Thermal properties of calcium carbonate powder reinforced vinyl ester composites: Pilot study

The viscoelastic properties of vinyl ester (VE) composites filled with calcium carbonate (CC) (CaCO₃) powder have been evaluated using the dynamic mechanical analysis (DMA) technique. It was found that irrespective of the percentage by weight of CaCO₃ powder, the VE composites postcured in an oven up to 60°C have higher glass transition temperatures (T_g) and storage modulus than their counterparts cured at ambient conditions. However, the loss moduli were lower for composites postcured in an oven than their ambient cured counterparts. It was also found that the crosslinking density of the composites slightly increased with particulate (CaCO₃) loading and composites postcured in an oven have higher crosslinking density than their counterparts cured at ambient conditions. These results confirmed an increase in stiffness for composites with postcuring treatment. Micrographs by SEM were obtained and confirmed a close inter phase adhesion of the CC filler with the VE resin matrix in the composites. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Properties of novel diallyl phthalate resin modified with sulfur‐containing allyl ester compounds

Sulfur‐containing allyl ester, which reacts with diallyl phthalate (DAP) resin to have allyl groups, was synthesized by the reaction of allyl phthalic acid with bisphenol having sulfur atoms. The sulfur‐containing allyl ester compound was blended with DAP resin to improve the adhesive properties to copper. By modification with sulfur‐containing allyl ester compound, the T‐peel adhesive strength and the lap shear adhesive strength to copper was improved. In particular, the adhesive strength was greatly improved when the resin was modified with the allyl ester compound having a disulfide bond (?S?S?) (DADS). It is concluded that this result is due to the improvement of the interfacial adhesive strength because the sulfur atom was found to be located in the surface of the copper by Fourier transform infrared (FTIR) analysis. The glass transition temperature (T_g) and the thermal decomposition temperature (T_d) of the cured DAP resin modified with DADS slightly decreased with increasing concentration of DADS. The lowering of T_g is because the crosslinking density of the DAP resin modified with DADS is smaller than that of DAP resin. Moreover, from thermogravimetric analysis, the lowering of Td of the DAP resin modified with DADS is because DADS is likely to pyrolyze. © 2013 Society of Chemical Industry     

Dynamic mechanical characterization of a soy based epoxy resin system

Epoxidized allyl soyate (EAS), a novel soy based epoxy resin, has been prepared by the process of transesterfication and epoxidation of regular food grade soybean oil. Two types of crosslinking agents were employed in this study. The effects of the concentration of EAS and the type of crosslinking agent on the dynamic mechanical behavior of the soy based resin system have been investigated. The room temperature storage moduli (E′) and the glass transition temperatures (T_g) increased for the anhydride cured and decreased for the amine cured resins. The loss tangent maximum (tan δ)_max decreased for anhydride cured resins and increased for amine cured resins. The effect of frequency on the storage modulus was also studied. Master curves were constructed by the time‐temperature superpositioning technique (TTS) to predict the storage modulus at times and temperatures that are not experimentally feasible. The results indicate that soy based epoxy resins with appropriate concentrations hold great potential as a replacement for petroleum based materials in noise and vibration attenuation applications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1772–1780, 2005     

Synthesis and characterization of bis(4‐cyanato‐3,5‐dimethylphenyl)anisylmethane/epoxy/glass fiber composites

Bis(4‐cyanato‐3,5‐dimethylphenyl)anisylmethane was prepared by treating CNBr with bis(4‐hydroxy‐3,5‐dimethylphenyl)anisylmethane and blended with commercial epoxy resin in different ratios and cured at 120°C for 2 h, 180°C for 1 h, and postcured at 220°C for 1 h using diamino diphenyl methane as curing agent. Castings of neat resin and blends were prepared and characterized. The composite laminates were also fabricated with glass fiber using the same composition. The tensile strength of the composites increased with increase in cyanate content (3, 6, and 9%) from 322 to 355 MPa. The fracture toughness values also increased from 0.7671 kJ/m², for neat epoxy resin, to 0.8615 kJ/m², for 9% cyanate ester‐modified epoxy system. The 10% weight loss temperature of pure epoxy (358°C) was increased to 390°C by the incorporation of cyanate ester resin. The incorporation of cyanate ester up to 9% in the epoxy resin increases the T_g from 143 to 147°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Toughening of vinylester–urethane hybrid resins through functionalized polymers

Liquid nitrile rubber, hyperbranched polyester, and core/shell rubber particles of various functionality, namely, vinyl, carboxyl, and epoxy, were added up to 20 wt % to a bisphenol‐A‐based vinylester–urethane hybrid (VEUH) resin to improve its toughness. The toughness was characterized by the fracture toughness (K_c) and energy (G_c) determined on compact tensile (CT) specimens at ambient temperature. Toughness improvement in VEUH was mostly achieved when the modifiers reacted with the secondary hydroxyl groups of the bismethacryloxy vinyl ester resin and with the isocyanate of the polyisocyanate compound, instead of participating in the free‐radical crosslinking via styrene copolymerization. Thus, incorporation of carboxyl‐terminated liquid nitrile rubber (CTBN) yielded the highest toughness upgrade with at least a 20 wt % modifier content. It was, however, accompanied by a reduction in both the stiffness and glass transition temperature (T_g) of the VEUH resin. Albeit functionalized (epoxy and vinyl, respectively) hyperbranched polymers were less efficient toughness modifiers than was CTBN, they showed no adverse effect on the stiffness and T_g. Use of core/shell modifiers did not result in toughness improvement. The above changes in the toughness response were traced to the morphology assessed by dynamic mechanical thermal analysis (DMTA) and fractographic inspection of the fracture surface of broken CT specimens. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 672–680, 2002; DOI 10.1002/app.10392     

The glass‐forming ability and thermal stability of novolac–phenolic resin

Glass‐forming ability and thermal stability of novolac–phenolic resin with different contents of curing agent hexamethylenetramine (HMTA) are investigated. Melt fragility (M_g) and T_gd (T_gd = T_g/T_d) are proposed to characterize glass‐forming ability and thermal stability of the novolac–phenolic resin, respectively. It is found that M_g has a negative linear relationship with T_gd. The lower M_g represents the better glass‐forming ability of liquid phenolic resin while the higher T_gd represents the better thermal stability of the fully cured phenolic resin. Further more, M_g establishes a kinetic relationship between glass‐forming ability of liquid uncured and thermal stability of fully cured novolac–phenolic resin in terms of comparing with T_gd. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Influence of accelerated ageing on methacrylate‐based denture resins heterogeneity as viewed by ESR‐spin‐probe method

The electron‐spin‐resonance (ESR) spin‐probe method, was used to study the heterogeneity of denture resins based on poly(methyl methacrylate). Results for three resins processed by microwave energy, conventional curing and cold curing (depending on the curing procedure and exposed to ageing in various environmental conditions) were compared. All three cured resins were stored over the same time (1200 h) in distilled water at ambient temperature and in artificial saliva at 348 K. The temperature‐dependent ESR spectra of a spin probe dispersed in the denture resins are analyzed in terms of line‐shapes and line‐widths. The appearance of two spectral components was taken as an indication of resin heterogeneity. The results reveal that the cold‐cured resin has a lower local density in comparison with microwave and conventionally cured resin. The amount of residual monomer also contributes to the local motion of polymer segments. The change of denture resins exposed to ageing is influenced both by the structure of the original resin and the ageing conditions. Restricted motion of a spin probe incorporated into the acrylic resins exposed to accelerated ageing suggests additional crosslinking of polymer chains. The differences are observed for all the investigated resins, but the highest change is observed with the cold‐cured resin. The ESR results are accompanied by T_g and T_m measurements. Copyright © 2005 Society of Chemical Industry     

Thermophysical properties of anhydride‐cured epoxy/nano‐clay composites

Polymer nano‐composites made with a matrix of anhydride‐cured diglycidyl ether of bisphenol A (DGEBA) and reinforced with organo‐montmorillonite clay were investigated. A sonication technique was used to process the epoxy/clay nano‐composites. The thermal properties of the nano‐composites were measured with dynamic mechanical analysis (DMA). The glass transition temperature T_g of the anhydride‐cured epoxy was higher than the room temperature (RT). For samples with 6.25 wt% (4.0 vol%) of clay, the storage modulus at 30°C and at (T_g + 15)°C was observed to increase 43% and 230%, respectively, relative to the value of unfilled epoxy. The clay reinforcing effect was evaluated using the Tandon‐Weng model for randomly oriented particulate filled composites. Transmission electron microscopy (TEM) examination of the nano‐composites prepared by sonication of clays in acetone showed well‐dispersed platelets in the nano‐composites. The clay nano‐platelets were observed to be well‐intercalated/expanded in the anhydride‐cured epoxy resin system. POLYM. COMPOS., 26:42–51, 2005. © 2004 Society of Plastics Engineers.     

Silicone‐Organic Resin Hybrid Matrix Composites

Summary: Glass fabric reinforced hybrid matrix composites of a toughened silicone resin and a vinyl ester resin were fabricated and their properties investigated. The hybrid composites consisted of multi‐layers of fiber reinforced silicone resins and vinyl ester resins. The toughened silicone resin, a crosslinkable phenylsilsesquioxane resin with high thermal and thermal oxidation resistance but relatively low T_g, was chosen to be the outer layers. The vinyl ester resin, with better strength, toughness and a much higher T_g than the toughened silicone resin, was used as the inner layers. A co‐cure process proved to establish a strong interface between the two in a hybrid composite. The hybrid composites had better flammability properties and much lower short term moisture absorption than the vinyl ester composites. The strength and modulus retention of the hybrid composites at elevated temperatures was higher than the composites using any single resin as the matrix. For example, when tested at 150 °C the flexural modulus and strength values of a twelve layer composite, with eight inner vinyl ester resin layers and four silicone outer layers, were almost an order of magnitude higher than the composite using the silicone resin alone, and were significantly higher than the one using vinyl ester resin alone. The room temperature short beam shear strength of the hybrid composites was also higher. DMA revealed that the inter‐diffusion of reactive components between the two resins was probably responsible for this synergistic effect, resulting in an α transition temperature of 182 °C for the hybrid composite, higher than that of either the silicone resin (85 °C) or the vinyl ester resin (162 °C).

     

Addition‐cure‐type phenolic resin based on alder‐ene reaction: Synthesis and laminate composite properties

A maleimide‐functional phenolic resin was reactively blended with an allyl‐functional novolac in varying proportions. The two polymers were coreacted by an addition mechanism through Alder‐ene and Wagner–Jauregg reactions to form a crosslinked network system. The cure characterization was done by differential scanning calorimetry and dynamic mechanical analysis. The system underwent a multistep curing process over a temperature range of 110–270°C. Although the cure profiles were independent of the composition, the presence of maleimide led to a reduced isothermal gel time of the blend. Increasing the allylphenol content decreased the crosslinking in the cured matrix, leading to enhanced toughness and improved resin‐dominant mechanical properties of the resultant silica laminate composites. Changing the reinforcement from silica to glass resulted in further amelioration of the resin‐reinforcement interaction, but the resin‐dominant properties of the composite remained unaltered. Increasing the maleimide content resulted in enhanced thermal stability. Integrating both the reactive groups in a single polymer and its curing led to enhanced thermal stability and T_g, but to decreased mechanical properties of the laminate composites. This can be attributed to a brittle matrix resulting from enhanced crosslinking facilitated by interaction of the reactive groups located on the polymer of an identical backbone structure. The cured polymers showed a T_g in the range of 170–190°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 737–749, 2001     

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     

Thermo‐chemical response of vinyl‐ester resin

This paper presents the thermo‐chemical characterization of Dow Derakane 411‐C50 commercial vinyl‐ester resin at low temperatures (20°C to 40°C). Differential Scanning Calorimetry (DSC) and Torsional Braid Analysis (TBA) are the experimental techniques used to characterize the material behavior. The cure kinetics are studied using DSC and are modeled using a modified autocatalytic equation with a maximum degree‐of‐cure term. Also, the effect of inhibitors in the resin system is accounted for by an inhibitor depletion model. The glass transition temperature (T^g) is also characterized using TBA and related to the degree of cure. It was found that the T_g and the degree of cure do not exhibit a linear relationship for this resin system. The findings presented in this work provide information for accurate cure modeling and process simulation of vinyl‐ester materials.     

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.     

The use of acrylated fatty acid methyl esters as styrene replacements in triglyceride‐based thermosetting polymers

Resins containing plant oil‐based cross‐linkers were studied with two reactive diluents: a styrene and an acrylated fatty acid methyl ester‐based (AFAME) monomer. Acrylated epoxidized soybean oil and maleinated castor oil monoglyceride were bio‐based cross‐linkers used. The viscosity and mechanical properties of the resulting polymers were measured and analyzed. Both bio‐based cross‐linkers prepared using the modified AFAME as diluent had a fairly high viscosity, so blends of AFAME and styrene were needed to meet the viscosity requirements established by the composite industry (<1000 cP at room temperature). In addition, the glass transition temperature (T_g) and stiffness of bio‐based cross‐linker/AFAME polymers were significantly lower than the resin/styrene polymers. Ternary blends of maleinated castor oil monoglyceride with AFAME and styrene improved the mechanical properties to acceptable comparable values (storage modulus at 30°C ～ 1200 MPa and T_g ～ 100°C). The addition of 5 wt% of chemically modified lignin led to an improvement in the mechanical properties of the polymeric matrix but caused an increase in the viscosity. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Time–temperature–transformation cure diagrams of phenol–formaldehyde and lignin–phenol–formaldehyde novolac resins

In this study, the time–temperature– transformation (TTT) cure diagrams of the curing processes of several novolac resins were determined. Each diagram corresponded to a mixture of commercial phenol–formaldehyde novolac, lignin–phenol–formaldehyde novolac, and methylolated lignin–phenol–formaldehyde novolac resins with hexamethylenetetramine as a curing agent. Thermomechanical analysis and differential scanning calorimetry techniques were applied to study the resin gelation and the kinetics of the curing process to obtain the isoconversional curves. The temperature at which the material gelled and vitrified [the glass‐transition temperature at the gel point (_gelT_g)], the glass‐transition temperature of the uncured material (without crosslinking; T_g0), and the glass‐transition temperature with full crosslinking were also obtained. On the basis of the measured of conversion degree at gelation, the approximate glass‐transition temperature/conversion relationship, and the thermokinetic results of the curing process of the resins, TTT cure diagrams of the novolac samples were constructed. The TTT diagrams showed that the lignin–novolac and methylolated lignin–novolac resins presented lower T_g0 and _gelT_g values than the commercial resin. The TTT diagram is a suitable tool for understanding novolac resin behavior during the isothermal curing process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Miscibility,crystallization behavior and specific intermolecular interactions in thermosetting polymer blends of novolac epoxy resin and polyethylene glycol

Thermosetting polymer blends of novolac epoxy resin (EPN) and polyethylene glycol (PEG) were studied. The miscibility and crystallization behavior of the blends before curing reaction were investigated by polarized optical microscopy and differential scanning calorimetry (DSC). Overall uncured blend compositions were homogeneous in amorphous state. Single composition‐dependent glass‐transition temperature (T_g) for each blend could be observed, and the experimental T_g's of blends with EPN content ≥40 wt% could be explained well by the Gordon–Taylor equation. Thermal properties of blends cured with 4,4′‐diaminodiphenylmethane were also determined by DSC. The capability of PEG to crystallize in cured blends was different from that in uncured ones because of the topological effect of highly crosslinking structure. On the basis of Fourier transform infrared spectroscopy results, it was judged that there were intermolecular hydrogen‐bonding interactions between EPN and PEG in both cured and uncured blends. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Biobased thermosetting resins composed of L‐lysine methyl ester and bismaleimide

Lysine methyl ester (LME), which was generated in situ by the reaction of lysine methyl ester dihydrochloride and triethylamine in dimethyl sulfoxide (DMSO), was prepolymerized with 4,4′‐bismaleimidodiphenylmethane (BMI) at 80°C for 2 h in DMSO. Then, the formed prepolymer was precipitated in water. The obtained LME/BMI prepolymers with molar ratios of 2:2, 2:3, and 2:4 were compression‐molded at a final temperature of 230°C for 2 h to produce cured lysine methyl ester/4,4′‐bismaleimidodiphenylmethane resins (cLBs; cLB22, cLB23, and cLB24, respectively). Fourier transform infrared (FTIR) analyses revealed that the Michael addition reaction of amino groups to the C?C bonds of the maleimide group occurred in addition to the homopolymerization of the maleimide group. The glass‐transition temperature (T_g) and 5% weight loss temperature (T₅) of the cured resin increased with increasing BMI feed content, and cLB24 showed the highest T_g (343°C) and T₅ (389°C). The flexural strengths (131–150 MPa) and moduli (3.0–3.6 GPa) of the cLBs were comparable to those of the conventionally cured resins of BMI and 4,4′‐diaminodiphenylmethane. Field emission scanning electron microscopy analysis revealed that there was no phase separation for all of the cured resins. Although cLB23 and cLB24 were not biodegradable, cLB22 had a biodegradability of 8.5% after 30 days in an aerobic aqueous medium containing activated sludge. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40379.     

Synthesis and characterization of UV‐curable acrylic resin containing fluorine groups

A novel fluorine‐containing acrylic resin, 4‐trifluoromethylphenyl glycerol dimethacrylate (TPGD), was synthesized and the structure was characterized by FTIR, ¹³C NMR, ¹H NMR, and ¹⁹F NMR spectroscopy. The conversion of cure reaction, thermal stability, glass transition temperature (T_g), and electrical properties of the TPGD acrylic resin cured with UV radiation were investigated. The thermal stability and T_g of the UV‐cured specimens show a maximum value at 1 wt% photoinitiator, due to the formation of advanced network structures. The cured specimens had a relatively low dielectric constant, attributed to the decreased deformation polarizability of segment motion in the fluorine‐containing resin. Copyright © 2004 Society of Chemical Industry     

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 characterization of polyfunctional naphthoxazines and related polymers

In pursuing the new polymers that could provide high mechanical properties and good thermal stabilities, a series of naphthoxazines are synthesized from different hydroxynaphthalenes with aniline and formaldehyde. The molecular structures are confirmed by NMR spectroscopy. After being polymerized in an autoclave, the naphthoxazine derived from 1,5-dihydroxynaphthalene is successfully cured to form the void-free resin. The density and tensile properties of these polynaphthoxazines are measured. Dynamic mechanical tests are performed to determine the T_g, crosslink density, and the activation enthalpy of the glass transition process for the polynaphthoxazines postcured in air at different temperatures. The effect of postcure temperature on the T_gs of the polynaphthzoxazines is investigated and discussed in terms of crosslink density. The polynaphthoxazine shows a T_g higher than the cure temperature. Fourier transform IR spectroscopy is applied for the molecular characterization of the curing systems. Thermal properties of these polynaphthzoxazines are studied in terms of the weight loss after isothermal aging in static air, the decomposition temperature from thermogravimetric analysis, and the change of dynamic storage moduli at high temperatures. © 1996 John Wiley & Sons, Inc.