Combined effect of zeolite and boric acid on thermal behavior of epoxy composites

The particles of natural zeolite in combination with boric acid were incorporated into the epoxy resin ED-20 in order to improve the thermal stability of epoxy polymer. Epoxy resin was cured using polyethylenepolyamine. Characterization of the epoxy composites was carried out by using Fourier transform infrared spectrometry, thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) under flow of air and argon. The thermal behavior of the zeolite/boric acid-based epoxy composites (total percentage 15 mass%) were compared with that of 15 mass% boric acid-based epoxy system and the neat epoxy resin. TG and DSC results revealed that the combination of 5 mass% zeolite and 10 mass% boric acid significantly increased the mid-point temperature and residue, and decreased the maximum decomposition rate of the epoxy composites at the heating.     

Biobased epoxy/carbon fiber composites: Effect on mechanical,thermo-mechanical and morphological properties

Biobased epoxy was synthesized from diglycidyl ether of bisphenol A (DGEBA) and epoxidized castor oil (ECO) at a ratio of 80:20. Carbon fiber (CF) was used as a reinforcing agent to fabricate composites using biobased epoxy as matrix. Mechanical, Thermal and morphological properties of neat epoxy and biobased epoxy composites were investigated. Mechanical test results revealed that the composites prepared using five plies were higher than those with three plies and one ply respectively. This phenomenon revealed the effective reinforcing effect of carbon fiber due to its higher strength and higher crosslinking density. The composites also demonstrate high damping behavior as compared with neat epoxy and biobased epoxy blend. With increasing number of plies the composites thermal properties also shows an improvement. The SEM micrographs of the composites depicted that the biobased epoxy was fully adhered to the carbon fiber, thus representing a strong interface between CF/epoxy matrix.     

单向纤维增强环氧复合材料的热膨胀系数

本文在123—413K的温度范围内,测量了单向玻璃纤维和碳纤维增强环氧树脂复合材料α_P~C(纤维方向),α_(T1)~C(横截面板厚度方向),α_(T2)~2(横截面板宽度方向)三个热膨胀系数.研究了纤维体积分数V_f和纤维表面处理对α_P~C和α_T~C的影响.结果表明,α_P~C在整个温度范围内不受纤维表面处理影响,随V_f的增加而减小,变化规律符合Schapery方程.对于横向热膨胀系数,在T<基体玻璃化温度T_g~m时,有α_(T1)~C α_(T2)~C=α_(T)~C,在V_f 0.3时,有α_T~C>α_m(基体的),而后随V_f的增加而减小,经分析也符合Schapery理论.在T>T_g~m时,α_(T1)~C和α_(T2)~C呈各向异性,特别在纤维表面未处理时更为显著.形态研究表明,其原因是在纤维铺层之间存在片状树脂层.     

Thermal properties of anhydride-cured bio-based epoxy blends

Epoxidized palm oil (EPO) (0–12 wt%) was added into petrochemical-based epoxy blends (diglycidyl ether of bisphenol-A (DGEBA)/cycloaliphatic epoxide resin/epoxy novolac resin) to develop a thermal curable bio-based epoxy system. The thermal behaviors of the EPO, epoxy blends (EB), and bio-based epoxy blends (EB/EPO) were characterized using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMT) and thermo-mechanical analysis (TM). The glass transition temperature (T _g) and storage modulus (E′) of the EB/EPO system was reduced with the increasing of the EPO loading. This is attributed to the plasticizing effect of the EPO. It was found that epoxy blends with higher loading of EPO possessed higher coefficient of thermal expansion (CTE) and tanδ value. This is due to the increase of the free volume and chain flexibility in the three-dimensional network of the epoxy blends. The internal thermal stresses of the EB/EPO were decreased as the increasing loading of EPO, owing to the reduction of crosslink density, modulus of elasticity, and T _g in the epoxy blends.     

Viscoelastic properties and residual stresses in polyhedral oligomeric silsesquioxane-reinforced epoxy matrices

Fiber-filled thermosetting polymer composites are extensively used in aerospace industries. One disadvantage of these materials is cure induced or thermally induced residual stresses in the matrix, which may result in deteriorated performance and premature failure. This article explores the use of epoxy/multifunctional polyhedral oligomeric silsesquioxane (POSS) nanocomposites as resins with reduced thermal stress coefficients that result in mitigated residual stresses. The effect of POSS loading on the thermal stress coefficient of the epoxy/POSS nanocomposite resins was investigated from below the β-relaxation to the α-relaxation, or glass transition temperature, (i.e., from −100 to 180 °C) by measuring the shear modulus and linear thermal expansion coefficient. The thermal stress coefficient of the epoxy/POSS nanocomposites is found to be a strong function of temperature, decreasing rapidly with decreasing temperature through the α-relaxation region, increasing in the vicinity of the β-relaxation, and then decreasing below the temperature associated with the peak in the β-relaxation. With increasing POSS content, the thermal stress coefficient is reduced compared with the neat resin in the vicinity of the α-relaxation; however, the thermal stress coefficient increases with increasing POSS content below the temperature of the β-relaxation peak. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2719–2732, 2008     

The dynamic mechanical behavior of random-in-plane short fiber-reinforced epoxy resin composites

In the present paper, the dynamic mechanical properties of random-in-plane short fiber-reinforced epoxy resin composites were studied by using a rheometrics solids analyzer. The three-point bend testing of the four composites (glass fiber/913 epoxy resin, glass fiber/924 epoxy resin, carbon fiber/913 epoxy resin and carbon fiber/924 epoxy resin) was carried out over temperatures from −100°C to 200°C at a frequency of 10 Hz and strain 0.05%. The composites based on 924 epoxy resin, which has been designed specially for high temperature applications, have less energy loss than the 913 epoxy resinbased composites. For the same resin, the carbon fiber-reinforced composites have less energy loss than the glass fiber-reinforced composites. All the composites have less energy loss than their corresponding matrices; the greater the fiber content, the lower the energy loss. The beta transition of 913 epoxy resin has been shifted to a higher temperature after being reinforced. It was shifted from −50°C to −30°C after being reinforced with glass fiber and made a diffuse shoulder-like peak commencing at −30°C after being reinforced with carbon fiber. The 924 epoxy resin has undergone the same change in beta transition as the 913 resin, though to a smaller extent. The phenomenon suggested that interactions between the macromolecules of the epoxy resins and the molecules along the fiber's surface.     

Effect of thermoplastic toughening agent on glass transition temperature and cure kinetics of an epoxy prepreg

The isothermal time–temperature-transformation (TTT) cure diagram is developed in this article to investigate the effect of thermoplastic toughening agent on glass transition temperature (T _g) and cure kinetics of an epoxy carbon fiber prepreg, Cycom 977-2 unidirectional (UD) tape. The glass transition temperature was measured using differential scanning calorimetry (DSC) over a wide range of isothermal cure temperatures from 140 to 200 °C. Times to gelation and vitrification were measured using shear rheometry. The glass transition temperature master curve was obtained from the experimental data and the corresponding shift factors were used to calculate the activation energy. The kinetic rate model was utilized to construct iso-T _g contours using the calculated activation energy. It was observed that the iso-T _g contours did not follow the behavior of the neat epoxy resin, since they deviated from the gel time curve. This deviation was believed to be the effect of the thermoplastic toughening agent. The behavior of the neat epoxy resin in 977-2 was shown by constructing the iso-T _g contours using the activation energy obtained from gel time modeling.     

Thermal behavior and flammability of epoxy/glass fiber composites containing clay and decabromodiphenyl oxide

Epoxy/glass fiber hybrid composites with organo-montmorillonite (OMMT) and decabromodiphenyl oxide (DBDPO) flame retardants were prepared by vacuum-assisted resin infusion technique. The effects of OMMT and DBDPO on the flammability properties of epoxy/glass fiber hybrid composites were evaluated through UL-94 vertical flammability test and limiting oxygen index (LOI). Thermal decomposition was studied by means of thermogravimetric analyzer (TG). Field emission scanning electron microscopy (FESEM) was used to study the char morphology of the epoxy hybrid composites after being subjected to UL-94 vertical flammability test. Epoxy/glass fiber/OMMT hybrid composites with DBDPO loading of 40 wt% showed V-1 rating, whereas an increase to 50 wt% loading showed V-0 rating. The LOI values increased from 22.7 to 39.9 % as the loading of DBDPO increased. The obtained TG results showed that the thermal stability of epoxy hybrid composites decreased as the DBDPO loading increased. DBDPO decomposed at a lower temperature to form bromine radicals, which reacted with the combustible gases to form hydrogen bromide to inhibit the flame spread in the gas phase. The condensed phase activity was shown in FESEM, in which a layer of compact and continuous char was formed in epoxy/glass fiber/OMMT/DBDPO hybrid composites.     

Characteristics of kenaf fibre/epoxy composites subjected to thermal degradation

Kenaf fibres are receiving much attention in the natural fibre composite industry due to its potential as polymer reinforcements. However, like all natural fibres, kenaf fibres have lower thermal resistance as compared to synthetic fibres. In this current work, the characteristics of kenaf fibre/epoxy composites, both treated and untreated using alkalization process, exposed to high temperature were studied. Thermogravimetric analysis (TGA) was used to study the thermal decomposition behaviour of treated and untreated kenaf/epoxy composites as well as their components, kenaf fibre and neat epoxy from room temperature up to 600 °C. The weight loss and physical changes of these samples were observed through furnace pyrolysis. Surface morphology of the composites after degradation was observed using scanning electron microscopy (SEM). The results from the TGA showed that the addition of kenaf fibres into the epoxy slightly improves both the charring and thermal stability of the samples. However, it was observed that alkalization causes reduction in these behaviours for the kenaf/epoxy composite. Generally, increased exposure time causes higher weight loss of the composites only up to 150 °C. At higher temperature, duration of exposure has little influence on the weight loss. Fibre-matrix debondings were observed on degraded samples implying mechanical degradation of the composites had occurred.     

Alkoxysilane functionalized polycaprolactone/polysiloxane modified epoxy resin through sol-gel process

Incorporating elastic polysiloxane and/or an inorganic silica network in epoxy resin could result in the enhancement of physico-chemical properties due to the existence of Si-O bonds. To improve the compatibility between polysiloxane and epoxy matrices and intensively strengthen the properties of the modified system, here polysiloxane was introduced into epoxy resin through compatibilizing epoxy-immiscible polysiloxane with epoxy-miscible polycaprolactone segments via a sol-gel process. To fulfill the process, a blend containing alkoxysilane-functionalized polycaprolactone/polydimethylsiloxane (PCS-2Si) was firstly synthesized using direct nucleophilic addition between -OH groups of polydiol and -NCO of a silane. And then a series of modified epoxy resins were prepared in different epoxy/PCS-2Si weight ratios. All the modified composites were characterized by conventional methods, and their morphological, thermal degradation and surface properties were studied. The results showed that increasing the PCS-2Si content caused the changes of miscibility between epoxy and polysiloxane. Also, the thermal stability of the modified composites was greatly improved. As for the temperature value at 5% weight loss, it reached to 308.5 °C for the composite containing 50-60% (wt%) PCS-2Si, over 150 °C higher than that for neat amine-cured epoxy resin. Similarly, the modified composites showed good hydrophobicity. The improvement of these properties came from the improved interaction between PCS-2Si and epoxy, the forming of Si-O-Si network and the enrichment of siloxane chains on the surface of films. Therefore, it is believed that this modified epoxy appears promising as new high performance and highly functional materials.     

Improving the dispersion and flexural strength of multiwalled carbon nanotubes-stiff epoxy composites through β-hydroxyester surface functionalization coupled with the anionic homopolymerization of the epoxy matrix

Multiwalled carbon nanotubes (MWNTs) were functionalized in a two-step acid-epoxy functionalization process, in which suitable surface condition and reactivity compatible with the DGEBA epoxy resin was introduced. The use of (4-dimethylamino)-pyridine as an initiator for DGEBA homopolymerization produced covalent bonds between the functionalized MWNTs and the epoxy matrix through chain transfer reactions involving the secondary hydroxyls. This process yielded uniform MWNTs-stiff epoxy composites with significant enhancement in flexural strength without sacrificing the elastic modulus when compared to the neat resin.     

Enhanced fracture toughness and mechanical properties of epoxy resin with rice husk-based nano-silica

This paper reports a novel approach to toughen epoxy resin with nano-silica fabricated from rice husk using a thermal treatment method with a particle size distribution in range of 40–80 nm. The nano-silica content was in the range, 0.03–0.10 phr, with respect to epoxy. The mechanical test showed that with the addition of 0.07 phr of rice husk based nano-silica, the fracture toughness of the neat epoxy resin increased 16.3% from 0.61 to 0.71 MPa m^1/2. The dynamic mechanical analysis test results showed that the glass transition temperature (T _g) of a 0.07 phr nano-silica dispersion in epoxy resin shifted to a higher temperature from 140 to 147°C compared to neat epoxy resin. SEM further showed that the nano-silica particles dispersed throughout the epoxy resin prevented and altered the path of crack growth along with a change in the fracture surface morphology of cured epoxy resin.     

Three-phase cyanate ester composites with fumed silica and negative-CTE reinforcements

Three-phase cyanate ester adhesives have been developed using a bisphenol E cyanate ester resin, fumed silica, and negative-CTE (coefficient of thermal expansion) reinforcements: short carbon fiber or zirconium tungstate (ZrW₂O ₈ ). Fumed silica was used to impart thixotropic behavior on the resin and decrease settling in the adhesives. The cured composites were evaluated using various thermal analysis techniques for their thermal-mechanical properties. Composites with short carbon fiber showed enhanced modulus and decreased thermal expansion (70% reduction for 20 vol%) and showed little phase separation. While settling of the dense ceramic particles could not be completely eliminated for the zirconium tungstate composites through rheological modification of the adhesive with added fumed silica, a reduction in CTE of 84% was achieved in the composite (58 vol%) compared to the neat resin. In addition, the effect of thermal history on the cure and temperature induced ZrW₂O₈ phase transitions, and their corresponding influence on thermal strains vs. temperature, are examined by thermomechanical analysis.     

Coir-fiber-based fire retardant nano filler for epoxy composites

Coir-fiber-based fire retardant nano filler has been developed for epoxy resin (ER). At first, the coir fiber was brominated with saturated bromine water and then treated with stannous chloride solution. After drying, it was grinded to nano dimension and mix well with ER for composites preparations. FTIR, DSC, and TG techniques were used to characterize the brominated coir fiber. Gravimetric analysis shows only 10% by mass of bromination on coir fiber. Bromination decreases the thermal stability of the coir fiber, but it does not affect the final stability of the composites. This study concentrates on the thermal, fire retardant, and morphological properties of nanocomposites prepared by direct mixing. The fire retardancy properties (smoke density and limiting oxygen index) of coir–epoxy nanocomposites have increased significantly.     

Morphology, flexural, and thermal properties of sepiolite modified epoxy resins with different curing agents

A bisphenol A-based epoxy resin was modified with 5 wt% organically modified sepiolite (Pangel B40) and thermally cured using two different curing agents: an aliphatic diamine (Jeffamine D230, D230) and a cycloaliphatic diamine (3DCM). The morphology of the cured materials was established by scanning and transmission electron microscopy analysis. The thermal stability, thermo-mechanical properties, and flexural behaviour of the sepiolite-modified matrices were evaluated and compared with the corresponding neat matrix. The initial thermal decomposition temperature did not change with the addition of sepiolite. 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 D230 increased by a 10% while the sepiolite modified resin cured with 3DCM resulted in a lower flexural strength compared with the unmodified resin. The reduced flexural strength was attributed to the stress concentrations caused by the sepiolite modifier, which rendered the resins more brittle.     

Influence of T31 content on combustion and thermal degradation behaviors on flame-retardant epoxy composites

To study the influence of the T31 content on the combustion properties and thermal degradation behaviors of flame-retardant epoxy composites, a series of flame-retardant epoxy composites were prepared using E-44 epoxy resin as matrix, T31 curing agent as curing agent, and intumescent flame retardant (IFR, based on phosphorus acid, melamine, and pentaerythritol) as flame retardant. The influence of T31 content on combustion behaviors and thermal degradation properties of the flame-retardant epoxy composites were studied using cone calorimeter test (CCT) and thermal-gravimetric analysis (TG), respectively. The cone calorimeter test results indicate that the decrease of T31 can significantly decrease the HRR, THR, SPR, and enhance the char residue of the epoxy composites. EP-4 with 7.0 wt% T31 shows the lowest HRR, SPR and the highest char residue. Furthermore, the TG results indicate that the EP-4 has the highest char residue among all the epoxy composites.     

An investigation of the accelerated thermal degradation of different epoxy resin composites using X-ray microcomputed tomography and optical coherence tomography

Epoxy resin composites reinforced with hollow glass microspheres, microlight microspheres, 3D parabeam glass, and E-Glass individually were subjected to accelerated thermal degradation conditions. X-ray microcomputed tomography (XμCT) was used to evaluate density changes, reinforcement filler damage, homogeneity, cracks and microcracks in the bulk of the different epoxy resin composites. XμCT 3D images, 2D reconstructed images and voids calculations revealed microspheres damage, filler distributions and showed cracks in all composites with different shapes and volume in response to the thermal degradation conditions. In addition, expansion of air bubbles/voids was observed and recorded in the microsphere and microlight epoxy composite samples. In a complementary way, optical coherence tomography (OCT) was used as a novel optical characterisation technique to study structural changes of the surface and near-surface regions of the composites, uncovering signs of surface shrinkage caused by the thermal treatment. Thus, combining XμCT and OCT proved useful in examining epoxy resin composites' structure, filler-resin interface and surface characteristics.     

The crosslinking of epoxy resins at interfaces. II. At an aromatic polyamide surface

The first 200–400 nm of crosslinked epoxy resin adjacent to an aromatic polyamide (aramid) surface were characterized by internal reflection spectroscopy (IRS) using an aramid-coated IRS element. The crosslinking kinetics and final crosslinked state of an anhydride-cured epoxy resin were strongly affected by the aramid surface, which produced a localized increase in the rate of anhydride consumption and a decrease in the yield of ester products. An aromatic amine-cured epoxy resin was less affected by the aramid surface. Unidirectional aramid fiber:epoxy composites were examined by dynamic mechanical analysis (DMA), and differential scanning calorimetry (DSC). The chemical changes detected spectroscopically were shown to correlate with mechanical and thermal transition data obtained by DMA and DSC. These results are rationalized on the basis of the effect of absorbed moisture in the aramid on the crosslinking chemistry.     

Epoxy‐based composite adhesives: Effect of hybrid fillers on thermal conductivity,rheology, and lap shear strength

Thermal management is an important parameter in an electronic packaging application. In this work, three different types of fillers such as natural graphite powder (Gr) of 50‐μm particle size, boron nitride powder (h‐BN) of 1‐μm size, and silver flakes (Ag) of 10‐μm particle size were used for thermal conductivity enhancement of neat epoxy resin. The thermal properties, rheology, and lap shear strength of the neat epoxy and its composite were investigated. The analysis showed that the loading of different wt% of Gr‐based fillers can effectively increase the thermal conductivity of the epoxy resin. It has also been observed that the thermal conductivity of the hybrid filler (Gr/h‐BN/Ag) reinforced epoxy adhesive composite increased six times greater than that of neat epoxy resin composite. Further, the viscosity of hybrid filler reinforced epoxy resin was found to be increased as compared with its virgin counterpart. The adhesive composite with optimized filler content was then subsequently subjected to determine single lap shear strength. The degree of filler dispersion and alignment in the matrix were determined by scanning electron microscopy (SEM) analysis.     

In situ thermoset molecular composites

The polymerization of rigid rod polymer precursors in a reactive matrix precursor, which is later cured in the mold, constitutes the in situ process. A poly-azomethine (PAM) was used as the rigid rod molecule. The resin used was an epoxy. We discuss the prediction of mechanical properties using micromechanics equations for chopped fiber composites. The chemistry used to synthesize the rigid rod polymer PAM in the epoxy precursor is reviewed. Approaches to better control the cure of these epoxy systems through cure kinetics and cure rheology studies completes the thermoset in situ molecular composite process. There was a 71% increase in tensile modulus in comparison to that of the neat epoxy resin. Molecular modeling simulations and continuum mechanics are used to help understand these findings. PAM/epoxy systems were used as a matrix material in the fabrication of unidirectional glass fiber/(PAM/epoxy) structural composites. © 1994 John Wiley & Sons, Inc.