Effects of chemical structure changes on thermal,mechanical, and crystalline properties of rigid rod epoxy resins

Effects of chemical structure changes on the thermal, mechanical, and crystalline properties of rigid rod epoxy resins have been studied for azomethine epoxy, biphenol epoxy, and tetramethyl biphenol epoxy. Rigid rod epoxies have exhibited better properties than those of the flexible bisphenol A epoxy. The chemical structures of both rigid rod epoxy and curing agent control the properties of cured rigid rod epoxies. When a flexible curing agent (methyl cyclohexane 1,2‐dicarboxylic anhydride) was used, the chemical structure of rigid rod epoxy has dominated effects on the properties. Thus, the azomethine epoxy has shown the best thermal and mechanical properties among three rigid rod epoxies. While a rigid curing agent (sulfanilamide) was used, the physical properties of cured epoxies are not only dependent on the chemical structures of epoxies but also on the ease of formation of ordered network. Among the cured rigid rod epoxies, only the biphenol epoxy cured by sulfanilamide exhibits a liquid crystalline network. It has the highest glass transition temperature (219°C) and the lowest coefficient of thermal expansion (20.8 μm/m°C). However, the most thermal stable system is azomethine epoxy cured with sulfanilamide. It has a weight loss (39%) at 450°C. Their excellent thermal and mechanical properties of rigid rod epoxies are useful in composites, printed wiring boards, integrated circuit encapsulations, etc. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 446–451, 2000     

Characterization of epoxy resin surface energetics

This study has characterized the energetics of both the liquid state and the solid state of two commercially available epoxy resins: a DGEBA- and a TGMDA-based epoxy system. The surface properties of the liquid epoxies were evaluated by wetting measurements using a dynamic contact angle analysis (DCA). The Lifshitz-van der Waals components of the surface tension were found to be similar for both epoxy systems, while the acid-base components were found to be slightly different. Two different techniques were used to characterize the cured epoxy surface properties: wetting measurements and vapor adsorption measurements by means of inverse gas chromatography (IGC). The Lifshitz-van der Waals components of the surface energy were observed to be nearly the same for both epoxies, confirming that both resins have the same potential for non-specific interactions, in both liquid and solid states. Evaluations of the acid-base components of the work of adhesion by DCA and the Gibbs free energy change by IGC suggest that both cured epoxies show non-negligible specific interactions with both acidic and basic probes. However, computations of the accepticity and donicity parameters showed that both cured epoxies are predominantly basic, but also possess non-negligible acidity. It is likely that the presence of water on the solid surface contributes to the acidic character of the cured epoxies. The temperature dependence of the liquid surface tension for both epoxy systems was investigated. The same temperature dependence was observed: the surface tension decreased with temperature, following a linear regression. Corrections for viscous-drag effects on the liquid surface tension measurements were also made.     

氰酸酯树脂/环氧树脂共混物的化学和性能

氰酸酯 (CE)树脂 /环氧 (EP)树脂是一类具有特殊反应活性的树脂混合物。CE/EP的固化物由于自身独特的结构特征 ,是一类性能优异的树脂共混物。重点介绍了CE/EP的反应机理和主要性能。     

The impact of water released from boehmite nanoparticles during curing in epoxy-based nanocomposites

The enhancing effect on mechanical properties of boehmite (γ-AlOOH) nanoparticles (BNP) in epoxy-based nanocomposites on the macroscopic scale encouraged recent research to investigate the micro- and nanoscopic properties. Several studies presented different aspects relatable to an alteration of the epoxy polymer network formation by the BNP with need for further experiments to identify the mode of action. With FTIR-spectroscopic methods this study identifies interactions of the BNP with the epoxy polymer matrix during the curing process as well as in the cured nanocomposite. The data reveals that not the BNP themselves, but the water released from them strongly influences the curing process by hydrolysis of the anhydride hardener or protonation of the amine accelerator. The changes of the curing processes are discussed in detail. The changes of the curing processes enable new explanation for the changed material properties by BNP discussed in recent research like a lowered glass transition temperature region (T_g) and an interphase formation.     

Preparation of a light color cardanol-based curing agent and epoxy resin composite: Cure-induced phase separation and its effect on properties

A light color cardanol-based epoxy curing agent (MBCBE) was synthesized from cardanol butyl ether, formaldehyde and diethylenetriamine. In comparison, a phenalkamine with a similar structure was also prepared. The chemical structures were confirmed by GC–MS and FTIR. The cure behaviors of diglycidyl ether of bisphenol A (DGEBA) with these two curing agents was studied by differential scanning calorimetry (DSC). The morphology, mechanical properties, thermal properties of the cured epoxies were also investigated. The DSC results indicated that MBCBE is less reactive than the phenalkamine. The morphology of the cured MBCBE/DGEBA consisted of cavities dispersed within a continuous epoxy matrix. The cavities markedly improved the lap shear strength and impact strength of the cured resin. Both the two cured resins indicated a two-stage decomposition mechanism. Compared with PKA/DGEBA, the weight loss of MBCBE/DGEBA at the first stage was mainly resulted from the dispersed phase in the epoxy matrix.     

Confocal microscopy study of phase morphology evolution in epoxy/polysiloxane thermosets

The morphology of stoichiometric initially immiscible reactive blends of DGEBA epoxy resin and poly(3-aminopropylmethylsiloxane) has been characterized by laser scanning confocal microscopy. Observations were done on samples cured isothermally at different curing temperatures in the range 20-120 °C as well as in situ and in real time at 60 °C. Three different processes were revealed: coalescence, which occurs primarily at very low conversion, diffusion of DGEBA through polysiloxane-rich domains and chemical reaction, which occurs at the interphase between both phases. The interphase-thickness and compositional gradients were characterized by laser scanning confocal microscopy (LSCM). Results show that as curing temperature increases within the studied range, the material becomes more homogeneous although the interphase thickness remains almost constant.     

Synthesis and study of new radial organic/inorganic hybrid epoxides

A new approach to the synthesis of reactive organic/inorganic hybrid molecules was developed. Alternating hydrocarbon and siloxane segments were introduced into the arms of radial oligomers using hydrosilation chemistry. Cycloaliphatic and glycidyl epoxy‐terminal systems with bisphenol A‐based aromatic hydrocarbon cores and siloxane units derived from 1,1,3,3‐tetramethyldisiloxane were synthesized and fully characterized (molecules 7 and 6 , respectively). The cationic UV and thermal curing behavior of these two new radial hybrid epoxies was investigated using photo‐ and thermal‐ differential scanning calorimetry. Hybrid cycloaliphatic epoxy 7 exhibited good UV curing kinetics and photopolymerized to high conversion. The glycidyl analog 6 exhibited poor UV curing kinetics, but was readily cured using 2‐ethyl‐4‐methylimidazole as a nucleophilic curing agent. Both hybrid epoxysiloxanes exhibited extensive thermal cationic cure. The physical properties of cured films of the two new radial epoxysiloxanes were studied and compared with various commercially available hydrocarbon and siloxane benchmark materials. The cured systems exhibited lower moisture uptake and better thermal stability than most hydrocarbon epoxies examined. Several visually compatible blends of the new hybrid molecules with common hydrocarbon resins were identified, and in general organic compatibility was found to be intermediate among selected siloxane‐containing benchmarks. Molecules 6 and 7 represent progress towards the goal of synthesizing highly functional organic/inorganic hybrid molecules which combine the best attributes of both hydrocarbon epoxides and siloxane materials. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Interaction of Epoxy/Dicyandiamide Adhesives with Metal Substrates

The molecular structure of the interphase formed by curing a model adhesive system consisting of the diglycidyl ether of bisphenol-A (DGEBA) and dicyandiamide (DDA) against mechanically polished aluminum and electrogalvanized steel (EGS) substrates was determined using reflection-absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). RAIR analysis suggested that DGEBA/DDA mixtures created an interphase with a different molecular structure from the bulk of the adhesive when cured in contact with aluminum. The formation of this unique interphase was mainly due to interactions between DDA and the Al surface. XPS analysis indicated that aluminum ions exposed by heating the substrate surface were necessary for this interaction. DDA was found to adsorb onto the aluminum surface via the lone pair of electrons on the nitrogen atoms of the nitrile groups. A slight decrease in the nitrile stretching frequency suggested an additional back-bonding interaction between aluminum ions and the nitrile groups. Slight back donation of electrons from the metal to DDA resulted in a reduction product that led to the formation of the carbodiimide form of DDA. This specific reaction caused a decrease in the concentration of nitrile groups in the interphase and changed the extent of the reaction between DDA and DGEBA by inhibiting the formation of oxazolidine structures. The interaction of DDA with EGS surfaces followed a similar trend. However, the effects were much more pronounced with EGS and the extent of the curing reaction and the cross-linking rate near the metal surface were strongly affected by EGS/DDA interactions.     

Partially fluorinated polymer networks: Synthesis and structural characterization

Functionalizacion of epoxy‐based networks by the preferential surface enrichment of perfluorinated tails to achieve hydrophobic surface is described. The selected fluorinated epoxies (FE) were: 2,2,3,3,4,4,5,5,6,6,7,7,8,9,9,9‐hexadecafluoro‐8‐trifluoromethyl nonyloxirane (FED3) and 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9‐heptadecafluoro nonyloxirane (FES3). Two series of crosslinked fluorinated epoxy‐based materials containing variable fluorine contents (from 0 to 5 wt % F) were prepared using formulations based on partially fluorinated diamine, epoxy monomer and a curing agent. The epoxy monomer was based on diglycidyl ether of bisphenol A (DGEBA) while the curing agents were either propyleneoxide diamine (JEFFAMINE) or 4,4′‐methylenebis(3‐chloro 2,6‐diethylaniline) (MCDEA). It was found that depending on the curing agent employed, homogeneous distribution of fluorine or phase separation distinguishable at micrometer or nanometer scale was obtained when curing blends initially homogeneous. The morphology and composition of partially fluorinated networks were investigated on a micrometer scale combining scanning electron microscopy and X‐ray analysis. When curing with JEFFAMINE, samples were homogeneous for all fluorine proportions. In contrast, MCDEA‐cured blends showed fluorine‐rich zones dispersed in a continuous epoxy‐rich phase. A completely different morphology, characterized by a distribution of irregular fluorine‐rich domains dispersed in an epoxy‐rich phase, was obtained when curing blends initially immiscible. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Interaction of Epoxy/Dicyandiamide Adhesives with Metal Substrates

The molecular structure of the interphase formed by curing a model adhesive system consisting of the diglycidyl ether of bisphenol-A (DGEBA) and dicyandiamide (DDA) against mechanically polished aluminum and electrogalvanized steel (EGS) substrates was determined using reflection–absorption infrared spectroscopy (RAIR) and X-ray photoelectron spectroscopy (XPS). RAIR analysis suggested that DGEBA/DDA mixtures created an interphase with a different molecular structure from the bulk of the adhesive when cured in contact with aluminum. The formation of this unique interphase was mainly due to interactions between DDA and the Al surface. XPS analysis indicated that aluminum ions exposed by heating the substrate surface were necessary for this interaction. DDA was found to adsorb onto the aluminum surface via the lone pair of electrons on the nitrogen atoms of the nitrile groups. A slight decrease in the nitrile stretching frequency suggested an additional back-bonding interaction between aluminum ions and the nitrile groups. Slight back donation of electrons from the metal to DDA resulted in a reduction product that led to the formation of the carbodiimide form of DDA. This specific reaction caused a decrease in the concentration of nitrile groups in the interphase and changed the extent of the reaction between DDA and DGEBA by inhibiting the formation of oxazolidine structures. The interaction of DDA with EGS surfaces followed a similar trend. However, the effects were much more pronounced with EGS and the extent of the curing reaction and the cross-linking rate near the metal surface were strongly affected by EGS/DDA interactions.     

Experimental Study and CFD Simulation of Hydrodynamic Behaviours in an External Loop Airlift Slurry Reactor

The local hydrodynamic behaviours in an external loop airlift slurry reactor, including the gas holdup, bubble rise velocity, bubble size, were measured with a fibre optic probe. The liquid circulation velocity was measured with an ultrasound Doppler velocimetry. Two‐dimensional simulations were carried out in the framework of Two‐Fluid formulation coupled with a k‐? turbulence model. The lateral forces and interphase turbulence were taken into account and good agreement between the experimental and simulation results was obtained. The simulations show that the lateral forces and interphase turbulence have noticeable influence and should be included in the CFD model.     

Kinetic study by FTIR,TMA, and DSC of the curing of a mixture of DGEBA resin and γ‐butyrolactone catalyzed by ytterbium triflate

A mixture of diglycidylether of bisphenol A (DGEBA) and γ‐butyrolactone (γ‐BL) was cured in the presence of ytterbium triflate as a catalyst. The kinetics of the various elemental processes that occur in the curing process were studied by means of isothermal curing in the FTIR spectrometer. The kinetics of the contraction during the curing was also evaluated by TMA. In both cases, the kinetics was analyzed by means of isoconversional procedure and the kinetic model was determined with the so‐called compensation effect (isokinetic relationship). The isothermal kinetic analysis was compared with that obtained by dynamic curing in DSC. We found that all the reactive processes and the contraction follow a surface‐controlled reaction type of kinetic mechanism, R₃. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 381–393, 2004     

CURING OF PARA-TERT-BUTYLPHENOL FORMALDEHYDE EPOXY-ACRYLIC RESIN IN THE PRESENCE OF REACTIVE DILUENTS

Para-tert-butylphenol formaldehyde epoxy-acrylic resin was synthesized starting from para-tert-butylphenol formaldehyde resin in reaction with glycidyl acrylate. It was cured as such, or in the presence of reactive diluents based on glycidyl ethers of phenol, para-tert-butylphenol, as well as para-nonylphenol, respectively. The curing reaction was studied by the viscometry technique at temperatures in the range 60–90°C. The curing starts with gelation and with resin measurable rates only in the case of the resin diluted with both para-tert-butylphenol and para-nonylphenol epoxy-acrylic diluents. The analyzed samples heated on 110°C, duration 16 h, show that the curing reaction depends very much on the structure of the reactive diluents.     

Thermal and mechanical properties of aminopropoxylate-cured epoxy matrices

Bisphenol A diglycidyl ether–aminopropoxylate mixtures have been characterized with respect to their viscosities in the presence and absence of butanediol diglycidyl ether (reactive diluent), and their curing patterns have been studied at room temperature with or without 2,4,6-tris(dimethylaminomethyl)phenol (initiator/accelerator). A priori, these mixtures are expected to provide low connectivities to infinite networks at gelation, a prediction supported by the multiple glass-transition-temperature (T_g) behaviour of their cured forms. The effect of the aminopropoxylate curing agent chemistry/functionality, and the presence or absence of accelerator and reactive diluent on the tensile and impact behaviour of cured materials, is reported. An expectation of increased importance of polymerization with increases in the initiator/accelerator levels, alongside epoxy–amine addition reactions, has not been evidenced by the mechanical measurements. For diglycidyl ether bisphenol A–aminopropoxylate epoxy systems, in the glycidyl ether/reactive hydrogen molar ratio range 0·80 (set A) to 1·95 (set B), the tensile failure mode is brittle fracture. For the set A formulations, this mode of failure persists up to reactive diluent loadings of 1·01wt% based on the weight of bisphenol A diglycidyl ether. Beyond 1·01wt% reactive diluent loadings, the set A formulations show ductile failure with yielding; the tensile toughness increases with increases in reactive diluent levels. For the set B formulations, and for all reported loading levels of reactive diluent, the castings failed in brittle fashion with pronounced cavitation and stress whitening. © 1998 Society of Chemical Industry     

Curing of composite components by ultraviolet radiation: A review

Curing of polymer matrices by ultraviolet (UV) irradiation can be applied to a variety of processes in the production of composite components, as long as the component can be directly irradiated. Wet lay‐up techniques, vacuum infusion type processes with UV‐transparent membranes, filament winding, and prepreg processes have been adapted to UV curing. Unlike in thermal curing, the curing time is in the order of magnitude of minutes rather than hours, which means a significant reduction in cycle time. The radiation can be generated by a variety of sources suitable for various specific applications and different curing strategies. The most frequently used radiation sources are mercury arc lamps. Because of the absorption of radiation passing through matter, the thickness of laminates for efficient application of UV curing is limited. The curing mechanism is either radical polymerization for acrylate‐based resins or cationic polymerization for epoxies and vinyl ethers. The properties of the UV‐cured polymer matrix are determined by the cross‐linking density. This depends on the type and concentration of the photoinitiator and of the (optional) diluents, the intensity and the duration of the irradiation, and the temperature at which the curing process takes place. POLYM. COMPOS., 27:119–128, 2006. © 2006 Society of Plastics Engineers.     

Neutral Polymeric Bonding Agents (NPBA) and Their Use in Smokeless Composite Rocket Propellants Based on HMX‐GAP‐BuNENA

Very few efficient bonding agents for use in solid rocket propellants with nitramine filler materials and energetic binder systems are currently available. In this work, we report the synthesis, detailed characterization, and use of neutral polymeric bonding agents (NPBA) in isocyanate‐cured and smokeless composite rocket propellants based on the nitramine octogen (HMX), the energetic binder glycidyl azide polymer (GAP), and the energetic plasticizer N‐butyl‐2‐nitratoethylnitramine (BuNENA). These polymeric bonding agents clearly influenced the viscosity of the uncured propellant mixtures and provided significantly enhanced mechanical properties to the cured propellants, even at low NPBA concentrations (down to 0.001 wt‐% of propellant). A modified NPBA more or less free of hydroxyl functionalities for interactions with isocyanate curing agent provided the same level of mechanical improvement as regular NPBA containing a substantial number of reactive hydroxyl groups. However, some degree of reactivity towards isocyanate is essential for function.     

Crystallization,dispersion behavior and the induced properties through forming a controllable network in the crosslinked polyester‐SiO2 nanocomposites

This article describes the synthesis and characterization of two types of benzoxazine monomers based on phenol or bisphenol, aniline, and formaldehyde. Their characterization was achieved by Fourier transform infrared, ¹H-nuclear magnetic resonance, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). Lignin polymer was characterized by infrared, DSC, and TGA. The curing behavior of mixtures of benzoxazine monomers and lignin was investigated by DSC. The mass ratios of benzoxazine monomers/lignin of a series of samples were 100 : 0, 95 : 05, 90 : 10, 85 : 15, 80 : 20, 75 : 25, and 70 : 30. The results indicate that the maximum curing temperatures of the mixtures were lower than that of the pure benzoxazine monomers, and that they decreased with increasing contents of lignin in the mixture. The heat of polymerization (ΔH) of the benzoxazine monomers and lignin mixtures as a function of the mass ratio and the structure of the benzoxazine monomers shows no definite trend. The samples were cured according to the following conditions: 170°C/2h + 200°C/2h and analyzed by DSC and TGA. In all the samples, the glass transition temperature of the benzoxazines increased upon mixing with increasing amounts of lignin. The changes may be due to the formation of a more compact network structure in the mixtures. The thermal stability of the isothermally cured resins is found to be dependent on the mass ratio of benzoxazine/lignin and structure of the benzoxazine monomers. The more lignin in the mixture, the higher is the char yield in the mixture. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

木质素碱催化苯酚液化物纤维固化工艺

以木质素碱催化苯酚液化物为原料,加入六次甲基四胺后熔融纺丝,将熔纺纤维置于甲醛和盐酸混合溶液中固化处理制得固化纤维,研究了碱存在条件下木质素苯酚液化物的成纤性及初生纤维固化条件。结果表明:木质素碱催化苯酚液化物具有很好的成纤性;所得纤维性能与纺丝条件和固化工艺相关。在收丝辊转速450r/min、压力0.02 MPa、固化液盐酸质量分数15%、甲醛质量分数18.5%、固化温度95℃、升温速率10℃/h、固化时间4 h条件下,所得纤维性能较好,适于制备碳纤维。     

Main‐chain benzoxazine oligomers: Effects of molecular weight on the thermal,mechanical, and viscoelastic properties

With the intent to study materials processing properties during the curing process, oligomeric benzoxazines of different molecular weight and distribution were obtained from 4‐tert‐butylphenol, bisphenol A, 4,4′‐diaminodiphenylmethane and paraformaldehyde by varying the amounts of phenolic compounds. Average molecular weight and distribution of prepared mixtures of polybenzoxazine precursors were determined by gel permeation chromatography analysis. By knowing the molecular weight distribution of prepared mixtures of polybenzoxazine precursors its effect on thermal, mechanical, and viscoelastic properties of the resin during processing and polymerization could be investigated. Mixtures of polybenzoxazine precursors of higher average molecular weight and broader molecular weight distribution displayed faster curing, lower curing conversions, and higher crosslinking densities of cured resins leading to polybenzoxazines with improved properties. This investigation was oriented towards the material processing aspects with the focus on the effect of molecular weights and viscoelastic properties of starting materials on the proceeding of the curing, including changes in material properties, and sample molding. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46659.     

Room temperature‐curable VARTM epoxy resins: Promising alternative to vinyl ester resins

The objective of this investigation is to characterize various room temperature (RT)‐curable epoxies for vacuum‐assisted resin transfer molding (VARTM) of large structure manufacturing. Six epoxy candidate resins: X‐40, 780‐33, 780‐35, 8601/8602, 8602, 8603, and two vinyl ester resins (VE), 411‐350 and 411‐510A, are physically and thermochemically characterized. All the resins are cured at RT with extended period of time. The degree of cure for 24‐h RT‐cured samples ranges from 70 to 85% for epoxies and is comparable with the baseline VE systems (75%). After 1 year at RT, the degree of cure increases from 90 to 98%. Most of the epoxies show a single transition in dynamic mechanical analysis and differential scanning calorimetry. However, two heterogeneous transitions are observed for the VE systems. The glass transition temperature increases monotonically with exposure time, except X‐40, that rapidly achieves a plateau and remains constant. The degree of cure for the majority of the systems increases logarithmically with RT curing time with excellent fitting (R² varies from 0.92 to 1). Consistent with the increase in degree of cure, the storage modulus increases and (tan δ)_max decreases with time of exposure. A negative correlation between the curing temperature range and the total heat of reaction is observed among the epoxy systems. However, the VE systems show the reverse trend. RT curing epoxy resin (X‐40) shows promising overall result to VE system and can be a viable alternative to VE for VARTM processing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010