemical modification on MWCNTs. Nanocomposites were manufactured by a three‐roll milling process with 0.1, 0.5, and 1.0 wt % of MWCNT–COOH and MWCNT–COTETA. A series of nanocomposites with 5.0 wt % of reactive diluent was also prepared. Tensile and impact tests were conducted to evaluate the effects of the nanofillers and diluent on the mechanical properties of the nanocomposites. The results showed higher gains (258% increase) in the impact strength for nanocomposites manufactured with aminated MWCNTs. Optical microscopy (OM), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) were used to investigate the overall filler distribution, the dispersion of individual nanotubes, and the interface adhesion on the nanocomposites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42587.     

Thermal stability and molecular interaction of polyurethane nanocomposites prepared by in situ polymerization with functionalized multiwalled carbon nanotubes

Polyurethane (PU) nanocomposites were prepared through conventional and in situ methods with multiwalled carbon nanotubes (MWNTs) functionalized with poly(ϵ-caprolactone). The thermal degradation and stability of PU–MWNT nanocomposites were investigated with nonisothermal thermogravimetry and were explained in terms of the interaction between MWNTs and PU molecules with Fourier transform infrared spectroscopy. The difference in thermal stability between the conventional and in situ nanocomposites was also compared. The thermal degradation of all the nanocomposite samples took place in two stages and followed a first-order reaction. The degradation temperature of the in situ nanocomposites was higher than that of the conventional nanocomposites with the same loading of MWNTs. The activation energy at 10% degradation and the half-life period were also higher in the in situ nanocomposites compared to the conventional nanocomposites. Such higher thermal stability of the in situ nanocomposites was ascribed to covalent bond formation between MWNTs and PU chains, which could result in better dispersion of MWNTs in the PU matrix for the in situ nanocomposites than for the conventional nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Lifetime prediction of the epoxy system DGEBA (n = 0)/1,2‐DCH modified with an epoxy reactive diluent by thermogravimetric analysis

Thermogravimetric analysis was used to predict the lifetime of two three‐component systems of diglycidyl ether of bisphenol A (n = 0)/1,2‐diamine cyclohexane [DGEBA (n = 0)/1,2‐DCH] modified with different concentrations of an epoxy reactive diluent, vinylcyclohexene dioxide (VCHD). Experimental results were treated using two methods. The first method was independent of the degradation mechanism, and the second was based on the thermodegradation kinetic mechanism. The activation energies of the reaction were determined using the Flynn–Wall–Ozawa method. These values were compared with those obtained using Kissinger's method. From experimental results it was found that the optimum temperature of service for these materials were different, so one or the other must be selected, depending on the application temperature considered. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3835–3839, 2003     

Thermal degradation kinetics of a commercial epoxy resin—Comparative analysis of parameter estimation methods

The thermal degradation behavior of a commercial epoxy resin, EpoFix® (Struers), has been investigated by thermogravimetry (TG), differential thermal gravimetry (DTG), and differential thermal analysis (DTA) under nonisothermal conditions in an argon atmosphere. Different methods (Kissinger, Flynn–Wall–Ozawa (FWO), Friedman isoconversion methods, and nonlinear least‐squares (NLSQ) estimation method) have been used to analyze the thermal degradation process and determine the apparent kinetic parameters. The methods produce similar results in terms of activation energy estimations. Nevertheless, the NLSQ method has several advantages over the other methods in terms of both characterizing the activation energy and modeling the thermal degradation—i.e., including this model in a resin degradation process simulation. However, it is interesting to combine the NLSQ method with other isoconversion methods: they can reflect the dependence and variability of the activation energies during pyrolysis processes, while providing a good starting point for a nonlinear procedure, especially with respect to the activation energy E. This work is the first step (apparent kinetic reaction) of complete simulation of experimental oven of degradation of epoxy resin coating of impregnate nuclear fuel sample. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42201.     

Dielectric properties of epoxy composites with modified multiwalled carbon nanotubes

We report here a high dielectric percolative polymer nanocomposite, fabricated by a combination of triethylene-tetramine (TETA) modified multiwalled carbon nanotube (named as TETA-MWNT) within epoxy resin matrix. In this composite system, with various TETA-MWNT volume fractions, the dielectric constant (K) is well fitted by the scaling law of the percolation theory with the percolation threshold f _c is 0.042 and the critical exponent p is 0.786. At 1,000 Hz of room temperature, the value of the dielectric constant is as high as 421 with the TETA-MWNT content of 4.14vol%, which is almost 60 times higher than that of epoxy resin. In contrast, a simple blend of pristine MWNT in epoxy composite shows evident lower dielectric constant and much higher loss with the same volume fraction.     

Thermal stability and kinetics analysis of rubber‐modified epoxy resin by high‐resolution thermogravimetric analysis

A dynamic heating rate mode of high‐resolution thermogravimetric analysis was used to study the thermal and thermal‐oxidative stability, as well as kinetics analyses, of a model liquid rubber‐modified epoxy resin, Ep/CTBN, made up of bisphenol A diglycidyl ether‐based epoxy and carboxyl‐terminated butadiene acrylonitrile rubber (CTBN). Results show that the thermal degradation of Ep/CTBN resin in nitrogen and air consists of two and three independent steps, respectively. Moreover, Ep/CTBN has a higher initial degradation temperature and higher activation energy than those of pure epoxy resin in both gases, indicating that the addition of CTBN to epoxy can improve the thermal and thermal‐oxidative stability of pristine epoxy resin. Kinetic parameters such as activation energy, reaction order, and preexponential factor of each degradation step of both Ep/CTBN and pure epoxy resins in air and nitrogen were calculated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3594–3600, 2003     

Cure behavior and thermal stability analysis of multiwalled carbon nanotube/epoxy resin nanocomposites

As‐received multiwalled carbon nanotubes (MWCNTs) were first treated by a 3 : 1 (v/v) mixture of concentrated H₂SO₄/HNO₃ and further functionalized by ethylenediamine/dicyclohexylcarbodiimide/tetrahydrofuran solution. MWCNT/epoxy nanocomposites were prepared. Their cure behaviors were investigated by dynamic differential scanning calorimetry. Quantitative analysis of the activation energy as a function of the degree of curing was carried out by the Flynn‐Wall‐Ozawa method. The fitted multiple regression equations for values of the activation energy of different systems were obtained. MWCNTs have the retardation effect on the cure reaction of epoxy resin, while the functional groups on the surface of amine‐modified MWCNTs could accelerate the cure reactions. Thermal stability was studied by thermogravimetric analysis. The filling of amine‐modified MWCNTs is beneficial to lower the cure activation energy and improve thermal stability of the nanocomposite. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Electrical conductivity of chemically modified multiwalled carbon nanotube/epoxy composites

The electrical conductivity of oxidized multiwalled carbon nanotubes (MWNT)/epoxy composites is investigated with respect to the chemical treatment of the MWNT. The oxidation is carried out by refluxing the as-received MWNT in concentrated HNO₃ and H₂O₂/NH₄OH solutions, respectively, under several different treatment conditions. The oxidized MWNT are negatively charged and functionalized with carboxylic groups by both solutions. The MWNT oxidized under severe conditions are well purified, but their crystalline structures are partially damaged. It is recognized that the damage to the MWNT has considerable influence on the electrical properties of the MWNT composites, causing the electrical conductivity to be lowered at a low content of MWNT and the percolation threshold to be raised. The MWNT oxidized by the mixture of H₂O₂ and NH₄OH solution provides epoxy composites with a higher conductivity than those produced with the MWNT oxidized by nitric acid over the whole range of MWNT, independently of the oxidation conditions.     

Mechanical properties of carbon fiber reinforced bisphenol A dicyanate ester composites modified with multiwalled carbon nanotubes

A novel electrophoretic deposition (EPD) method was employed for grafting multiwalled carbon nanotubes (MWCNTs) on carbon fibers, which, after impregnation with bisphenol A dicyanate ester (BADCy), synergistically reinforced BADCy matrix composites (CNT‐C/BADCy). The effect of MWCNT presence on the mechanical properties of the composites was investigated. Composite tensile strength increased by 45.2% for an EPD duration of 2 min, while flexural strength exhibited a decreasing trend with EPD duration. Optical microscopy revealed that the existence of MWCNTs enhanced the fiber‐matrix interface while a large number of CNTs were observed to have pulled‐out from the matrix, a finding which explained the observed tensile strength increase in terms of energy dissipation by the specific toughening mechanism. The flexural strength decrease of the composites with CNTs as compared to specimens without nanotubes was found linked to the increased stress concentration in the BADCy matrix due to tube presence which weakens the adhesion between carbon fabrics. In a word, carbon nanotubes will enhance the micro interface and weaken the macro interface of the composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45100.     

Reinforcement of epoxy resins with multi-walled carbon nanotubes for enhancing cryogenic mechanical properties

Epoxy resins are widely applied in cryogenic engineering and their cryogenic mechanical properties as important parameters have to be improved to meet the high requirements by cryogenic engineering applications. Carbon nanotubes (CNTs) are regarded as exceptional reinforcements for polymers. However, poor carbon nanotube (CNT)–polymer interfacial bonding leads to the unexpected low reinforcing efficiency. This paper presents a study on the cryogenic mechanical properties of multi-walled carbon nanotube reinforced epoxy nanocomposites, which are prepared by adding multi-walled carbon nanotubes (MWCNTs) to diglycidyl ether of bisphenol-F epoxy via the ultrasonic technique. When the temperature decreases from room temperature to liquid nitrogen temperature (77 K), a strong CNT–epoxy interfacial bonding is observed due to the thermal contraction of epoxy matrix because of the big differences in thermal expansion coefficients of epoxy and MWCNTs, resulting in a higher reinforcing efficiency. Moreover, synthetic sequence leads to selective dispersion of MWCNTs in the brittle primary phase but not in the soft second phase in the two phase epoxy matrix. Consequently, the cryogenic tensile strength, Young's modulus, failure strain and impact strength at 77 K are all enhanced by the addition of MWCNTs at appropriate contents. The results suggest that CNTs are promising reinforcements for enhancing the cryogenic mechanical properties of epoxy resins that have potential applications in cryogenic engineering areas.     

Toughening of cycloaliphatic epoxy resin by multiwalled carbon nanotubes

The toughness of cycloaliphatic epoxy resin 3,4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexane carboxylate (ERL‐4221) has been improved by using multiwalled carbon nanotubes (MWCNTs) treated by mixed acids. The MWCNT/ERL‐4221 composites were characterized by Raman spectroscopy and their mechanical properties were investigated. A significant increase in the tensile strength of the composite from 31.9 to 55.9 MPa was obtained by adding only 0.05 wt % of MWCNTs. And a loading of 0.5 wt % MWCNTs resulted in an optimum tensile strength and cracking energy, 62.0 MPa and 490 N cm, respectively. Investigation on the morphology of fracture surface of the composites by field emission scanning electron microscopy demonstrated the crack pinning‐front bowing and bridging mechanisms of toughening. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Potentiometric stripping analysis of bismuth based on carbon paste electrode modified with cryptand [2.2.1] and multiwalled carbon nanotubes

An electrochemical method based on potentiometric stripping analysis (PSA) employing a cryptand [2.2.1] (CRY) and carbon nanotube (CNT) modified paste electrode (CRY-CNT-PE) has been proposed for the subnanomolar determination of bismuth. The characterization of the electrode surface has been carried out by means of scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronocoulometry (CC). It was observed that by employing CRY-CNT-PE, a 9-fold enhancement in the PSA signal (dt/dE) was observed as compared to plain carbon paste electrode (PCPE). Under the optimized conditions, dt/dE (s/V) was proportional to the Bi(III) concentration in the range of 5.55 × 10⁻⁸ to 9.79 × 10⁻¹¹ M (r = 0.9990) with the detection limit (S/N = 3) of 3.17 × 10⁻¹¹ M. The practical analytical utilities of the modified electrode were demonstrated by the determination of bismuth in pharmaceutical formulations, human hair, sea water, urine and blood serum samples. The prepared modified electrode showed several advantages, such as a simple preparation method, high sensitivity, very low detection limits and excellent reproducibility. Moreover, the results obtained for bismuth analysis in commercial and real samples using CRY-CNT-PE and those obtained by atomic absorption spectroscopy (AAS) are in agreement at the 95% confidence level.     

Cure study of epoxy resin reinforced with multiwalled carbon nanotubes by Raman and luminescence spectroscopy

Carbon nanotubes (CNTs) were annealed at high temperature under vacuum, followed by a chemical treatment using acids and ethylenediamine. The presence of acid and amine chemical groups on CNT surface was confirmed by infrared spectra. The amount of iron remaining in the CNTs after the treatments was evaluated by thermogravimetry and by energy dispersion spectroscopy. The crystalline property of CNTs was evaluated by Raman spectroscopy, showing that the acid treatment performed after the thermal treatment did not damage the nanotubes walls. Micrographs showed that the most dispersed CNTs were obtained after the amine functionalization step. The curing process of the neat resin and composites was studied by Raman and Luminescence spectroscopies and both techniques showed similar results. The presence of CNTs, functionalized or not, increased the cure degree of the epoxy resin when the same cure time was used in the comparison. Nanocomposites synthesized with annealed CNT and acid‐treated CNT had cure rates considerably higher at the beginning of the reaction. The difference in the cure rate was explained by means of the sample's homogeneity and the presence of chemical groups. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Pseudoreinforcement effect of multiwalled carbon nanotubes in epoxy matrix composites

The carbon nanotube possesses outstanding physical properties. Theoretically, adding carbon nanotubes into a polymer matrix can remarkably improve the mechanical properties of the polymer matrix. In the present work, a series of composites was prepared by incorporating multiwalled carbon nanotubes (MWNTs) into an epoxy resin. The influences of MWNT content and curing temperature on the flexural properties of the epoxy resin were investigated. The results showed that a very low MWNT content should be used to ensure homogeneous dispersion of MWNTs in the epoxy matrix. A higher MWNT content may lead to deteriorated mechanical properties of the composites because of the aggregation of MWNTs. A decline in the flexural properties of the neat epoxy resin with increasing curing temperature was found. However, under the same curing conditions, improvement in flexural properties was observed for the composite with the low MWNT content and a mild curing temperature. The improvement was far beyond the predictions of the traditional short‐fiber composite theory. In fact, this improvement should be attributed to the retarding effect of MWNTs on the curing reaction of epoxy matrix. Therefore, the improvement in the flexural properties was only a pseudoreinforcement effect, not a nano‐reinforcement effect of the MWNTs on the epoxy resin. Perhaps, it is better for MWNTs to be used as functional fillers, such as electrical or thermal conductive fillers, than as reinforcements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3664–3672, 2006     

Isothermal crystallization kinetics and melting behavior of multiwalled carbon nanotubes/polyamide‐6 composites

Pristine and functionalized multiwalled carbon nanotubes (MWNTs) were used to fabricate polyamide 6 (PA6) composites through melt blending. The functionalized MWNTs were obtained by grafting 1,6‐hexamethylenediamine (HMD) onto the pristine MWNTs to improve their compatibility with PA6 matrix. The effect of MWNTs on the isothermal crystallization and melting behavior of PA6 was investigated by differential scanning calorimetry (DSC) and X‐ray diffraction (XRD). The Avrami and Lauritzen–Hoffmann equations are used to describe the isothermal crystallization kinetics. The values of the Avrami exponent found for neat PA6, the pristine MWNTs/PA6 and functionalized MWNTs/PA6 composite samples are about 4.0, 1.7, and 2.3, respectively. The activation energies are determined by the Arrhenius method, which is lower for the composites, ?320.52 KJ/mol for pristine MWNTs/PA6 and ?293.83 KJ/mol for functionalized MWNTs/PA6, than that for the neat PA6 (?284.71 KJ/mol). The following melting behavior reveals that all the isothermally crystallized samples exhibit triple melting endotherms at lower crystallization temperature and double melting endotherms at higher crystallization temperature. The multiple melting endotherms are mainly caused by the recrystallization of PA6 during heating. The resulting equilibrium melting temperature is lower for the composites than for neat PA6. In addition, polarizing microscopy (PLM) and small angle light scanning (SALS) were used to study the spherulite morphology. The results show that the MWNTs reduce the spherulite radius of PA6. This reduction is more significant for pristine MWNTs. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synergetic effects on the mechanical and fracture properties of epoxy composites with multiscale reinforcements: Carbon nanotubes and short carbon fibers

The ball‐milling/liquid‐phase oxidation (BMLPO) method was used to fabricate surface‐modified short carbon fibers (SCFs). Multiscale epoxy composites reinforced with a combination of SCFs and multiwalled carbon nanotubes (MWNTs) were prepared. Atomic force microscopy observations and contact angle measurement were used to investigate the modification effect of the BMLPO method. Mechanical tests and scanning electron microscopy observations were used to study the effects of the SCFs, MWNTs, and their combination on tensile properties, impact strength, and fracture toughness of the epoxy composites. The results show that the surface roughness of the SCFs after BMLPO treatment increased, and the wettability of the SCFs was improved as well. The combined use of the SCFs and MWNTs had a synergetic effect on the tensile strength, fracture toughness, and impact strength of the epoxy composites. The addition of MWNTs promoted the plastic deformation of the epoxy matrix and decreased the stress‐concentration level near the SCF/matrix interface; these were considered the main causes of the synergetic effect. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43500.     

Thermal conductivity and dynamic mechanical property of glycidyl methacrylate‐grafted multiwalled carbon nanotube/epoxy composites

The well dispersed multiwalled carbon nanotube (MWCNT)/epoxy composites were prepared by functionalization of the MWCNT surfaces with glycidyl methacrylate (GMA). The morphology and thermal properties of the epoxy nanocomposites were investigated and compared with the surface characteristics of MWCNTs. GMA‐grafted MWCNTs improved the dispersion and interfacial adhesion in epoxy resin, and enhanced the network structure. The storage modulus of 3 phr GMA‐MWCNTs/epoxy composites at 50°C increased from 0.32 GPa to 2.87 GPa (enhanced by 799%) and the increased tanδ from 50.5°C to 61.7°C (increased by 11.2°C) comparing with neat epoxy resin, respectively. Furthermore, the thermal conductivity of 3 phr GMA‐MWCNTs/epoxy composite is increased by 183%, from 0.2042 W/mK (neat epoxy) to 0.5781 W/mK. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Controlled dispersion of multiwalled carbon nanotubes modified by hyperbranched polylysine

Hyperbranched polymers have been found effective in controlling the dispersibility of carbon nanotubes in aqueous solutions. In this study, hyperbranched polylysine (HBPL) was synthesized using lysine and N,N′‐methylenebisacrylamide as precursors via Michael addition. The HBPL then was used to noncovalently modify multiwalled carbon nanotubes (MWCNTs) to prepare MWCNTs‐HBPL. The obtained MWCNTs‐HBPL composites were characterized using FTIR spectroscopy, Raman spectroscopy, thermogravimetric analysis, and scanning electron microscopy. The results showed that the HBPL was successfully attached to the surface of MWCNTs via noncovalent interactions. The dispersibility of the MWCNTs‐HBPL composites in aqueous solutions was investigated using digital photographs, ultraviolet–visible absorption spectroscopy, and zeta potential measurements. The results demonstrated that both the mass ratio of MWCNT to HBPL and the pH of the solution had a significant impact on the dispersibility of the MWCNTs/HBPL solution, suggesting that HBPL treatment is an effective method of controlling the dispersibility of MWCNTs in aqueous solutions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46249.     

Preparation and properties of plasticized starch/multiwalled carbon nanotubes composites

In this work we have studied the utilization of multiwalled carbon nanotubes (MWCNTs) as filler‐reinforcement to improve the performance of plasticized starch (PS). The PS/MWCNTs nanocomposites were successfully prepared by a simple method of solution casting and evaporation. The morphology, thermal behavior, and mechanical properties of the films were investigated by means of scanning electron microscopy, wide‐angle X‐ray diffraction, differential scanning calorimetry, and tensile testing. The results indicated that the MWCNTs dispersed homogeneously in the PS matrix and formed strong hydrogen bonding with PS molecules. Compared with the pure PS, the tensile strength and Young's modulus of the nanocomposites were enhanced significantly from 2.85 to 4.73 MPa and from 20.74 to 39.18 MPa with an increase in MWCNTs content from 0 to 3.0 wt %, respectively. The value of elongation at break of the nanocomposites was higher than that of PS and reached a maximum value as the MWCNTs content was at 1.0 wt %. Besides the improvement of mechanical properties, the incorporation of MWCNTs into the PS matrix also led to a decrease of water sensitivity of the PS‐based materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Thermal properties and stability of n‐octadecane based composites containing multiwalled carbon nanotubes

In this study, multiwalled carbon nanotubes (MWNT) were added to n‐octadecane at weight percentages of 1.25, 2.5, 5, 10 and changes of thermal properties of n‐octadecane were analyzed. Structural characterization of the materials was carried out by transmission electron microscope (TEM) and optical microscope. Thermal properties of n‐octadecane and its composites were evaluated through differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The thermal measurements show that the highest contribution to latent heat absorbing capacity with 18% was provided by the addition of 1.25% MWNT to n‐octadecane. The thermal properties and the thermal stability of pure n‐octadecane and its composites with MWNT were also investigated by subjecting the samples to 1440 melting‐cooling cycles. The sample with 1.25% MWNT content also showed the best thermal stability. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers