Effect of cure history on dynamic mechanical properties of an epoxy resin

The effect of cure history on the dynamic thermomechanical properties of a high temperature curing epoxy resin has been studied using torsional braid analysis. In isothermal cures “full cure” is not possible except at temperatures above the maximum glass transition temperature (T_g) of the cured resin, hence the necessity of a “post-cure” after lower temperature isothermal cures. The highest T_g and maximum cross-linking in the cured resin was for a linear heating rate of 0.05°C/min from 30 to 200°C; higher heating rates lead to lower glass transition temperatures.     

Synthesis and properties of methyl hexahydrophthalic anhydride‐cured fluorinated epoxy resin 2,2‐bisphenol hexafluoropropane diglycidyl ether

The fluorinated epoxy resin, 2,2‐bisphenol hexafluoropropane diglycidyl ether (DGEBHF) was synthesized through a two‐step procedure, and the chemical structure was confirmed by ¹H n uclear magnetic resonance (NMR), ¹³C NMR, and Fourier transform infrared (FTIR) spectra. Moreover, DGEBHF was thermally cured with methyl hexahydrophthalic anhydride (MHHPA). The results clearly indicated that the cured DGEBHF/MHHPA exhibited higher glass transition temperature (T_g 147°C) and thermal decomposition temperature at 5% weight loss (T₅ 372°C) than those (T_g 131.2°C; T₅ 362°C) of diglycidyl ether of bisphenol A (DGEBA)/MHHPA. In addition, the incorporation of bis‐trifluoromethyl groups led to enhanced dielectric properties with lower dielectric constant (D_k 2.93) of DGEBHF/MHHPA compared with cured DGEBA resins (D_k 3.25). The cured fluorinated epoxy resin also gave lower water absorption measured in two methods relative to its nonfluorinated counterparts. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2801–2808, 2013     

Curing and properties comparison of an unsaturated polyester resin,varying crosslinking reaction conditions

In this work four different curing modes were used to crosslink a general-purpose unsaturated polyester resin. Styrene was used as monomer and glass fiber mat as reinforcement. The four curing modes included a traditional convection oven, a long-wavelength infrared (IR) radiation oven, a medium-wavelength IR radiation oven, or room temperature for an open-curing condition without oven heating. Some samples were cured using initiator only, and others were cured combining initiator and promoter. For oven curing, chamber temperature was 85°C. For the samples, final curing conversion (using Fourier transform IR spectroscopy), as well as glass transition temperature (T_g), Young's modulus, impact strength, and Shore D hardness were measured and compared. The medium-wavelength IR radiation oven as curing condition offered the best option for highest conversion, T_g, and mechanical properties. Polym. Compos. 25:662–666, 2004. © 2004 Society of Plastics Engineers.     

Carbazole‐based poly(aryl ether ketone) containing crosslinkable allyl groups on the side chains: synthesis,characterization and properties

This paper presents a feasible method for introducing crosslinkable groups into a polymer to achieve excellent chemical resistance and improved thermal stability. Here, 3,6‐bi(4‐fluorobenzenzoyl)‐N‐allylcarbazole, a novel allyl‐containing difluoroketone monomer, is synthesized and characterized. The resulting monomer is polymerized with phenolphthalein through the aromatic nucleophilic substitution reaction at 160 °C to provide the soluble poly(aryl ether ketone) (PAEK) with a pendant allyl group. The obtained PAEK is characterized using Fourier transform infrared spectroscopy, NMR and gel permeation chromatography. The crosslinking reaction of the polymer occurs at 270 °C, and it imparts excellent solvent resistance. DSC analysis shows that the glass transition temperature (T_g) of the cured polymer increases to 262–306 °C when the curing temperature is elevated or when the curing time is extended within certain limits. The rate of increase of T_g and the rate of the crosslinking reaction decrease as the curing time is extended under all of the investigated curing temperatures. The cured PAEKs possess good thermal stability with 5% weight loss temperatures up to 450 °C. The tensile strength and Young's modulus of the polymer film cured at 300 °C for 2 h are 65 MPa and 1.4 GPa, respectively. In addition, the polymer films before and after curing exhibit similar UV?visible absorption and blue light emission. © 2014 Society of Chemical Industry     

The boron trifluoride monoethyl amine complex cured epoxy resins

The curing exotherm pattern is affected by the equivalent ratio of curing agent, boron trifluoride monoethylamine complex (BF₃ · MEA), to epoxy resin. The diglycidyl ether of 9,9-bis(4-hydroxyphenyl) fluorene (DGEBF) cures more slowly than the diglycidyl ether of bisphenol A (Epon 828). The glass transition temperatures (T_g's) of BF₃ · MEA cured Epon 828 are increased with inceasing concentration of curing agent (0.0450–0.1350 eq.) cured DGEBF. The activation energies for the thermal decomposition for BF₃ · MEA (0.0450–0.1350 eq.) cured DGEBF. The activation energies for the thermal decomposition for BF₃ · MEA (0.0450 eq./epoxy eq.) cured Epon 828 and DGEBF are almost equivalent 43 and 44 kcal/mol, respectively. DGEBF when added to DGEBA improves the T_g and char yield with the BF₃ · MEA curing system. The T_g of both resin systems can be increased by longer post cure, whereas the char yield does not appear to change significantly. No ester group formation is found for the BF₃ · MEA-cured DGEBF, although this has been previously reported for the DGEBA system. The BF₃ · MEA cure at 120°C is better than at 140°C because of vaporization and degradation of the curing agent at the higher temperature. The rapid gelation of the epoxy resin may be another reason for the lower degree of cure at high temperature.     

N‐(2‐biphenylenyl)‐4‐[2′‐phenylethynyl] phthalimide: 2. Detailed study of the monomer cure and properties of the resulting polymer

A detailed study is presented of the high‐temperature cure of the difunctional monomer N‐(2‐biphenylenyl)‐4‐[2′‐phenylethynyl]phthalimide (BPP) and the thermal properties of the resulting homopolymer. Although the phenylethynyl groups are consumed within 1 h at 370 °C, other reactions continue well after this, leading to a cured polymer whose glass transition temperature (T_g) is highly dependent on cure time and temperature. A T_g of 450 °C is achieved after a 16 h cure at 400 °C. Use of chemometrics to analyse the infrared spectra of curing BPP provides evidence for changes in the aromatic moieties during cure, perhaps indicative of co‐reaction between the biphenylene and phenylethynyl groups; however, other processes also contribute to the overall complex cure mechanism. Despite the high T_g values, BPP homopolymer exhibits unacceptably poor thermo‐oxidative stability at 370 °C, showing a weight loss of about 50 % after 100 h ageing. This is perhaps a result of formation of degradatively unstable crosslink structures during elevated‐temperature cure. Copyright © 2004 Society of Chemical Industry     

Preparation and properties of UV-autocurable BTDA-based polyurethane methacrylates

Syntheses of several UV-autocurable methacrylourethanes and the effects of polyol type on their properties are investigated. Autocurable benzophenone tetracarboxylic dianhydride (BTDA)-based polyurethane methacrylates are prepared by addition reaction from benzophenone tetracarboxylic dianhydride (BTDA), 2,4-toluene diisocyanate (TDI), 2-hydroxyethyl methacrylate (HEMA), and polyol (polyethylene glycol, polydiethylene succinate, polydiethylene maleate, or polydiethylene hexamethylene-dicarbamate). Autocurable oligomers possess good pot life and are cured rapidly when exposed to ultraviolet (UV) radiation without the addition of photoinitiator. The different polyols are used to obtain wide range properties of cured films with a glass transition temperature (T_g) range of -10.5-5.5°C. Increasing the T_g of polyol shifts the dynamic mechanical storage modulus and loss factor of the cured film to high temperature. For practical application, oligomer is mixed with reactive monomers to bring the systems to a workable viscosity at room temperature. Among the monomers, the higher the composition of hydroxyethyl acrylate in the oligomer-monomer system, the higher the curing rate of the system as compared with neat oligomer. Moreover, increasing the chain length of dimethacrylate monomers results in a decrease in breaking strength from 160 to 140 kg/cm², in Young's modulus from 771 to 400 kg/cm², and in glass transition temperature from 18 to 6.5°C, while the elongation at breaking increases from 70 to 130%.     

Preparation and properties of a new polytriazole resin made from dialkyne and triazide compounds and its composite

A new kind of polytriazole resins were prepared from a triazide and a dialkyne compounds and characterized. These resins can be cured at 80 °C. The curing process for a resin was traced by FT-IR. The glass transition temperature T_g and thermal decomposition temperature T_d5 of the cured resin with the molar ratio of azide group to alkyne group [a]/[b]=1.0:1.0 reach 216 °C and 360 °C, respectively. The flexural strength of the cured resin and its glass fiber reinforced composite arrive at 183.6 MPa and 963.4 MPa, respectively. The resin would be a good candidate for the matrices of advanced composites.     

Thermal properties of epoxy resins crosslinked by an aminated lignin

Aminated lignin possessing significant amount of reactive amino groups was studied as a curing agent of epoxy resin. Fourier transform infrared spectroscopy results proved the reactivity of the aminated lignin with the epoxy resin. Both appearance features and scanning electron microscopy images indicated that the transparent and homogeneous epoxy resin films could be formed with the aminated lignin less than 40% in the hardener mixture. In addition, thermogravimetric analysis and dynamic thermomechanical analysis results revealed that the epoxy resin cured by aminated lignin had better thermal stability compared with ones cured by a common hardener. The mass loss of the epoxy resin cured by the aminated lignin before 300°C was small around only 2.5%. The T_g (the glass transition temperature) of epoxy resin sample after cured by mixed hardener increased from 79°C to 93°C. The obvious difference (70–84°C) of T_d (the thermal deformation temperature) was also observed from the samples with and without the aminated lignin after cured at a high temperature. POLYM. ENG. SCI., 55:924–932, 2015. © 2014 Society of Plastics Engineers     

Morphology,rheology, and mechanical properties of dynamically cured EPDM/PP blend: Effect of curing agent dose variation

The structure development, rheological behavior, viscoelastic, and mechanical properties of dynamically cured blend based on the ethylene–propylene–diene terpolymer (EPDM) and polypropylene (PP) with a ratio of 60/40 by weight were studied. The variation of two‐phase morphology was observed and compared as the level of curing agent was increased. Meanwhile, as the level of curing agent increased, viscosity as a function of shear stress always increased at a shear stress range of 2.2 × 10⁴ to 3.4 × 10⁵ Pa at the temperature of 200°C, yet viscosity of the blend approached each other at high shear stress. Dynamic mechanical spectra at different temperatures show that dynamic modulus (E′) of the blend exhibits two drastic transitions corresponding to glass transition temperature (T_g) of EPDM and T_g of PP, respectively. In the blends T_gs of EPDM increase and T_gs of PP almost remain unchangeable with an increase in curing agent level. Tensile strength increased, yet elongation at break decreased as the level of curing agent is increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 357–362, 2004     

Vitrification and further structural relaxation in the isothermal curing of an epoxy resin

Isothermal curing of an epoxy resin based on diglycidyl ether of bisphenol A, using a hardener derived from phthalic anhydride, has been performed at curing temperatures between 30 and 130°C. Samples were cured isothermally at various intervals of time and analyzed by differential scanning calorimetry (DSC), the glass transition temperature T_g, and the conversion degree being determined by the residual enthalpy technique. The vitrification phenomenon and a further structural relaxation process, occurring at curing temperatures (T_c) lower than the maximum T_g (109°C), at which T_g equalizes T_c, have been studied at curing temperatures between 30 and 100°C. The structural relaxation process is analyzed by the endothermic peak that appears superposed on T_g in dynamic DSC scans. The area of this peak (Q) is a measure of the recovery enthalpy, and thus of the extent of the relaxation process. This process begins at higher curing times (t_c) when T_c decreases because the vitrification of the system starts later. Both the enthalpy recovery (Q) and the temperature of the endothermic peak (T_m) increase with the annealing time (t_a), calculated as the difference between t_c and the time in which vitrification occurs, and tend to have a limiting value due to the fact that the system loses mobility when the free volume decreases during its asymptotic approach toward the metastable equilibrium state. Furthermore, the dependence of Q and T_m on t_a at different T_c shows that the relaxation process in partially cured resins depends on the conversion degree of the system and consequently on the crosslinking density of the network.     

Highly reversible and repeatable PTCR characteristics of PMMA/Ag‐coated glass bead composites based on CTE mismatch phenomena

Positive temperature coefficient of resistivity (PTCR) behavior of poly(methyl methacrylate) PMMA/silver (Ag)‐coated glass bead composites has been investigated with reference to the conventional PMMA/carbon black (CB) composites. The PMMA/CB composites showed a sudden rise in resistivity (PTC trip) at 115°C, close to the glass transition temperature (T _g, 113°C) of the PMMA. However, the PTC trip temperature (92°C) of PMMA/Ag‐coated glass bead composites was appeared well below the T _g of PMMA. The room temperature resistivity and PTC trip temperature of the composites were also very much stable upon thermal cycling. Addition of 1 phr of nanoclay increased the PTC trip temperature of PMMA/CB composites to 120°C, close to the T _g (118°C) of PMMA/clay nanocomposites, while PMMA/clay/Ag‐coated glass bead nanocomposites showed the PTC trip at 98°C. We proposed that the mismatch in coefficient of thermal expansion (CTE) between PMMA and glass beads played a key role that led to a disruption in continuous network structure of Ag‐coated glass beads even at a temperature well below the T _g of PMMA. The decrease in dielectric permittivity of PMMA/Ag‐coated glass bead composites on increasing frequency indicated possible use of the PTC composites as dielectric material. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Annealing studies on a fully cured epoxy resin: Effect of thermal prehistory,and time and temperature of physical annealing

The dynamic mechanical behavior at about 1 Hz of a fully cured epoxy resin (maximum glass transition temperature, T_g∞, ca. 170°C) ahs been studied during and after isothermal annealing in terms of the influence of thermal prehistory, time of annealing, and temperature of annealing (T_a). Annealing temperatures ranged from T_g ? 15 to T_g ? 130°C. The rate of isothermal annealing was observed to decrease by a decade for each decade increase of annelaing time when the material was far from equilibrium. Annealing at high temperatures did not measurably affect the mateiral properties during cooling (for T ? T_a); similarly the effect of annealing at low temperatures was not measurale during heating (for T ? T_a).     

PET interleaving veils for improved fracture toughness of glass fibre/low‐styrene‐emission unsaturated polyester resin composites

The use of interleaved polyethylene terephthalate (PET) veils to increase the interlaminar fracture toughness of glass fiber‐reinforced, low‐styrene emission, unsaturated polyester resin composites, was investigated. PET, being chemically similar to the unsaturated polyester resin, was expected to exhibit good wetting and strong interaction with the matrix. Composite laminates were manufactured by hand lay‐up, with the veil content varying up to 7%. The effects of PET veils on the interlaminar shear strength, flexural strength, flexural modulus, glass transition temperature, damping parameters, and Mode‐I interlaminar fracture toughness of the composite were studied. The veils were found to enhance most of these properties, with only minor negative effects on flexural stiffness and T_g. The PET/resin bonding did indeed prove to be strong, but the enhancement of fracture toughness was not as much as expected, because of the weaker glass/resin interface providing an alternative crack propagation path. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42877.     

Microwave processing of SiC nanoparticles infused polymer composites: Comparison of thermal and mechanical properties

The goal of this study is to compare thermal and mechanical properties of an epoxy resin system reinforced with SiC nanoparticles using both conventional thermal curing and microwave irradiation techniques. The microwave curing technique has shown potential benefits in processing polymeric nanocomposites by reducing the curing time without compromising the thermo‐mechanical performances of the materials. It was observed from this investigation that, the curing time was drastically reduced to ～30 min for microwave curing instead of 12 h room temperature curing with additional 6 h post curing at 75°C. Ductile behavior was more pronounced for microwave curing technique while thermal curing showed brittle like behavior as revealed from flexural test. The maximum strain to failure was increased by 25–40% for microwave‐cured nanocomposites over the room temperature cured nanocomposites for the same loading of nanofillers. The glass transition temperature (T_g) also increased by ～14°C while curing under microwave irradiation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41708.     

Hybrid fiber fabric composites from poly ether ether ketone and glass fiber

Poly ether ether ketone (PEEK) polymer was extruded into filaments and cowoven into unidirectional hybrid fabric with glass as reinforcement fiber. The hybrid fabrics were then converted into laminates and their properties with special reference to crystallization behavior has been studied. The composite laminates have been evaluated for mechanical properties, such as tensile strength, interlaminar shear strength (ILSS), and flexural strength. The thermal behavior of the composite laminates were analyzed using differential scanning calorimeter, thermogravimetric analyzer, dynamic mechanical analyzer (DMA), and thermomechanical analyzer (TMA). The exposure of the fabricated composite laminates to high temperature (400 and 500°C) using radiant heat source resulted in an improvement in the crystallanity. The morphological behavior and PEEK resin distribution in the composite laminates were confirmed using scanning electron microscope (SEM) and nondestructive testing (NDT). Although DMA results showed a loss in modulus above glass transition temperature (T_g), a fair retention in properties was noticed up to 300°C. The ability of the composite laminates to undergo positive thermal expansion as confirmed through TMA suggests the potential application of glass–PEEK composites in aerospace sector. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci 117:1446–1459, 2010     

Rubber modification of low temperature cure cyanate ester matrices and the performance in glass fabric composites

Low temperature cure cyanate ester resin systems were developed and modified with epoxy‐terminated butadiene acrylonitrile rubber (ETBN) and impregnated into woven glass fabric. Mode I and mode II interlaminar fracture toughness values of the cured laminates were evaluated as a function of rubber concentration. Mode I fracture toughness increased to almost twice that of the unmodified system, while mode II fracture toughness remained essentially unchanged. Composite samples were subjected to aging experiments in water and the absorption/desorption behavior was investigated as was the effect on thermal performance. The presence of rubber was found to reduce the rate of matrix deterioration but also caused a substantial increase in water uptake. It was found that although the addition of rubber to the matrices decreased the unconditioned (dry) T_g all specimens showed the same reduction in T_g, after equilibrium water absorption.     

Thermal and dynamic mechanical properties of microwave and heat‐cured poly(methyl methacrylate) used as dental base material

In this study, the particle size distribution, molecular weight, thermal analysis (TGA) differential scanning calorimetry (DSC) and thermogravimetric analysis, and dynamic mechanical analysis (DMA) of poly(methyl methacrylate) used as dental base material were investigated. The commercial raw material used were prepared for microwave curing, and they were cured by microwave and conventional heat methods. The average particle size of the powder studied (103.1 μm) were much larger than that of the commercial powders (50–78 μm) for conventional curing. The particle size dietribution were almost symmetrical and narrow. The viscosity‐average molecular weight were larger for microwave curing and increased with curing time. The glass transition temperature T_g measured (about 110°C) by DSC increased with curing period in microwave oven. The values of T_g were close to each other for both curing techniques. The degradation temperature range observed by TGA were 200–377°C. The movements of molecular chains in their conformations were studied by DMA in the form of changes in different mechanical properties with temperature. It was shown that crosslinking increased with increase of curing time. The changes were more noticeable in microwave curing compared to conventional heat curing. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2971–2978, 1999     

Time-temperature-transformation (TTT) cure diagrams: Relationships between Tg,cure temperature,and time for DGEBA/DETA systems

Isothermal curing of a bisphenol A diglycidyl ether-based epoxy-resin-based, using an aliphatic polyamine, has been performed at temperatures between 20 and 60°C. Samples were cured isothermally at various intervals of time, and analyzed by differential scanning calorimetry (DSC). The glass transition temperature (T_g) and the conversion ratio cure determined by residual enthalpy analysis is used as an isothermal cure-controlled reaction. A time-temperature-transformation (TTT) isothermal cure diagram was carried out to include the time to vitrification and iso-T_g curves. © 1996 John Wiley & Sons, Inc.