Tailoring the viscoelasticity of epoxy thermosets

This research work is aimed to understand the effect of epoxy resin chemistry on the viscoelasticity of the cured epoxy thermosets. In this article, two model systems are selected based on epoxy‐amine reactants. In the model Systems I, the functionality of the epoxy is varied. In model System II, the pendant (side) chain length in the amine is varied. It is found that by varying the initial properties (e.g., functionality, pendant chain length, mixing ratio (r), aromaticity, etc.) the network properties (crosslink density and flexibility) of the cured (or hardened) epoxy changed. The changes (or shift) in the viscoelastic properties (or viscoelasticity) of the cured epoxy is mainly due the changes in the network properties. Further, to study the time and temperature effects the viscoelastic master curves for the two model systems are generated using Time‐Temperature‐Superposition (TTS) principle. The shift in the viscoelastic master curves is modeled with a simple Kohlrausch‐Williams‐Watts (KWW) fit function. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improving glass transition temperature of unsaturated polyester thermosets: Conventional unsaturated polyester resins

Highly crosslinkable unsaturated polyester resins (UPR) have attracted many interests in the application as reinforced matrix materials. Here, we present a systematical study of the influence of different curing conditions and styrene concentrations on resin viscosity and dynamic-mechanical properties of the thermoset. The pure maleic Palapreg® P18-03 was selected as model UPR because of its broad industrial use. By applying newly developed thermal curing profiles (without thermal initiators) and by raising the styrene content, the T_g of the network could be increased up to 206/215°C (1/10 Hz). For the first time, a fast curable UPR based on propylene glycol and neopentyl glycol with a T_g of up to 215°C is described. A partial substitution of problematic styrene with methylmethacrylate, tert-butylacrylate, and maleic anhydride (MA) was studied as well. MA leads to significantly improved resin reactivity. A resin containing 42 wt% styrene and 8 wt% MA yields thermosets with remarkably improved mechanical properties and with a narrower glass transition range compared to the original P18-03.     

Aspects of reproducibility and stability for partial cure of epoxy matrix resin

Partial cure of thermosets is a promising approach to enhance manufacturing possibilities of reinforced and unreinforced polymers. If partial cure is taken into consideration as a genuine process parameter, novel manufacturing technologies can be developed by exploiting the specific properties of incomplete polymer networks. A main concern in this context is to control the kinetic reaction avoiding inhomogeneous or instable degrees of cure. Based on a combination of numerical simulations and experiments, a methodology is presented that enables a systematic assessment of the reproducibility and stability of partial cure. Special attention is paid to the interaction of thermal boundary conditions and the cure kinetic of thick samples as well as the storability of partially cured resin under different conditions. Guidelines for cure cycle selection, mold design, and storage are derived. The possibility to use complex multistep cure schedules and extended storage periods is demonstrated for an unmodified noninhibited epoxy resin. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals Inc. J. Appl. Polym. Sci. 2020 , 137, 48342.     

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     

Enhanced film forming ability of benzoxazine–urethane hybrid polymer network by sequential cure method

Uniform copolymer films of benzoxazine resin (BA‐a) and urethane prepolymer (PU) were prepared at various BA‐a/PU mass ratios (100/0, 80/20, 60/40, 40/60, 20/80, and 0/100) via sequential cure method comprising of moisture cure and thermal cure steps. In the moisture cure step, Fourier Transform Infrared (FT‐IR) spectra revealed the network formation between NCO‐terminated group and moisture to firstly produce PU solid film. Then in the thermal cure step, the change of tri‐substituted benzene ring to tetra‐substituted benzene ring was observed suggesting polybenzoxazine network formation in this step. Moreover, the spectra reveal that isocyanate groups in polyurethane structure could react with phenolic hydroxyl groups of BA‐a to form biuret and allophanate groups. Dynamic mechanical analysis (DMA) confirms a synergistic behavior in glass transition temperature (T_g) of the alloys with the highest T_g value of 275°C which is uniquely observed in these alloys obtained from traditionally thermal cure method. The proposed sequential cure method above is found to be highly useful for uniform coating or film casting process which lacks in traditional, low A‐stage viscosity, benzoxazine resin. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40502.     

Shape memory CTBN/epoxy resin/cyanate ester ternary resin and their carbon fiber reinforced composites

Carboxylated-terminated liquid acrylonitrile rubber (CTBN) and epoxy resin (JEF-0211) were coreacted with cyanate ester (CE) to form CTBN/EP/CE ternary resin systems. Further, the ternary resin system was applied as prepreg for carbon fiber composites with vacuum bag degassing molding process. CTBN/EP/CE ternary shape memory polymer (SMP) exhibited relatively high tensile strength, Young's modulus, impact strength, and excellent shape memory properties. Compared with CTBN/EP/CE ternary SMP, CTBN/EP/CE carbon fiber composites showed much higher mechanical properties, such as their tensile strength and Young's modulus were high to 570 MPa and 36.7 GPa, respectively. Furthermore, CTBN/EP/CE carbon fiber composites exhibited good shape memory properties, their shape fixity ratio and shape recovery ratio were more than 95% after 30 times repeating shape memory tests. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48756.     

A new approach to estimate the curing mode of thermosetting polymer films with regard to physical aging and slow chemical processes

We propose an original method to determine the temperature and time required for additional curing of physically aged partially cured glass-shaped systems, based on the example of epoxy amine systems. The approach consists of the plotting of temperature–time–transformation (TTT) diagrams, supplemented with lines, which illustrate the shift in glass transition temperature (T_g) as a result of the processes of physical aging (enthalpy relaxation) and with isoconversion curves. Then we should determine T_g of partially cured and aged sample at a certain temperature. Having known this T_g value, the position of the isoconversion curve at a given point and T_g,∞ as well, we can determine the postcuring time at T = T_g,∞ + 5 K. Thus, the method provides information about the temperatures and the duration of these two consecutive steps. The TTT diagrams are based on experimental results obtained by differential scanning calorimetry in dynamic mode with preliminary heated samples in an external thermostat. The proposed approach based on epoxy amine systems allows the prediction of the optimal curing mode for thermosetting systems to provide the highest degree of cure. Our method is applicable to a wide range of thermosetting polymer systems that complete transition to a glassy state before full conversion is achieved.     

Low k epoxy resin containing cycloaliphatic hydrocarbon with high crosslinking density

High performance epoxy resins have attracted much research interest in the last decades. Herein, two novel epoxy monomers containing cycloaliphatic hydrocarbon, 1,4‐bis(4‐(N,N‐diglycidylamino)phenoxy)cyclohexane (CyhEP) and 1,3‐bis(4‐(N,N‐diglycidylamino)phenoxy)adamantane (AdaEP) were synthesized and characterized. They were cured with 4‐methylhexahydrophthalic anhydride (MHHPA) to prepare the highly crosslinked thermosets. Both epoxy resins show good thermal stability (T_d5 > 300 °C), high glass transition temperature (> 200 °C), and high storage modulus (> 3.2 GPa) due to their highly crosslinked structure. The AdaEP/MHHPA resin shows a low dielectric constant (3.4 at 1 MHz) because of the introduction of bulky rigid adamantane into the polymer. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43456.     

Molecular modeling of physical aging in epoxy polymers

Epoxy resins are often exposed to prolonged periods of sub‐T_g temperatures which cause physical aging to occur. Because physical aging can compromise the performance of epoxies and their composites and because experimental techniques cannot provide all of the necessary physical insight that is needed to fully understand physical aging, efficient computational approaches to predict the effects of physical aging on thermomechanical properties are needed. In the current study, a new method is developed to efficiently establish molecular models of epoxy resins that represent the corresponding molecular structure at specific aging times. Although this approach does not simulate the physical aging process directly, it is useful in establishing molecular models that resemble physically aged states of epoxies. Such models are useful for predicting the thermomechanical properties of aged epoxy resins to facilitate the design of durable engineering structures. For demonstration purposes, the developed method is applied to an EPON 862/diethylene toluene diamine epoxy system for three different crosslink densities. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Adjustable amine–epoxy composition in a stratified thin film with a spin‐coating process: A useful tool for establishing relationships between the local glass‐transition temperature at the interface and the network structure

An easy method for preparing supported homogeneous epoxy–amine thin films on a silica surface consisting of two distinct layers was developed via spin coating from epoxy–amine solutions. Because of these two layers had the controlled properties of the upper layer, we showed that it was possible to precisely control the epoxy–amine stoichiometry in the sublayer through the initial epoxy–amine ratio, the spin‐cast process, and the overall film thickness. First, in the thin films, the primary amine–epoxy conversion was constant, whatever the thickness and initial epoxy–amine stoichiometry for a given curing schedule. As the primary amine conversion can be independently tuned in thin films, it thus provided a rather unique and easy method for better understanding the relationship between the network structure curing at the interface and the resulting properties, such as the glass‐transition temperature (T_g) and elastic modulus. Here, we also showed that we could access the local T_g; this implied a potential application of these experimental data in predictive composite material properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42078.     

Toughening of epoxy novolac resin using cardanol based flexibilizers

In this work, two different cardanol based epoxies (Cardolite NC‐514 and Cardanol NC‐547) were employed as flexibilizers to toughen an epoxy novolac resin namely, poly[(phenylglycidyl ether)‐co‐formaldehyde] (PPGEF). 4,4′‐Diamino‐3,3′‐dimethyl dicyclohexyl methane (BMCHA) was used as a curing agent. Differential scanning calorimetry and dynamic mechanical thermal analysis of the composites showed a gradual decrease in glass transition temperatures (T_g) with increase in cardolite content confirming the incorporation of flexible moieties into the brittle resin matrix. Improvement in toughening of PPGEF/Cardolite composites was manifested by increase in the izod impact strength of both the composites. The tensile strength increased marginally for composites with increasing amount of Cardolite NC‐514 but decreased for the composites containing Cardolite NC‐547. This was attributed to the lack of rotational motion in the chain due to close proximity of rigid phenyl rings in NC‐547. SEM of the cryo‐fractured surfaces of composites showed good compatibility between PPGEF and cardanol based flexibilizers. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43318.     

Multiscale thermal modeling of cured cycloaliphatic epoxy/carbon fiber composites

Cycloaliphatic epoxies (CEs) are commonly used for structural applications requiring improved resistance to elevated temperatures, UV radiation, and moisture relative to other epoxy materials. Accurate and efficient computational models can greatly facilitate the development of CE‐based composite materials for applications such as Aluminum Conductor Composite Core high‐voltage power lines. In this study, a new multiscale modeling method is developed for CE resins and composite materials to efficiently predict thermal properties (glass‐transition temperature, thermal expansion coefficient, and thermal conductivity). The predictions are compared to experimental data, and the results indicate that the multiscale modeling method can accurately predict thermal properties for CE‐based materials. For 85% crosslink densities, the predicted glass‐transition temperature, thermal expansion coefficient, and thermal conductivity are 279 °C, 109 ppm °C^?1, 0.24 W m^?1 K^?1, respectively. Thus, this multiscale modeling method can be used for the future development of improved CE composite materials for thermal applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46371.     

Epoxy‐amine networks with varying epoxy polydispersity

Solid, high molecular weight DGEBA‐based epoxies were blended with high purity liquid DGEBA to create several resins with equivalent epoxy equivalent weights, but with polydispersity indices (PDIs) ranging from 3 to over 10. The resins were cured with a stoichiometric amount of polyetheramine and compared to a nonblended epoxy with PDI of 1.8. Modulus, glass transition temperatures, and molecular weight between cross‐links were measured using dynamic mechanical analysis. Coefficients of thermal expansion (CTE) were measured and used to extend room temperature density measurements as a function of temperature. Fracture properties were also measured. Overall, the increased polydispersity has almost negligible effect, with the main difference occurring in the slope of the glassy CTE, with more polydisperse epoxies having a slower increase in CTE. In comparison to previous work where bimodal amines were blended with DGEBA, we conclude that epoxy resins are far more sensitive to distributions in the flexible portion, rather than the more rigid one. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41503.     

Amino‐capped aniline trimer/epoxy resin intercrosslinked networks

An amino‐capped aniline trimer (ACAT) in emeraldine base form was reacted with an epoxy resin to produce intercrosslinked networks. The quinoid structure of the ACAT was able to crosslink on curing and, thus, led to a very high glass‐transition temperature of the cured resin. The epoxy resin cured with the ACAT showed superior thermal properties over the resins cured with p‐phenylenediamine and 4,4′‐diamino diphenylamine. These findings were based on differential scanning calorimetry, IR, dynamic mechanical analysis, and thermogravimetric analysis data. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 222–226, 2006     

Evolution of properties with increasing cure of a thermosetting epoxy/aromatic amine system: Physical ageing

Isothermal physical ageing below the glass‐transition temperature (T_g) of a high‐T_g thermosetting difunctional epoxy/tetrafunctional aromatic amine system was investigated at different ageing temperatures (T_a) and chemical conversions (monitored by the T_g) using the torsional braid analysis freely oscillating torsion pendulum technique. In the absence of chemical reaction during an isothermal ageing process, the rate of isothermal physical ageing passes through a minimum with increasing conversion. The minimum is related to the minimum in mechanical loss between the secondary relaxation in the glassy state (T_β) and the glass‐transition relaxation (T_g) (the temperatures of both of which increase with increasing conversion). If isothermal ageing rates for all conversions (beyond gelation) would have been measured directly from temperatures below T_β to above T_g, it is concluded that two maxima in isothermal ageing rate would have been observed corresponding to the two relaxation processes. There exists a superposition in isothermal ageing rate versus T_g ? T_a [by shifting horizontally (and vertically)], which implies that the ageing rate is independent of the details of the changing chemical structure attributed to cure. Controlling mechanisms during physical ageing are segmental mobility associated with the T_g region and more localized motion associated with the glassy‐state relaxation T_β. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2665–2675, 2003     

Enhancement of dynamic mechanical properties and flame resistance of nanocomposites based on epoxy and nanosilica modified with KR-12 coupling agent

The epoxy/silica nanocomposites containing a wide range of isopropyltri[di(octyl) phosphate] titanate coupling agent (KR-12) modified nanosilica (m-nanosilica) loading (0–7 wt%) cured with tetrabutyl titanate hardener were prepared. Their morphology, thermal stability, thermal expansion, and mechanical properties including hardness, abrasion resistance were investigated. The wetting ability of epoxy-nanosilica systems on glass surface was assessed based on static contact angle. The obtained results showed that the contact angle of the nanocomposites containing m-nanosilica is slightly changed as compared to the contact angle of pure epoxy resin and lower than that of the nanocomposite containing unmodified nanosilica. The data of dynamic mechanical analysis of the nanocomposites using different nanosilica content indicated that the presence of m-nanosilica lowered the recovery energy of the nanocomposites to 41.62% as compared to neat epoxy. The limiting oxygen index (LOI) of the nanocomposites confirmed that the m-nanosilica increased the flame retardance of epoxy matrix. When using 7 wt% of m-nanosilca, the LOI value of the nanocomposite was 27.4 while this index of neat epoxy was 21.6. The scanning electron microscopic images of residual char combustion of the nanocompsites indicated a formation of nanosilica layer contributed to restrain combustion of the material.     

Thermomechanical behavior of epoxy resins modified with epoxidized vegetable oils

Biobased epoxy materials were prepared from diglycidyl ether of bisphenol A (DGEBA) and epoxidized vegetable oils (EVOs) (epoxidized soybean oil and epoxidized castor oil) with a thermally latent initiator. The effects of EVO content on the thermomechanical properties of the EVO‐modified DGEBA epoxy resins were investigated using several techniques. Differential scanning calorimetry indicated that the cure reaction of the DGEBA/EVO systems proceeded via two different reaction mechanisms. Single and composition‐dependent glass transition temperature (T_g) mechanisms were observed for the systems after curing. The experimental values of T_g could be explained by the Gordon–Taylor equation [Gordon M and Taylor JS, J Appl Chem 2 :493 (1952)]. The thermal stability of the systems decreased as the EVO content increased, due to the lower crosslinking density of the DGEBA/EVO systems. The coefficient of thermal expansion of the systems was found to increase linearly with increasing EVO content. This could be attributed to the fact that the degrees of freedom available for motions of the segments of the macromolecules in the network structure were enhanced by the addition of EVO. Copyright © 2008 Society of Chemical Industry     

Kinetic and thermomechanical analysis of hydrophobic–hydrophilic copolymer thermosets synthesized via free‐radical polymerization

The synthesis of a crosslinked copolymer of hydrophobic and hydrophilic monomers, diglycidyl ether of bisphenol A vinyl ester (VE), and 2‐acrylamido 2‐methyl 1‐propane sulfonic acid (AMPS) respectively, is discussed. A methodology for real‐time monitoring of the copolymerization reaction using transmission mode near infrared (NIR) spectroscopy was employed that resolves overlapping peaks associated with the reactive double bonds. The influence of solvent, monomer ratio, and initiator concentration on the kinetic behavior of the system was investigated. The method of Mayo and Lewis was used to provide a qualitative understanding of the microstructure being formed. At low conversions (<15%) and within the compositions of interest, greater VE homopolymerization as compared with AMPS homopolymerization was observed and the product of the reactivity ratios (r_AMPS.r_VE) was close to 0.5, suggesting the formation of a moderately random copolymer structure. Thermo‐mechanical analysis shows large concentrations of AMPS had a plasticizing effect on the network structure. Solvent removal using supercritical carbon dioxide and thermal drying were compared, and the drying technique were shown to have an effect on the glass transition temperature (T_g), with the lowest T_g being 146°C for supercritically dried samples and 121°C for thermally dried systems. Gel permeation chromatography shows that there is a significant fraction of an unbound mobile phase within the network structure that might be acting as a plasticizing agent for the copolymer structure. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

The role of network architecture on the glass transition temperature of epoxy resins

A series of epoxy networks were synthesized in which the molecular weight between crosslinks (M_c) and crosslink functionality were controlled independent of the network chain backbone composition. The glass transition temperature (T_g) of these networks was found to increase as M_c decreased. However, the rate at which T_g increased depended on crosslink functionality. The dependency of M_c on T_g is well described by two models, one based on the concept of network free volume while the other model is based on the principle of corresponding states. Initially, neither model could quantitatively predict the effect of crosslink functionality in our networks. However, our tests indicated that both the glass transition and the rubbery moduli of our networks were dependent on M_c and crosslink functionality, while the glassy state moduli were independent of these structural variables. The effect of crosslink functionality on the rubbery modulus of a network has been addressed by the front factor in rubber elasticity theory. Incorporation of this factor into the glass transition temperature models allowed for a quantitative prediction of T_g as a function of M_c and crosslink functionality. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 387–395, 1997     

Triethanolamine–azodiisobutyronitrile mixture as a foaming agent for low‐density unsaturated polyester resin manufacturing at a low temperature

A triethanolamine (TEA)–azodiisobutyronitrile (AIBN) mixture was applied to the manufacturing of a low‐density unsaturated polyester resin (LDUPR) at a low temperature ranging from 53 to 66 °C. Hydrogen‐bonding activation in the TEA–AIBN mixture was put forward, and this agreed with the NMR and Fourier transform infrared (FTIR) spectroscopy results. A heat balance in the curing process of a vinyl ester unsaturated polyester resin (UPR) was examined and characterized by differential scanning calorimetry, FTIR spectroscopy, and scanning electron microscopy. The TEA–AIBN mixture decomposed easily because of the hydrogen‐bonding action between TEA and AIBN. The heat release of the activated AIBN decomposition led to the early endothermic polymerization of the vinyl ester UPR. Hydrogen‐bonding activation followed by the heat‐balance process enabled us to manufacture the LDUPR at low temperature. The optimal parameters of LDUPR manufacturing, including a ratio of TEA to AIBN of 0.4 and a dosage of TEA–AIBN mixture of 2.5 phr at a curing temperature of 60 ± 1 °C, were defined by the testing of the apparent density (ρ) and compressive strength of LDUPR. Under these conditions, ρ was 0.39 ± 0.01 g/cm³, and the specific compressive strength was 33.92 ± 1.31 MPa g^?1 cm^?3. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44797.