The effects of curing cycles on properties of the epoxy system 3221/RH glass fabric composites

In this work, the epoxy system 3221 and its glass fabric laminates were thermally cured under different curing temperatures. The curing degree of the resin was increased with elevated reaction temperature. Dynamic mechanical analysis was performed on the laminate coupons and glass transition temperature (T_g) and relative stiffness (E′) of composites were measured before and after soaked in distilled water at 70°C. A shift in glass transition temperature to higher values and the splitting of the tan δ curve were observed with extent of cure under dry conditions. T_g values shifted to lower temperatures after immersion. Under wet condition, the change in T_g1 was very small when the curing degree was up to 96%. The relative stiffness experienced a reduction both in initial modulus and the initial sharp drop temperature after immersion. It also suggested that the excessively high curing temperature (>130°C) had a negative effect on the retention of relative stiffness under wet condition. Both the interlaminar shear strength and dielectric properties of laminates were determined before and after immersion. The compared results demonstrated that the elevated curing temperature played a good influence on both of the properties before aged. However, for samples cured above 130°C, lower retention of interlaminar shear strength and poor dielectric properties were observed during immersion due to their higher moisture contents. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Short term isothermal aging of epoxy resin and epoxy-carbon fiber composites

Short term isothermal aging of a neat epoxy resin and one ply epoxy-carbon fiber composite has been performed. The glass transition temperature, T_g of the neat epoxy resin aged at 204°C increased with aging time. The weight loss of the neat epoxy resin due to aging increased with aging temperature and aging time. The weight loss of the epoxy–carbon fiber composite during aging was slightly less than that of the neat resin. SEM microscopy showed the presence of voids and pores on the surface of the composite due to loss of low molecular weight volatiles. The amount and the size of the voids formed during aging increased with aging temperature and time.     

Effects of acid,alkaline, and seawater aging on the mechanical and thermomechanical properties of glass fiber/epoxy composites filled with carbon nanofibers

Owing to the superior corrosion resistance, fiber-reinforced polymer (FRP) composites are the prime choice of structural materials for various marine and chemical industries, where there is a long-term direct contact of the components takes place with corrosive fluids. In this present work, glass fiber/epoxy (GE) composites have been fabricated with and without carbon nanofibers (CNFs), and aging has been carried out in acidic (pH = 1), seawater (pH = 8.2), and alkaline (pH = 13) solutions for 150 days. The resistance of CNF-filled GE composites toward the corrosive fluids has been evaluated in terms of alteration in the mechanical (flexural), microstructural (fractography analysis by field emission scanning electron microscope), and thermomechanical (dynamic mechanical analysis) behavior of the materials. It is revealed that as the immersion time increases, there is a continuous decrement in flexural strength and modulus, and glass-transition temperature (T_g) of all the materials in all these solutions. Compared to the 1% CNF-filled GE composite, control GE composite showed more degradation in the case of alkaline aging and seawater aging. Maximum reduction (56%) in the strength of GE composite was observed due to 150 days of alkaline aging. However, the control GE composite showed better resistance to the acidic solution than that of CNF-filled GE composite. Possible failure modes, changes in the chemistry of the material due to aging have been studied by fractography analysis. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48434.     

Effect of NBR on epoxy/glass prepregs properties

Solid acrylonitrile‐butadiene rubber (NBR) was used in epoxy resin for toughening and also for increasing the tack of epoxy/glass prepregs. The NBR used in this study was a rubber with 33% acrylonitrile content. The changes in thermal and mechanical properties such as glass transition temperature (T_g), curing characteristics and lap‐shear strength have been studied. For this purpose, three types of prepregs with two levels of NBR content of 3 and 5%, were prepared. Prepregs were made by solvent type impregnation apparatus. In this method, resin impregnates satin textile glass fiber under the controlled and constant condition of line speed and oven temperature. Prepregs were B‐staged for about 3%. The cure characterization, T_g and flow behavior were evaluated using differential scanning calorimetry and rheological analysis. Results showed that increasing the rubber content caused the following effects: (a) delay in gel time of prepregs, (b) increase in activation energy of prepregs, and (c) decrease in total heat of curing reaction. It is interesting that NBR increased the tack of epoxy/glass prepreg but, had no effect on its resin flow behavior. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Moisture absorption behavior of epoxies and their S2 glass composites

The influence of moisture exposure on the behavior of three toughened epoxy–amine systems (scrimp resins SC11, SC15, and SC79, Applied Poleramic, Inc., Benicia, CA) was investigated. Neat resin samples were conditioned by immersion in distilled water at 71°C and in an environmental chamber at 85% relative humidity and 87.8°C until saturation. The equilibrium weight gain ranged from 1.8 to 3.8% for the resins. The long-chain, low-crosslink-density epoxy system (SC11) absorbed the highest amount of water and was saturated first, and it was followed by the medium-crosslink-density (SC15) and high-crosslink-density materials (SC79). The moisture diffusivity decreased with the increasing crosslink density of the resins. The percentage reduction of the glass-transition temperature (T_g) at equilibrium moisture absorption was highest for the low-crosslink molecule. The percentage reductions for the medium-crosslink and higher crosslink systems were comparable. A net weight loss after drying was observed for the SC11 and SC79 resin systems. Fourier transform infrared analysis confirmed the segment breakage and leaching of molecules from the epoxy–amine network. The effects of moisture cycling on T_g were dependent on the epoxy–amine morphology. During the drying stage, T_g increased to a value higher than that of the unaged dry systems. The S₂ glass composite samples were conditioned under identical conditions for the resin system. Composite systems absorbed less moisture than the neat resins as expected. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Intercalation and exfoliation behavior of epoxy resin/curing agent/montmorillonite nanocomposite

The epoxy resin/curing agent/montmorillonite nanocomposite was prepared by a casting and curing process. The intercalation and exfoliation behaviors of epoxy resin in the presence of organophilic montmorillonite were investigated by X‐ray diffraction (XRD) and dynamic mechanical thermal analysis (DMTA). For the diethylenetriamine curing agent, the intercalated nanocomposite was obtained; and the exfoliated nanocomposite would be formed for tung oil anhydride curing agent. The curing condition does not affect the resulting kind of composite, both intercalation or exfoliation. For intercalated nanocomposite, the glass transition temperature T_g, measured by DMTA and affected by the curing temperature of matrix epoxy resin is corresponded to that of epoxy resin without a gallery. The α′ peak of the loss tangent will disappear if adding montmorillonite into the composite. It was also found that the T_g of the exfoliated nanocomposite decreases with increasing montmorillonite loading. © 2002 John Wiley & Sons, Inc. J Appl Polym Sci 84: 842–849, 2002; DOI 10.1002/app.10354     

Dynamic mechanical properties of extruded nylon–wood composites

Dynamic mechanical properties determine the potential end use of a newly developed extruded nylon–wood composite in under‐the‐hood automobile applications. In this article, the dynamic mechanical properties of extruded nylon–wood composites were characterized using a dynamic mechanical thermal analyzer (DMTA) to determine storage modulus, glass transition temperature (T_g), physical aging effects, long‐term performance prediction, and comparisons to similar products. The storage modulus of the nylon–wood composite was found to be more temperature stable than pure nylon 66. The T_g range of the nylon–wood composite was found to be between 23 and 56°C, based on the decrease in storage modulus. A master curve was constructed based on the creep curves at various temperatures from 30 to 80°C. The results show that the relationship between shift factors and temperature follows Arrhenius behavior. Nylon–wood composites have good temperature‐dependent properties. Wood fillers reduced the physical aging effects on nylon in the wood composites. The comparison of the nylon–wood composite with other similar products shows that nylon–wood composites are a promising low cost material for industrial applications. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Erasure below glass‐transition temperature of effect of isothermal physical aging in fully cured epoxy/amine thermosetting system

The erasure below the glass‐transition temperature (T_g) of the effect of isothermal physical aging (at aging temperature T_a) in a fully cured epoxy/amine thermosetting system is investigated using the torsional braid analysis (TBA) dynamic mechanical analysis technique and the differential scanning calorimetry (DSC) technique. From the TBA temperature scans, the intensity of the localized perturbation of the moduli in the vicinity of the T_a (90°C), due to isothermal physical aging, is decreased by heating to below the T_g (T_g∞ = 177°C), indicating that the physical aging effect can be eliminated by heating to below the T_g. The isothermal aging effect in the vicinity of the T_a is almost completely eliminated by heating to 50°C above the T_a (i.e., 140°C); however, a competing aging effect occurs above T_a at higher temperatures during the heating. Erasure below T_g of the isothermal physical aging effect is inferred from DSC experiments from the diminished relaxation enthalpy in the vicinity of the T_g, which is measured from the difference in areas between the aged (T_a = 150°C) and deaged thermograms. A comparison of the TBA and DSC results is made. Implications on the heterogeneous nature of the amorphous glassy state of polymers are discussed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 396–404, 2001     

Physical aging in graphite/epoxy composites

Matrix-dominated mechanical behavior of a graphite/epoxy composite has been found to be affected by sub-T_g annealing. Postcured (±45°)_4S specimens of Thornel 300 graphite/Narmco 5208 epoxy were quenched from above T_g and given a sub-T_g annealing at 140°C for times up to 10⁵ min. The ultimate tensile strength, strain-to-break, and toughness of the composite material were found to decrease as functions of sub-T_g annealing time. No weight loss was observed during the sub-T_g annealing. The time-dependent change in mechanical behavior is explained on the basis of free-volume changes that are related to the physical aging of the nonequilibrium glassy network-epoxy. The results imply possible changes in composite properties with service time.     

Preparation of emulsion‐type thermotolerant sizing agent for carbon fiber and the interfacial properties of carbon fiber/epoxy resin composite

A modified resin was synthesized through the reaction between dodecylamine and tetraglycidyldiaminodiphenylmethane (TGDDM), which was used as the film former of sizing agent for carbon fiber (CF). The sizing agents were prepared through phase inversion emulsification method. Fourier transform infrared spectroscopy (FTIR) was utilized to analyze the modified resin. Particle sizes of the sizing agents were tested to evaluate their stabilities. Differential scanning calorimetry (DSC) results demonstrated that the glass transition temperature (T_g) of the modified TGDDM is much higher than the T_g of the cured epoxy resin E‐44. The influences of the sizing treatment on CF were investigated by abrasion resistance, fluffs, and stiffness tests. The maximum abrasion resistance increased by 172.8%, compared with the abrasion resistance of the desized CF. Interlaminar shear strength (ILSS) results of the CF/TGDDM composites indicated that the interfacial adhesion between CF and matrix resin was greatly improved after CF was sized. The maximum ILSS value could obtain a 29.16% improvement, compared with the ILSS of the desized CF composite. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41882.     

Influence of cure conditions on glass transition temperature and density of an epoxy resin

The glass transition temperature T_g and density of a TGDDM-DDS epoxy resin system were studied as a function of cure times at various cure temperatures. Both T_g and density asymptotically increased toward a maximum value with increasing cure time. The T_g and density measurements were related to the extent of cure, and the relationship in both cases was found to be independent of cure temperature.     

Novel effect of barbituric acid on glass transition temperature of bismaleimide–epoxy resin systems

Barbituric acid (BTA) has a novel influence on glass transition temperature (T_g) of bismaleimide (BMI)–epoxy resin systems. It causes the T_g of a BMI–epoxy resin system to rise significantly. The BTA's influence on T_g was investigated by changing the molar ratio of the reactants. In addition, the influence of benzoperoxide (BPO) on T_g was compared with that of BTA. The reaction selectivity of BTA and diamino-diphenyl sulfone (DDS) toward BMI and epoxy individually in the BMI–epoxy blended systems were studied using the DSC and GPC. By controlling the amount of DDS and BTA, epoxy and BMI could form intercrosslinking networks.     

Influence of Matrix Properties on Fragmentation Test

Physical aging was used to vary the mechanical properties of model single fiber composites without changing the chemistry at the interface in order to study how property changes affect the measurement of interfacial adhesion by the fragmentation test. The properties of epoxy matrix/AS4 single fiber composites driven to full cure (T_g = 166°C) are altered by annealing below T_g . Neat resin samples with identical thermal histories are tested. All aged panels show roughly the same embrittlement with aging characterized by an average 30% decrease in tensile failure strain and 7.3% increase in compressive yield relative to quenched samples. Fragmentation results indicated no change between aged and quenched samples. Results are discussed in terms of micromechanics models for the fragmentation test. Strain at fragmentation increased with aging. This was related to the residual stress state in the model composite and the possibility of the zero stress state of the single fiber composites increasing with thermal annealing.     

Development of high Tg epoxy resin and mechanical properties of its fiber‐reinforced composites

A new epoxy resin with high glass transition temperature (T_g) (～ 180°C) and a viscosity low enough for infiltration into dry reinforcements at 40°C was developed for the vacuum‐assisted resin transfer molding process. To study the curing behavior and viscosity, several blends were formulated using multifunctional resin, aromatic hardener, and reactive diluents. Effects of these components on the viscosity and T_g were investigated by thermomechanical analysis, dynamic scanning calorimetry, and rheometer. Experimental results showed that a liquid aromatic hardener and multifunctional epoxy resin should be used to decrease the viscosity to <1 Pa·s at 40°C. Moreover, the addition of a proper reactive diluent decreased the viscosity and simultaneously minimized the deterioration of T_g. Mechanical properties of the composite produced with the optimized blend were evaluated at both room‐temperature and high‐temperature conditions. According to the results, the composite showed comparable mechanical properties with that of the current commercial resin. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Isothermal physical aging of thin PMMA films near the glass transition temperature

Isothermal physical aging and the glass transition temperature (T _g) of PMMA thin films were investigated by means of differential scanning calorimetry (DSC). Freestanding thin films of different molecular weights (M _w = 120,000, 350,000, 996,000 g/mol) and film thicknesses (40–667 nm) were obtained by spin coating onto a silicon wafer substrate and then releasing the coated film using a water floating technique. The thin films were stacked in a DSC pan and isothermally aged for different aging times (t _a = 1 and 12 h) and aging temperatures (T _a = 105, 110, and 115 °C) below but near T _g. Enthalpy relaxation (ΔH _Relax), resulting from the isothermal physical aging, initially increased with increasing ΔT (T _g − T _a, driving force of aging), reached a maximum value, and then decreased with further increase in ΔT. Below ~100 nm film thickness, ΔH _Relax of samples aged near their T _g (i.e., T _a = 110 and 115 °C) decreased with decreasing film thickness, indicating the suppression of physical aging. Up to 9.9 °C depression in T _g was observed for thinner films (~40 nm), when compared to the thicker films (~660 nm) in this study. The decrease in ΔH _Relax with decreasing film thickness at a given T _a appears to be associated with the reduction in T _g.     

Effect of physical annealing on the dynamic mechanical properties of a high-Tg amine-cured epoxy system

Physical annealing of a fully cured amine/epoxy system has been investigated using the freely oscillating TBA torsion pendulum technique. The material densifies spontaneously during annealing in an attempt to reach equilibrium, thereby changing material behavior. The dynamic mechanical behavior of a film specimen (T_g = 174°C, 0.3 Hz) and of a glass braid composite specimen (T_g = 182°C, 0.9 Hz) was monitored during isothermal annealing at sub-T_g temperatures (ranging to 230°C below T_g); after annealing, the behavior was measured vs. temperature and compared with that of the unannealed state. Isothermally, the storage modulus (G′) of the film specimen and the relative rigidity (1/P²) of the composite specimen increased almost linearly with log time, whereas the logarithmic decrement (Δ) decreased with time. The isothermal rates of annealing were determined from the rates of changes in G′ and in 1/P² for the film and composite specimens, respectively. In a wide temperature range between T_g and the secondary transition temperature, T_sec (≈ ?30°C, 2.3 Hz by TBA), the isothermal rates of annealing at the same annealing time appeared to be the same. Thermomechanical spectra of the isothermally annealed material revealed a maximum deviation in thermomechanical behavior from the unannealed material in the vicinity of the annealing temperature. The effects of physical aging were the same for the film and composite specimens. Effects of sequential annealing at two isothermal temperatures on the thermomechanical behavior were also investigated; when the second temperature was higher than the first, the effect of only the high-temperature annealing was evident, whereas the effect of annealing at both temperatures was revealed when the second temperature was lower than the first. Results suggest that physical annealing at different temperatures involves different length scales of chain segment relaxation and that the effects of isothermal aging can be eliminated by heating to below T_g.     

Monitoring the reaction progress of a high‐performance phenylethynyl‐terminated poly(etherlmide). Part II: Advancement of glass transition temperature

The cure schedule for carbon fiber‐reinforced, phenylethynyl‐terminated Ultem™ (GE Plastics) composites was studied in an attempt to optimize the resultant glass transition temperature, T_g. Reaction progress and possible matrix degradation were monitored via the T_g. On the basis of previous research, matrix degradation induced T_g reduction was expected for increases in cure time or temperature beyond approximately 70 minutes at 350°C. Using the central composite design (CCD) of experiment technique, composite panels, neat resin, and polymer powder‐coated tow (towpreg) were cured following various cure schedules to allow for the measurement of the glass transition temperatures resulting fronm cure time and temperature variations. The towpreg and neat resin specimens were cured in a differential scanning calorimeter. The glass transition temperatures of all specimens were measured via differential scanning calorimetry; the composite glass transition temperatures were also measured with dynamic mechanical thermal analysis. The composite panels and towpreg specimens showed similar trends in T_g response to cure schedule variations. Composite and towpreg glass transition temperatures increased to a plateau with increasing cure time and temperature, whereas, the neat resin showed an optimal T_g followed by T_g reduction with increasing cure time and temperature. The optimal neat resin T_g occurred within a cure time and temperature significantly below that required to maximize the composite and towpreg glass transition temperatures.     

Improvement of fracture toughness and glass transition temperature of DGEBA‐based epoxy systems using toughening and crosslinking modifiers

Several toughening and crosslinking modifiers were tested in two epoxy resin systems based on the diglycidyl ether of bisphenol A (DGEBA) with the objective to improve the critical stress intensity factor K_IC and the glass transition temperature (T_g) simultaneously. An amine hardener (isophorone diamine (IPD)) and a homopolymerization initiator (1‐ethyl‐3‐methylimidazolium acetate (EMIM Ac)) were used as curing agents. The highest effect on the K_IC value of the resin system DGEBA/IPD (K_IC = 0.72 MPa^1/2; T_g = 164°C) was achieved with the dendric polymer Boltorn P501 (10 wt%), but it decreased the T_g (K_IC = 1.39 MPa^1/2; T_g = 136°C). A high toughening effect with a low decrease of T_g was achieved with a combination of a self‐organized block copolymer (Nanostrength M22N) and silica nanoparticles (Nanopox F400) (K_IC =1.15 MPa^1/2; T_g =157°C). The K_IC value of the resin system DGEBA/EMIM Ac was improved from 0.44 to 0.66 MPa^1/2. An improvement of both, the thermal and mechanical properties was established for a combination of a poly(tetrahydrofuran) as toughening modifier (PolyTHF2000) with the post‐crosslinking modifier diethylphosphite (DEP) in the resin system DGEBA/IPD (K_IC = 0.86 MPa^1/2; T_g = 180°C). A system with chemical linkages between both modifiers was investigated for comparison but yielded inferior results. POLYM. ENG. SCI., 59:86–95, 2019. © 2018 Society of Plastics Engineers     

Glass‐transition temperature based on dynamic mechanical thermal analysis techniques as an indicator of the adhesive performance of vinyl ester resin

Vinyl ester resins are being used extensively as matrices in fiber‐reinforced polymer composite materials, but their use as a structural adhesive has been limited. Initial studies investigating the durability of a vinyl ester as a wood adhesive showed unsatisfactory performance in comparison with other adhesives. In this work, the glass‐transition temperatures (T_g's) of a vinyl ester and a E‐glass/vinyl ester composite material, fabricated by the Composites Pressure Resin Infusion System, were determined with dynamic mechanical thermal analysis. The results indicated that the resin cured under ambient conditions had a much lower T_g (～60°C) than the postcured material (～107°C). This suggested undercuring, that is, incomplete crosslinking, of the resin when it was cured at room temperature. E‐glass/vinyl ester samples, however, showed virtually no difference in T_g between room‐temperature‐cured and postcured samples. The exact reasons for this are not currently known but are thought to be both mechanical and chemical in nature. On the basis of the findings presented in this article, it can be concluded that if this vinyl ester resin is to be used as a structural adhesive, postcuring or formulation to ensure a high degree of crosslinking under ambient conditions is necessary. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2221–2229, 2005     

Elaboration and dielectric property of modified PZT/epoxy nanocomposites

Composites of lead zirconate titanate (PZT) 50 nm nanoparticles and epoxy resins have been produced with various PZT contents from 0 to 20 wt%. The morphology and thermal properties of prepared composites were characterized using scanning electron microscopy and differential scanning calorimetry. The PZT nanoparticles were found to be well dispersed in the epoxy resin matrix. The glass transition temperature (T_g) value of the nanocomposites increases from 164 to 178°C with increasing the PZT weight fraction. The dielectric composites properties dependences were studied via a wide range of frequency from 10 Hz to 100 kHz. The dielectric constant of PZT/epoxy composite was increased from 5.56 to 6.29 (at f = 1 kHz, T = 30°C), respectively to the incorporated PZT amount, and these values are higher than that the dielectric constant of pure cured epoxy resin, ε = 4.86. POLYM. COMPOS., 37:455–461, 2016. © 2014 Society of Plastics Engineers