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.     

Shape memory polymers based on uniform aliphatic urethane networks

Aliphatic urethane polymers have been synthesized and characterized, using monomers with high molecular symmetry, to form amorphous networks with very uniform supermolecular structures, which can be used as photo‐thermally actuable shape memory polymers (SMPs). The monomers used include hexamethylene diisocyanate (HDI), trimethylhexamethylenediamine (TMHDI), N,N,N′,N′‐tetrakis(hydroxypropyl)ethylenediamine (HPED), triethanolamine (TEA), and 1,3‐butanediol (BD). The new polymers were characterized by solvent extraction, NMR, XPS, UV/VIS, DSC, DMTA, and tensile testing. The resulting polymers were found to be single phase amorphous networks with very high gel fraction, excellent optical clarity, and extremely sharp single glass transitions in the range of 34–153°C. Thermomechanical testing of these materials confirms their excellent shape memory behavior, high recovery force, and low mechanical hysteresis (especially on multiple cycles), effectively behaving as ideal elastomers above T_g. We believe these materials represent a new and potentially important class of SMPs, and should be especially useful in applications such as biomedical microdevices. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

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.     

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     

Low temperature cure of epoxy thermosets attaining high Tg using a uniform microwave field

It is demonstrated for the first time that an epoxy thermoset resin can be cured at temperatures well below its T_g∞. This study compared the use of a uniform variable frequency microwave (VFM) field to standard oven curing at temperatures above and below T_g∞. Using T_g, tan δ, modulus, and FTIR measurements, it is shown that the reaction of BFDGE with MDA to attain a product with T_g∞ of 133 °C is achieved by VFM at temperatures from 100 to 140 °C; in contrast, the thermal cure normally requires 170 °C to attain the same T_g∞ and the same extent of cure. By following the pregel cure reaction with ¹³C‐NMR spectroscopy, it was determined that the lower cure temperatures of VFM cure predominately lead to chain extension and smaller amounts of crosslinking compared to the thermal cure. To explain these results, it is suggested that, after gelation, with VFM cure there is higher mobility from dipole rotations that continues the cure to completion without vitrification. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44222.     

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.     

Viscous,damping, and mechanical properties of epoxy asphalt adhesives containing different penetration-grade asphalts

Epoxy asphalt adhesive (EAA) is a thermosetting polymer modified asphalt that has been widely applied on steel bridge decks as a strong adhesive and waterproof layers. In this study, the influence of the asphalt penetration grade on the viscosity, damping and mechanical properties, bond strength, and microstructures of EAAs was investigated. The viscosity of the EAAs increased with increasing asphalt penetration grade. The presence of base asphalt increased the glass-transition temperature (T _g) of the neat epoxy. The asphalt penetration grade had a negligible effect on the T _g values of the EAAs. The existence of base asphalt improved the damping behaviors of the neat epoxy. Moreover, the damping properties of the EAAs increased with increasing asphalt penetration grade. The tensile strength, elongation at break, and bond strength values of the EAAs increased with increasing asphalt penetration grade. The bond strengths of the EAAs were 7- to 10-fold higher than that of the neat asphalt. The asphalt penetration grade had a negligible effect on the bond strengths of the EAAs. Morphological observations revealed that the average size of the dispersed asphalt particles in the epoxy decreased with increasing asphalt penetration grade. A more homogeneous phase separation was formed in the EAA with a higher penetration-grade asphalt. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47027.     

Enhancing thermal and dynamic-mechanical properties of epoxy reinforced by amino-functionalized microcrystalline cellulose

In this study, microcrystalline cellulose (MCC) was chemically modified with 3-(aminopropyl)triethoxysilane and added to epoxy to improve chemical, thermal and dynamic-mechanical characteristics of the composites. The composites were manufactured aided by sonication with 1.0%, 2.5%, or 5.0% wt/wt of untreated MCC or amino-functionalized MCC (MCC-Si). The epoxy/MCC-Si composites showed a decrease in the ─OH band by Fourier-transform infrared spectroscopy, and X-ray diffraction analysis indicated better dispersion. The incorporation of MCC-Si in epoxy resin decreased the heat of reaction, increased activation energy values (E_a) and pre-exponential factor (A), and did not affect thermal degradation. All conversion degree (α) versus temperature curves for the composites showed a sigmoidal shape. MCC-Si composites showed better dynamic-mechanical properties than the MCC counterparts, and the functionalization effect was evidenced in storage modulus (E') and loss modulus (E"). At 2.5% wt/wt of MCC-Si content an increase of 119% in E' at the glassy region, 127% in E' at the rubbery region and 173% in E" was observed compared to the neat resin, whereas the T_g barely changed among samples. Good adhesion between the amino-functionalized MCC and the epoxy matrix was observed at the fracture surface, evidencing that surface modification of MCC improves their chemical interaction.     

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.     

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

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

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     

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.     

An efficient plasticizer based on waste cooking oil: Structure and application

Recently, phthalates have been continuously banned in numerous fields by many countries. Therefore, the development of sustainable and efficient plasticizers has become particularly urgent. The waste cooking oil was used as the main raw materials in this study to synthesize an efficient plasticizer (acetylated-fatty acid methyl ester-trimellitic acid ester, AC-FAME-TAE). The structure of AC-FAME-TAE was characterized by FT-IR and ¹H NMR. The performance of the poly(vinyl chloride) (PVC) plasticized by AC-FAME-TAE was tested and compared with those of the PVC plasticized with di-2-ethylhexyl phthalate (DOP) and EFAME (epoxy fatty acid methyl ester), respectively. DSC results indicated that AC-FAME-TAE had excellent plasticizing efficiency for PVC. The mechanical properties of PVC plasticized by AC-FAME-TAE were as comparable as PVC plasticized by DOP from the results of tensile test. In addition, the PVC plasticized by AC-FAME-TAE had excellent thermal stability and solvent resistance by the results of leaching test and TGA.     

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     

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.     

Improved shape memory effects in multiwalled‐carbon‐nano‐tube reinforced thermosetting polyurethane composites

Shape memory thermosetting polyurethane (SMPU) composites containing different amount of multiwalled carbon nanotube (MWCNT) ranging from 0 to 0.250 phr were prepared. The shape memory behavior, tensile stress, and recovery stress were determined by using conventional thermomechanical cycle; however, the modified thermomechanical cycle designated as progressive stretch–relax–stretch (PSRS) cycle was also employed to create shape memory effects in studied composites. The test was carried out in water bath which was equipped with an electric heater, temperature controller, and tensile stress and strain measuring setup. The recovery and tensile stresses both were showing higher values for PSRS samples as compared with conventional samples. Loading of MWCNT improved the recovery stress of SMPU, thereby confirming reinforcing effect. The maximum recovery stress of 2.17 MPa for 0.188 phr MWCNT loading was observed as compared with 1.09 MPa of unreinforced SMPU specimen. The recovery time was also improved on reinforcement as demonstrated in this article. The morphology of fractured surface and degree of dispersion of MWCNT was studied using Field Emission Scanning Electron Microscope. The impact on glass transition temperature was also observed for MWCNT reinforcement on SMPU, which depends on the degree of dispersion and loading of MWCNT in the specimen. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44389.     

Effect of heat and frying on sunflower,oil stability

Sunflowers are one of the most important sources of vegetable oils in the world, second only to soybeans. Although in use throughout many parts of the world, sunflower seed are just now beginning to attact attention and use in the United States. Composition of the oil appears to be dependent on area of production. Sunflower oil from seed grown in northern US typically contains 70% linoleic acid. In contrast, oil from seed produced in the South generally contains 40–50% linoleic acid and is higher in mono-unsaturated fats. For most of the edible oil market, sunflower oil appears to have an advantage over most other vegetable oils. Lightly hydrogenated sunflower oil was compared with a cottonseed-corn oil mixture for frying potato chips. Organoleptic evaluation indicated that chips did not differ significantly. We also evaluated the useful life of various sunflower seed oils for deep-fat frying. Hydrogenated and unhydrogenated sunflower oils and a commercial shortening were used to deep-fry raw potatoes. A plot of the log of the Active Oxygen Method (AOM) values of the oils versus time gave a straight line, the slope of which reflects the oxidizability of the oil. Data indicated that lightly hydrogenated northern sunflower oil was much less prone to oxidation after abuse than the commercial shortening and was useful for a longer time. The southern oil deteriorated faster than the northern sunflower oil, but the two oils were processed differently. Thus, in recent work, care was taken to process both northern and southern grown sunflower seed under identical conditions. Frying studies indicated that oil from southern grown seed was more stable than that from northern seed as would be expected from their fatty acid composition.     

Influence of very long aging on the relaxation behavior of flame‐retardant printed circuit board epoxy composites under mechatronic conditions

Very long aging times, up to 15,100 h (629 days) at 110°C, were achieved on flame‐retardant printed circuit board laminates commonly used in automotive design. This composite was fabricated from glass fibers embedded in an epoxy resin. Aging was performed in an oven under an air atmosphere at a temperature lower than the glass‐transition temperature. Temperature‐modulated differential scanning calorimetric analysis was used to investigate the influence of such aging on the glass‐transition phenomena. A new amorphous phase appeared during aging. By extending the analysis to samples collected at different thicknesses, we demonstrated the existence of a time‐dependent gradient of the properties. A skin–core structure was evidenced, and this slowed down oxidation and allowed physical aging to occur in the bulk sample. An exponential law described the variations of the glass‐transition of the new external compound. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 786‐792, 2013     

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     

Biobased epoxy resin from canola oil

Epoxidized canola oil (ECO)‐based thermoset epoxy resins were formulated with phthalic anhydride (PA) as the curing agent for different ratios of ECO to PA (1:1, 1:1.5, and 1:2 mol/mol) at curing temperatures of 155, 170, 185, and 200°C. The gelation process of the epoxy resins and the viscoelastic properties of the systems during curing were studied by rheometry, whereas the dynamic mechanical and thermal properties of the cured resins were studied by dynamic mechanical analysis (DMA) and differential scanning calorimetry. We found that the thermomechanical properties of the resins were not strongly dependent on the curing temperature of the resin, although elevated temperatures significantly accelerated the curing process. However, an increase in the curing agent (PA) amount significantly altered both the reaction rate and the thermomechanical properties of the final resin. Thus, in the ECO/PA system, the selection of the combination of the curing temperature and the molar ratios of the curing agent could be used to design thermoset resins with unique thermomechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40142.