Kinetics studies on the accelerated curing of liquid crystalline epoxy resin/multiwalled carbon nanotube nanocomposites

A new class of nanocomposite has been fabricated from liquid crystalline (LC) epoxy resin of 4,4′‐bis(2,3‐epoxypropoxy) biphenyl (BP), 4,4′‐diamino‐diphenyl sulfone (DDS), and multiwalled carbon nanotubes (CNTs). The surface of the CNTs was functionalized by LC epoxy resin (ef‐CNT). The ef‐CNT can be blended well with the BP that is further cured with an equivalent of DDS to form nanocomposite. We have studied the curing kinetics of this nanocomposite using isothermal and nonisothermal differential scanning calorimetry (DSC). The dependence of the conversion on time can fit into the autocatalytic model before the vitrification, and then it becomes diffusion control process. The reaction rate increases and the activation energy decreases with increasing concentration of the ef‐CNT. At 10 wt % of ef‐CNT, the activation energy of nanocomposite curing is lowered by about 20% when compared with the neat BP/DDS resin. If the ef‐CNT was replaced by thermal‐insulating TiO₂ nanorods on the same weight basis, the decrease of activation energy was not observed. The result indicates the accelerating effect on the nanocomposite was raised from the high‐thermal conductivity of CNT and aligned LC epoxy resin. However, at ef‐CNT concentration higher than 2 wt %, the accelerating effect of ef‐CNTs also antedates the vitrification and turns the reaction to diffusion control driven. As the molecular motions are limited, the degree of cure is lowered. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Thermal curing behavior of MWCNT modified vinyl ester‐polyester resin suspensions prepared with 3‐roll milling technique

This study aims to investigate the curing behavior of a vinyl ester‐polyester resin suspensions containing 0.3 wt % of multiwalled carbon nanotubes with and without amine functional groups (MWCNTs and MWCNT‐NH₂). For this purpose, various analytical techniques, including Differential Scanning Calorimetry (DSC), Fourier infrared spectroscopy (FTIR), Raman Spectroscopy, and Thermo Gravimetric Analyzer (TGA) were conducted. The resin suspensions with carbon nanotubes (CNTs) were prepared via 3‐roll milling technique. DSC measurements showed that resin suspensions containing CNTs exhibited higher heat of cure (Q), besides lower activation energy (E_a) when compared with neat resin. For the sake of simplicity of interpretation, FTIR investigations were performed on neat vinyl ester resin suspensions containing the same amount of CNTs as resin. As a result, the individual fractional conversion rates of styrene and vinyl ester were interestingly found to be altered dependent on MWCNTs and MWCNT‐NH₂. The findings obtained from RS measurements of the cured samples are highly proportional to those obtained from FTIR measurements. TGA measurements revealed that CNT modified nanocomposites have higher activation energy of degradation (E_d) compared with the cured polymer. The findings obtained revealed that CNTs with and without amine functional groups alter overall thermal curing response of the surrounding matrix resin, which may probably impart distinctive characteristics to mechanical behavior of the corresponding nanocomposites achieved. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1511–1522, 2009     

The effect of different treatment methods of multiwalled carbon nanotubes on thermal and flexural properties of their epoxy nanocomposites

Multiwalled carbon nanotubes (MWCNTs) were oxidized using four different acid‐treatment methods followed by their functionalization with 3‐aminopropyltriethoxysilane (3‐APTES). Diglycidyl ether of bisphenol A (DGEBA) nanocomposites with unmodified and silanized MWCNTs (0.2 wt %) were prepared by a cast molding method. The effect of functionalization of MWCNTs on thermal, flexural, and morphological properties of the epoxy nanocomposites were studied. The epoxy/MWCNTs nanocomposites were characterized by thermogravimetric analysis, flexural testing, and field emission electron microscopic analysis. The results showed that the silanization of MWCNTs which were oxidized by a two‐step process using nitric acid and hydrochloric acid showed better thermal and flexural properties due to good interfacial adhesion between MWCNTs and the epoxy matrix. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1175–1184, 2010     

Incorporation of carbon nanotubes into polyethylene by high energy ball milling: Morphology and physical properties

High energy ball milling (HEBM) was utilized, as an innovative process, to incorporate carbon nanotubes (CNTs) into a polyethylene (PE) matrix avoiding: high temperatures, solvents, ultrasonication, chemical modification of carbon nanotubes. Composites with 1, 2, 3, 5, and 10 wt % of carbon nanotubes were prepared. Films were obtained melting the powders in a hot press. Morphology and physical properties (thermal, mechanical, electrical properties) were evaluated. The used processing conditions allowed to obtain a satisfactory level of dispersion of CNTs into the PE matrix with a consequent improvement of the physical properties of the samples. The thermal degradation was significantly delayed already with 1–2% wt of CNTs. The mechanical properties resulted greatly improved for low filler content (up to 3% wt). The electrical measurements showed a percolation threshold in the range 1–3 wt % of CNTs. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 597–606, 2007     

A Review Featuring Fabrication,Properties and Applications of Carbon Nanotubes (CNTs) Reinforced Polymer and Epoxy Nanocomposites

Carbon nanotubes (CNTs) have long been recognized as the stiffest and strongest man-made material known to date.In addition,their high electrical conductivity has roused interest in the areas of electrical appliances and communication related applications.However,due to their miniature size,the excellent properties of these nanostructures can only be exploited if they are homogeneously embedded into light-weight matrices as those offered by a whole series of engineering polymers.In order to enhance their chemical affinity to engineering polymer matrices,chemical modification of the graphitic sidewalls and tips is necessary.The mechanical and electrical properties to date of a whole range of nanocomposites of various carbon nanotube contents are also reviewed in this attempt to facilitate progress in this emerging area.Recently,carbonaceous nano-fillers such as graphene and carbon nanotubes (CNTs) play a promising role due to their better structural and functional properties and broad range of applications in every field.Since CNTs usually form stabilized bundles due to van der Waals interactions,they are extremely difficult to disperse and align in a polymer matrix.The biggest issues in the preparation of CNTs reinforced composites reside in efficient dispersion of CNTs into a polymer matrix,the assessment of the dispersion,and the alignment and control of the CNTs in the matrix.An overview of various CNT functionalization methods is given.In particular,CNT functionalization using click chemistry and the preparation of CNT composites employing hyperbranched polymers are stressed as potential techniques to achieve good CNT dispersion.In addition,discussions on mechanical,thermal,electrical,electrochemical and applications ofpolymer/CNT composites are also included.     

Competitive absorption of epoxy monomers on carbon nanotube: A molecular simulation study

Position restrained (PR) molecular dynamics (MD) simulations were carried out on the bulk models for the two composite systems including epoxy monomers and carbon nanotube (CNT). The pair energies and the radial distribution functions (RDFs) were computed to evaluate the relative strength of the epoxy monomers binding to the CNT. It is found that the aromatic amine binds more strongly to the CNT than does the aliphatic amine. A vivid view indicates the aromatic rings tend to form π‐stacking with the CNT, and the compounds with aromatic rings prefer to wrap the CNT. These simulated results are in good agreement with those obtained previously from the vacuum models. This work demonstrates that curing agents affect the interactions between epoxy resin and CNT. Other comparisons of relative binding strength of epoxy monomers also depend upon the temperature. Further analyses suggest that the aliphatic amine exhibits more strong interactions with epoxy resin than does the aromatic amine, mainly due to the presence of hydrogen bonds (HBs) between them. Thus, the ultimate performance of epoxy‐CNT polymer nanocomposites should be affected by the two reverse interactions. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011.     

Dissolution of MWCNTs by using polyoxadiazoles,and highly effective reinforcement of their composite films

Nonmodified multiwalled carbon nanotubes (MWCNTs)/sulfonated polyoxadiazole (sPOD) nanocomposites are successfully prepared by a facile solution route. The pristine MWCNTs are dispersed in a sPOD solution, and the mixtures are fabricated into thin films by solution casting. The homogeneous dispersion of nanotubes in the composites is confirmed by transmission electron microscopy. The mechanical properties, thermal stability, and electrical conductivity are investigated. Tensile strength, elongation at break, and tensile energy to break are shown to increase by more than 28, 45, and 73%, respectively, by incorporating up to 1.0 wt % pristine MWCNTs. The experimental values for sPOD/MWCNTs composite stiffness are compared with Halpin‐Tsai and modified Halpin‐Tsai predictions. The storage modulus is found to increase up to 10% at low CNT loading. The composite films, which have an outstanding thermal stability, show an increase of up to 57 °C in the initial degradation temperature. The addition of 1.0 wt % MWCNTs increases the electrical conductivity of the sPOD matrix by two orders of magnitude. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

原位法制备纳米银修饰碳纳米管环氧导电复合材料

将碳纳米管(CNTs)和乙酸银同时引入到环氧树脂-咪唑固化体系中,在固化过程中原位热降解银-咪唑复合物生成纳米银修饰碳纳米管,差示扫描量热仪(DSC)表明改性碳纳米管对环氧固化有一定的促进作用.采用X-射线衍射(XRD)表征了乙酸银和咪唑配合物[Ag(2E4MZ)2]Ac的结构,并提出了原位降解生成纳米银的机理.XRD结果表明,单独的乙酸银-咪唑配合物热降解生成的纳米银粒径为21-24nm,而配合物在环氧基体中生成的纳米银粒径为11-13nm.添加80%(质量分数)片状微米银粉制备的纳米银/碳纳米管环氧导电复合材料其体积电阻率低达9×10-5Ω·cm.当纳米银和碳纳米管质量比为80:20时,复合材料导电性和剪切强度达到最佳;采用扫描电镜(SEM)表征了复合材料的形貌结构.     

Critical aspects related to processing of carbon nanotube/unsaturated thermoset polyester nanocomposites

Carbon nanotubes (CNTs) have outstanding mechanical, thermal and electrical properties. As a result, particular interest has been recently given in exploiting these properties by incorporating carbon nanotubes into some form of matrix. Although unsaturated polyesters with styrene have widespread use in the industrial applications, surprisingly there is no study in the literature about CNT/thermoset polyester nanocomposite systems. In the present paper, we underline some important issues and limitations during the processing of unsaturated polyester resins with different types of carbon nanotubes. In that manner, 3-roll mill and sonication techniques were comparatively evaluated to process nanocomposites made of CNTs with and without amine (NH₂) functional groups and polyesters. It was found that styrene evaporation from the polyester resin system was a critical issue for nanocomposite processing. Rheological behaviour of the suspensions containing CNTs and tensile strengths of their resulting nanocomposites were characterized. CNT/polyester suspensions exhibited a shear thinning behaviour, while polyester resin blends act as a Newtonian fluid. It was also found that nanotubes with amine functional groups have better tensile strength, as compared to those with untreated CNTs. Transmission electron microscopy (TEM) was also employed to reveal the degree of dispersion of CNTs in the matrix.     

Thermal degradation and kinetic analysis of biodegradable PBS/multiwalled carbon nanotube nanocomposites

In this study, carbon nanotubes (CNTs) were first modified using N,N′‐ dicyclohexylcarbodiimide (DCC) dehydrating agents. Subsequently, the poly(butylene succinate)/multiwalled carbon nanotube (PBS/MWNTs) nanocomposites were prepared through facile melt blending. Thermal degradation of these PBS/MWNT nanocomposites was investigated; the kinetic parameters of degradation were calculated using the Coats and Redfern, Ozawa, and Horowitz and Metzger methods, respectively. It was found that the degradation reaction mechanism of PBS and the CNT‐C18 containing nanocomposites at lower temperature was likely to produce an F1 model through reaction of random chain cleavage (cis‐elimination). However, the reaction mechanism at higher temperature was likely to be a D1 model because of the dominant diffusion control effect. Moreover, it was found that the activation energies of CNT‐C18‐containing PBS nanocomposites were first increased with the content of CNT‐C18, but then decreased after the content was larger than 0.5 wt % for all models at differing heating rates. This may be due to the formation of a conductive network of CNTs in the polymer matrix at higher content of CNTs, which lead to better heat and electrical conductivity. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1231–1239, 2009     

形状记忆聚偏氟乙烯/丙烯酸酯/碳纳米管纳米复合材料的导电及导热性能

利用聚偏氟乙烯（PVDF）微小结晶的物理交联点作用,制备了形状记忆性能优异的聚偏氟乙烯/丙烯酸酯聚合物（PVDF/ACM）共混材料,为提高其导电及导热性能,于其中引入了碳纳米管（CNT）,系统研究了PVDF/ACM/CNT三元体系纳米复合材料的导热及导电性能。 结果表明,碳纳米管在PVDF/ACM体系中分散均匀;在基本保持其形状记忆性能的前提下,碳纳米管的加入使材料导热性能及导电性能有较大程度的提高：质量分数为4%的CNT使材料25 ℃的电阻值降低至5000 Ω/square,导热系数提高至0.157 W/(m·K)。     

An infiltration method for preparing single‐wall nanotube/epoxy composites with improved thermal conductivity

Recent studies of SWNT/polymer nanocomposites identify the large interfacial thermal resistance at nanotube/nanotube junctions as a primary cause for the only modest increases in thermal conductivity relative to the polymer matrix. To reduce this interfacial thermal resistance, we prepared a freestanding nanotube framework by removing the polymer matrix from a 1 wt % SWNT/PMMA composite by nitrogen gasification and then infiltrated it with epoxy resin and cured. The SWNT/epoxy composite made by this infiltration method has a micron‐scale, bicontinuous morphology and much improved thermal conductivity (220% relative to epoxy) due to the more effective heat transfer within the nanotube‐rich phase. By applying a linear mixing rule to the bicontinuous composite, we conclude that even at high loadings the nanotube framework more effectively transports phonons than well‐dispersed SWNT bundles. Contrary to the widely accepted approaches, these findings suggest that better thermal and electrical conductivities can be accomplished via heterogeneous distributions of SWNT in polymer matrices. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1513–1519, 2006     

Novel conductive nanocomposites from perfluoropolyether waterborne polyurethanes and carbon nanotubes

The exceptional electrical conductivity of carbon nanotubes (CNTs) has been exploited for the preparation of conductive nanocomposites based on a large variety of insulating polymers. Among these, perfluoropolyether‐polyurethanes (PFPE‐PUs) represent a class of highly performing fluorinated materials with excellent water/oil repellency, chemical resistance, and substrate adhesion. The incorporation of highly conductive fillers to this class of highly performing materials allows them to be exploited in new technological and industrial fields where their unique properties need to be combined with the electrical conductivity or the electrostatic dissipation properties of carbon nanotubes. However, no studies have been presented so far on nanocomposites based on PFPE‐PUs and CNTs. In this work, polymer nanocomposites based on waterborne PFPE‐PUs and increasing amounts of carboxylated multiwall CNTs (COOH‐CNTs) were prepared and characterized for the first time. The effect of increasing concentration of COOH‐CNTs on the physical, mechanical, and surface properties of the nanocomposites was investigated by means of rheological measurements, dynamic mechanical analysis, thermal characterization, optical contact angle measurements, and scanning electron microscopy. In addition, electrical measurements showed that the highly insulating undoped PFPE‐PU system undergoes substantial modifications upon addition of COOH‐CNTs, leading to the formation of conductive nanocomposites with electrical conductivities as high as 1 S/cm. The results of this study demonstrate that the addition of COOH‐CNTs to PFPE‐PU systems represents a promising strategy to expand their possible use to technological applications where chemical stability, water/oil repellence and electrical conductivity are simultaneously required. Copyright © 2014 John Wiley & Sons, Ltd.     

Improving Thermal and Flame Retardant Properties of Epoxy Resin with Organic NiFe‐Layered Double Hydroxide‐Carbon Nanotubes Hybrids

To improve the dispersion of carbon nanotubes (CNTs) and flame retardancy of layered double hydroxide (LDH) in epoxy resin (EP), organic nickel‐iron layered double hydroxide (ONiFe‐LDH‐CNTs) hybrids were assembled through co‐precipitation. These hybrids were further used as reinforcing filler in EP. EP/ONiFe‐LDH‐CNTs nanocomposites containing 4 wt% of ONiFe‐LDH‐CNTs with different ratios of ONiFe‐LDH and CNTs were prepared by ultrasonic dispersion and program temperature curing. The structure and morphology of the obtained hybrids were characterized by different techniques. The dispersion of nanofillers in the EP matrix was observed by transmission electron microscopy (TEM). The results revealed a coexistence of exfoliated and intercalated ONiFe‐LDH‐ CNTs in polymer matrix. Strong combination of the above nanofillers with the EP matrix provided an efficient thermal and flame retardant improvement for the nanocomposites. It showed that EP/ONiFe‐LDH‐CNTs nanocomposites exhibited superior flame retardant and thermal properties compared with EP. Such improved thermal properties could be attributed to the better homogeneous dispersion, stronger interfacial interaction, excellent charring performance of ONiFe‐LDH and synergistic effect between ONiFe‐LDH and CNTs.     

Thermal degradation and stability of epoxy nanocomposites: Influence of montmorillonite content and cure temperature

The thermal behaviour and stability of epoxy nanocomposites were studied by thermogravimetric analysis (TGA). The nanocomposites consisted of a trifunctional epoxy resin, a hardener containing reactive primary amine groups and clay nanoparticles (i.e. montmorillonite), previously treated with octadecyl ammonium. Three levels of nanoclay content (0, 5 and 10%) and three temperature levels (120, 150 and 200 °C) were used. The exfoliation of nanoparticles within the material was analyzed by X-ray diffraction (XRD). The cure conversion was determined by Fourier transform infrared (FTIR) spectroscopy by selecting the suitable band for epoxide functional groups. The study demonstrated that the nanoclay greatly accelerates the cure, at the different cure temperatures studied. Finally, the thermal stability of the various nanocomposites was established by calculating various characteristic temperatures from thermograms as well as conversion and conversion derivative at maximum decomposition rate. The collisions between resin molecules, which are trapped within the nanoclay galleries, were less effective because they were protected against thermal degradation by the galleries. However, once the collision was effective, the thermal activation occurred more readily.     

Curing characteristics of o-cresol novolac epoxy resin modified by bismaleimide

Curing characteristics of o-cresol novolac epoxy resin modified by 4,4-diaminodiphenylmethane bismaleimide (DDM-BMI) using FTIR were investigated and the glass transition temperature was measured. With the addition of DDM as hardener, the relative curing reaction conversion of DDM-BMI increased with equivalent weight ratio [R₁ = (equiv wt summation of epoxy and DDM-BMI)/equiv wt of DDM] and weight ratio of epoxy and DDM-BMI (R₂ = wt of epoxy resin/wt of DDM-BMI). Using phenol novolac resin (PN) as hardener, the curing reaction conversion of DDM-BMI was hardly changed, but the variation of that in the epoxy resin was observed with R₂ change. © 1996 John Wiley & Sons, Inc.     

Rheological and dynamic-mechanical behavior of carbon nanotube/vinyl ester-polyester suspensions and their nanocomposites

Rheological properties of vinyl ester-polyester resin suspensions containing various amounts (0.05, 0.1 and 0.3 wt.%) of multi walled carbon nanotubes (MWCNT) with and without amine functional groups (-NH₂) were investigated by utilization of oscillatory rheometer with parallel plate geometry. Dispersion of corresponding carbon nanotubes within the resin blend was accomplished employing high shear mixing technique (3-roll milling). Based on the dynamic viscoelastic measurements, it was observed that at 0.3 wt.% of CNT loadings, storage modulus (G′) values of suspensions containing MWCNTs and MWCNT-NH₂ exhibited frequency-independent pseudo solid like behavior especially at lower frequencies. Moreover, the loss modulus (G″) values of the resin suspensions with respect to frequency were observed to increase with an increase in contents of CNTs within the resin blend. In addition, steady shear viscosity measurements implied that at each given loading rate, the resin suspensions demonstrated shear thinning behavior regardless of amine functional groups, while the neat resin blend was almost the Newtonian fluid. Furthermore, dynamic mechanical behavior of the nanocomposites achieved by polymerizing the resin blend suspensions with MWCNTs and MWCNT-NH₂ was investigated through dynamic mechanical thermal analyzer (DMTA). It was revealed that storage modulus (E′) and the loss modulus (E″) values of the resulting nanocomposites increased with regard to carbon nanotubes incorporated into the resin blend. In addition, at each given loading rate, nanocomposites containing MWCNT-NH₂ possessed larger loss and storage modulus values as well as higher glass transition temperatures (T_g) as compared to those with MWCNTs. These findings were attributed to evidences for contribution of amine functional groups to chemical interactions at the interface between CNTs and the resin blend matrix. Transmission electron microscopy (TEM) studies performed on the cured resin samples approved that the dispersion state of carbon nanotubes with and without amine functional groups within the matrix resin blend was adequate. This implies that 3-roll milling process described herein is very appropriate technique for blending of carbon nanotubes with a liquid thermoset resin to manufacture nanocomposites with enhanced final properties.     

碳纳米管改性环氧树脂的导热和阻燃性能

以双酚A二缩水甘油醚(DGEBA)环氧树脂(Epoxy Resin,EP)为基体、甲基六氢苯酐(MHHPA)为固化剂、以多壁碳纳米管(MWCNTs)为添加剂制备了环氧树脂/碳纳米管纳米复合材料。通过对微观结构、玻璃化转变温度(Tg)、热失重、热导率和锥形量热测试结果分析,研究了质量分数少于1.5%的MWCNTs对环氧树脂的导热和阻燃性能影响,结果表明,MWCNTs质量分数为1.5%时,复合材料发生团聚;纳米复合材料随着MWCNTs质量分数的增加Tg值先增加后降低;失重5%时,对应的温度先增加后降低,残炭量增加;样品的热导率呈现先升高后降低的趋势,当MWCNTs质量分数为1%时,复合材料的热导率最大;MWCNTs加入后环氧树脂的总释热量减少,释烟量增加,阻燃性得到一定程度的提高。     

Novel,environmentally friendly crosslinking system of an epoxy using an amino acid: Tryptophan‐cured diglycidyl ether of bisphenol A epoxy

Tryptophan, an amino acid, has been used as a novel, environmentally friendly curing agent instead of toxic curing agents to crosslink the diglycidyl ether of bisphenol A (DGEBA) epoxy resin. The curing reaction of tryptophan/DGEBA mixtures of different ratios and the effect of the imidazole catalyst on the reaction have been evaluated. The optimum reaction ratio of DGEBA to tryptophan has been determined to be 3:1 with 1 wt % catalyst, and the curing mechanism of the novel reaction system has been studied and elucidated. In situ Fourier transform infrared spectra indicate that with the extraction of a hydrogen from NH₃⁺ in zwitterions from tryptophan, the formed nucleophilic primary amine and carboxylate anions of the tryptophan can readily participate in the ring‐opening reaction with epoxy. The secondary amine, formed from the primary amine, can further participate in the ring‐opening reaction with epoxy and form the crosslinked network. The crosslinked structure exhibits a reasonably high glass‐transition temperature and thermal stability. A catalyst‐initiated chain reaction mechanism is proposed for the curing reaction of the epoxy with zwitterion amino acid hardeners. The replacement of toxic curing agents with this novel, environmentally friendly curing agent is an important step toward a next‐generation green electronics industry. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 181–190, 2007     

The effect of nanoparticles on structural morphology, thermal and flammability properties of two epoxy resins with different functionalities

The effect of layered silicate nanoclays, nano-silica and double-walled carbon nanotubes (DWNTs) on the thermal stability and fire reaction properties of two aerospace grade epoxy resins (a high temperature curing tetra-functional and a low temperature curing bi-functional resin) has been investigated using thermal analysis, cone calorimetry, LOI and UL-94 techniques. The morphology of the polymer-clay nanocomposites, determined by X-ray diffraction and transmission electron microscopy indicated intercalated structures. The addition of nanoclays (5-wt%) to both resins had a thermal destabilisation effect in the low temperature regime (<400 °C), but led to higher char yield at higher temperatures. The inclusion of nano-silica at 30-wt% significantly improved the thermal stability of the resins while DWNTs had an adverse effect due to their poor dispersion in the matrix. The nanoclays and carbon nanotubes significantly increased the fire resistance of the tetra-functional epoxy resin while a minimal effect was observed for the bi-functional resin.