Hydrothermal effects on the thermomechanical properties of high performance epoxy/clay nanocomposites

The effects of hydrothermal ageing on the thermomechanical properties of high performance epoxy and its nanocomposite were studied. The epoxy–clay nanocomposite was prepared through a recently developed “slurry‐compounding” approach. The cured samples were immersed in distilled water at 60°C for different periods of time before subjecting to characterization. The storage modulus, relaxation behavior, fracture toughness, and tensile properties were investigated. It was found that the storage modulus and α‐relaxation were strongly affected by water uptake, while the fracture toughness and Young's modulus were less influenced. Dependence of tensile strength and strain at break on water uptake was found to be different in neat epoxy and epoxy–clay systems. POLYM. ENG. SCI., 46:215–221, 2006. © 2005 Society of Plastics Engineers     

Morphology,viscoelastic properties,and mechanical behavior of epoxy resin modified with hydroxyl‐terminated poly(ether ether ketone) oligomer with pendent tert‐butyl groups

Hydroxyl‐terminated poly (ether ether ketone) with pendent tert‐butyl groups (PEEKTOH) synthesized from 4,4′‐difluorobenzophenone and tert‐butyl hydroquinone was blended with diglycidyl ether of bisphenol‐A (DGEBA) epoxy resin. A diamine, 4,4′‐diaminodiphenyl sulfone (DDS) was used as the curing agent. The thermal and mechanical properties, fracture toughness, and morphology of the blends were investigated. Morphological analysis of the blends revealed a particulate structure with PEEKTOH phase dispersed in the epoxy matrix. Unlike classical polymer blend systems, increase in concentration of PEEKTOH does not increase the domain size. Instead, a decrease is obtained. The fracture toughness increased with the addition of oligomer without much decrease in tensile and flexural strengths. Addition of 15 phr oligomer gave maximum toughness. The dispersed PEEKTOH initiated several mechanisms that improved the fracture toughness of the blends. The cross‐link density calculated from the storage modulus in the rubbery plateau region decreased with the increase in PEEKTOH. The thermal stability of epoxy resin remained unaffected even after blending with PEEKTOH. POLYM. ENG. SCI., 45:1645–1654, 2005. © 2005 Society of Plastics Engineers     

Toughening of an epoxy resin with hydroxy‐terminated poly(arylene ether nitrile) with pendent tertiary butyl groups

Hydroxy‐terminated poly(arylene ether nitrile) oligomers with pendent tert‐butyl groups (PENTOH) were synthesized by the nucleophilic aromatic substitution reaction of 2,6‐dichlorobenzonitrile with tert‐butyl hydroquinone in N‐methyl‐2‐pyrrolidone medium with anhydrous potassium carbonate as a catalyst at 200°C in a nitrogen atmosphere. The PENTOH oligomers were blended with diglycidyl ether of bisphenol A epoxy resin and cured with 4,4′‐diaminodiphenyl sulfone. The curing reaction was monitored with infrared spectroscopy and differential scanning calorimetry. The morphology, fracture toughness, and thermomechanical properties of the blends were investigated. The scanning electron micrographs revealed a two‐phase morphology with a particulate structure of the PENTOH phase dispersed in the epoxy matrix, except for the epoxy resin modified with PENTOH with a number‐average molecular weight of approximately 4000. The storage modulus of the blends was higher than that of the neat epoxy resin. The crosslink density calculated from the storage modulus in the rubbery plateau region decreased with an increase in PENTOH in the blends. The fracture toughness increased more than twofold with the addition of PENTOH oligomers. The tensile strength of the blends increased marginally, whereas the flexural strength decreased marginally. The dispersed PENTOH initiated several toughening mechanisms, which improved the fracture toughness of the blends. The thermal stability of the epoxy resin was not affected by the addition of PENTOH to the epoxy resin. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Epoxy‐tert‐butyl poly(cyanoarylene ether) blends: Phase morphology,fracture toughness,and mechanical properties

Tert‐butyl hydroquinone–based poly(cyanoarylene ether) (PENT) was synthesized by the nucleophilic aromatic substitution reaction of 2,6‐dichlorobenzonitrile with tert‐butyl hydroquinone using N‐methyl‐2‐pyrrolidone (NMP) as solvent in the presence of anhydrous potassium carbonate in a nitrogen atmosphere at 200°C. PENT‐toughened diglycidyl ether of bisphenol A epoxy resin (DGEBA) was developed using 4,4′‐diaminodiphenyl sulfone (DDS) as the curing agent. Scanning electron micrographs revealed that all blends had a two‐phase morphology. The morphology changed from dispersed PENT to a cocontinuous structure with an increase in PENT content in the blends from 5 to 15 phr. The viscoelastic properties of the blends were investigated using dynamic mechanical thermal analysis. The storage modulus of the blends was less than that of the unmodified resin, whereas the loss modulus of the blends was higher than that of the neat epoxy. The tensile strength of the blends improved slightly, whereas flexural strength remained the same as that of the unmodified resin. Fracture toughness was found to increase with an increase in PENT content in the blends. Toughening mechanisms like local plastic deformation of the matrix, crack path deflection, crack pinning, ductile tearing of thermoplastic, and particle bridging were evident from the scanning electron micrographs of failed specimens from the fracture toughness measurements. The thermal stability of the blends were comparable to that of the neat resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3536–3544, 2006     

Novel polymer composites based on a mixture of preformed nanosilica‐filled poly(methyl methacrylate) particles and a diepoxy/diamine thermoset system

In this work, a new material based on an epoxy thermoset modified with a thermoplastic filled with silica nanoparticles was investigated. When thermoplastic particles are filled with nanoparticles with unique properties such as high efficiency for absorbing ultraviolet light, electric or magnetic shielding, high electrical conductivity, and high dielectric constants, more than an enhancement of the mechanical properties is expected to be achieved for modified epoxy‐based thermosets. Particles of poly(methyl methacrylate) (PMMA) filled with silica nanoparticles were used to modify a thermoset based on a full reaction between diglycidyl ether of bisphenol A and 3‐(aminomethyl)benzylamine. When the preformed thermoplastic particles were mixed with the reactive constituents of the epoxy system under certain curing conditions in which total miscibility was avoided, uniform particle dispersions could be obtained. The relationships between the composition, morphology (nanoscale and microscale), glass‐transition temperature, mechanical properties, and fracture toughness were considered. Four main results were obtained for consideration of the potential of silica‐filled PMMA as an important modifier of brittle epoxy thermoset systems: (1) a good dispersion of the silica nanoparticles in the PMMA domains, (2) a good dispersion of the silica‐filled PMMA microparticles in the epoxy matrix, (3) the possibility of partial dissolution of the PMMA‐rich domains into the epoxy system, and (4) a slight increase in properties such as the hardness, indentation modulus, and fracture toughness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enhanced fracture toughness of epoxy resins with novel amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) triblock copolymers

Amine‐terminated poly(arylene ether sulfone)–carboxylic‐terminated butadiene‐acrylonitrile–poly(arylene ether sulfone) (PES‐CTBN‐PES) triblock copolymers with controlled molecular weights of 15,000 (15K) or 20,000 (20K) g/mol were synthesized from amine‐terminated PES oligomer and commercial CTBN rubber (CTBN 1300x13). The copolymers were utilized to modify a diglycidyl ether of bisphenol A epoxy resin by varying the loading from 5 to 40 wt %. The epoxy resins were cured with 4,4′‐diaminodiphenylsulfone and subjected to tests for thermal properties, plane strain fracture toughness (K_IC), flexural properties, and solvent resistance measurements. The fracture surfaces were analyzed with SEM to elucidate the toughening mechanism. The properties of copolymer‐toughened epoxy resins were compared to those of samples modified by PES/CTBN blends, PES oligomer, or CTBN. The PES‐CTBN‐PES copolymer (20K) showed a K_IC of 2.33 MPa m^0.5 at 40 wt % loading while maintaining good flexural properties and chemical resistance. However, the epoxy resin modified with a CTBN/8K PES blend (2:1) exhibited lower K_IC (1.82 MPa m^0.5), lower flexural properties, and poorer thermal properties and solvent resistance compared to the 20K PES‐CTBN‐PES copolymer‐toughened samples. The high fracture toughness with the PES‐CTBN‐PES copolymer is believed to be due to the ductile fracture of the continuous PES‐rich phases, as well as the cavitation of the rubber‐rich phases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1556–1565, 2002; DOI 10.1002/app.10390     

Hydroxyl terminated poly(ether ether ketone) with pendant methyl group‐toughened epoxy clay ternary nanocomposites: Preparation,morphology, and thermomechanical properties

Hydroxyl terminated poly(ether ether ketone) oligomer with pendant methyl group (PEEKMOH) was prepared. Ternary nanocomposites were processed by blending PEEKMOH oligomer with diglycidyl ether of bisphenol‐A (DGEBA) epoxy resin along with organically modified montmorillonite (Cloisite 25A) followed by curing with 4,4'‐diamino diphenyl sulfone. Tensile moduli and flexural moduli were increased, while the tensile strength and Izod impact strength were decreased with increase in clay content. Similarly, storage moduli and loss moduli were increased and glass transition temperature was decreased as the percentage of clay increased. X‐ray diffractograms showed exfoliated morphology even with higher concentration of clay content (8 phr). Scanning electron microscopy of fractured surfaces and tensile failed specimens revealed slow crack propagation and increase in river markings with nanoclay incorporation confirming the improvement in toughness. The domain size of PEEKMOH was decreased with the incorporation of nanoclay into the epoxy matrix, indicating the restriction of growth mechanism by nucleation during phase separation. With increase in clay content, phase separation disappeared indicating gelation occurs before phase separation. Fracture toughness was increased with the addition of PEEKMOH and clay in epoxy resin. Coefficient of thermal expansion of nanocomposites decreases up to 3 phr clay concentrations thereafter it increases. A marginal increase in thermal stability was observed with increase in clay content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Toughening of epoxy/polycaprolactone composites via reaction induced phase separation

A series of melt processable thermoset/thermoplastic blends were prepared by mixing bisphenol‐A diglycidyl ether (Epon‐828)/diaminodiphenyl sulfone (DGEBA/DDS) system with two grades of polycaprolactone resin. Phase separation behavior of the blends was investigated by means of optical microscopy, microstructure by scanning electron microscopy (SEM), and thermo‐mechanical properties. The toughness of polycaprolactone modified epoxies was measured by instrumented falling weight impact (IFWI) testing. Various blend morphologies were observed depending upon the cured epoxy network/thermoplastic composition. Spinodal decomposition as characterized by modulated structure of unique periodicity and phase connectivity was found to be the probable mechanism of phase separation. SEM examination of fracture surfaces indicated a strong adhesion between the epoxy‐rich and polycaprolactone‐rich phases. Optimum improvement in failure energy was obtained for the compositions containing 10‐20% polycaprolactone without significantly compromising the elastic modulus and the thermo‐mechanical stability of the epoxy. In light of morphological evidences, a possible toughening effect was postulated in terms of tearing of the thermoplastic component and induced plastic deformation of the epoxy matrix.     

Toughening of dicyandiamide-cured DGEBA-based epoxy resins by CTBN liquid rubber

Toughening of a diglycidyl ether of bisphenol-A (DGEBA)-based epoxy resin with liquid carboxyl-terminated butadiene acrylonitrile (CTBN) copolymer has been investigated. For this purpose six blend samples were prepared by mixing DGEBA with different concentrations of CTBN from 0 to 25 phr with an increment of 5 phr. The samples were cured with dicyandiamide curing agent accelerated by Monuron. The reactions between oxirane groups of DGEBA and carboxyl groups of CTBN were followed by Fourier-transform infrared (FTIR) spectroscopy. Tensile, impact, fracture toughness and dynamic mechanical analysis of neat as well as the modified epoxies have been studied to observe the effect of CTBN modification. The tensile strength of the blend systems increased by 26 % when 5 phr CTBN was added, and it remained almost unchanged up to 15 phr of CTBN. The elongation-at-break and Izod notched impact strength increased significantly, whereas tensile modulus decreased gradually upon the addition of CTBN. The maximum toughness of the prepared samples was achieved at optimum concentration of 15 phr of CTBN, whereas the fracture toughness (K _IC) remained stable for all blend compositions of more than 10 phr of CTBN. The glass transition temperature (T _g) of the epoxy resin significantly increased (11.3 °C) upon the inclusion of 25 phr of CTBN. Fractured surfaces of tensile test samples have been studied by scanning electron microscopic analysis. This latter test showed a two-phase morphology where the rubber particles were distributed in the epoxy resin with a tendency towards co-continuous phase upon the inclusion of 25 phr of CTBN.     

Development of an epoxy system characterized by low water absorption and high thermomechanical performances

Water absorption and thermomechanical properties of epoxy systems based on multifunctional dicyclopentadiene epoxy novolac resin Tactix556 cured with 4,4′ diaminodiphenilsulfone (4,4′DDS) as curing agent has been studied. The base system was modified by the addition of a novel 40 : 60 PES : PEES (Polyethersulphone : Polyetheretheresulphone) amine‐ended copolymer to improve toughness properties. The effect of thermoplastic addition on water adsorption was studied by gravimetric experiments. The viscoelastic properties of the resulting blend were analyzed by means of dynamic mechanical thermal analysis. The formulated systems were compared with a system based on tetraglycidyl‐4,4′diaminodiphenylmethane resin (MY721) cured with 4,4′ diaminodiphenilsulfone. The use of Tactix556 resin showed that water uptake values were minimized while retaining high glass transition temperatures, and toughness values were found in the same range of standard toughened matrices used for aerospace composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4880–4887, 2006     

Effect of resin modifiers on the structural properties of epoxy resins

Thermomechanical, mechanical and fracture mechanical properties of modified epoxy resins with two different modifiers are investigated. Carboxyl‐terminated butadiene‐acrylonitrile (CTBN) is used as toughening agent and hexanediole diglycidyl ether (HDDGE) as reactive diluent. Both modifiers are admixed in contents from 0 up to 100 phr (parts per hundred resin) and exhibit flexibilizing and toughening qualities. The glass transition temperature is strongly depressed by the admixed reactive diluent, whereas the tensile modulus exhibits greater dependency on the toughening agent contents. The tensile strength and strain at break values are higher for the formulations with diluent compared to resins with toughening agent. Up to a content of 45 phr both modified systems exhibit comparable fracture toughness values. Only the toughened systems comprise increasing values for modifier amounts higher than 45 phr. For the formulation with both modifiers (toughening agent and diluent) a significantly higher toughness but a reduced glass transition temperature was obtained. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45348.     

杂萘联苯聚芳醚酮改性环氧树脂的结构与性能

采用新型耐高温高性能热塑性树脂杂萘联苯聚芳醚酮(PPEK)对环氧树脂(EP)进行共混改性.研究了共混物的结构和热力学性能,并对其增韧机理进行了分析.结果表明,EP/PPEK/4,4'-二氨基二苯砜共混物的热性能得到了提高而断裂韧性整体呈下降趋势.在添加15份PPEK时,共混物的临界应力强度因子(KIC)略有提高,即韧性...     

Study of morphological and mechanical performance of amine‐cured glassy epoxy–clay nanocomposites

The effect of three different alkylammonium‐modified montmorillonite on morphological and mechanical properties of glassy epoxy‐amine nanocomposites is reported. Small amounts of clays <10 phr (part per hundred of resin) were used in each system of nanocomposite. The morphology of the prepared nanocomposites was performed by means of X‐ray diffraction and transmission electron microscopy. Differential scanning calorimetry (DSC) was used to investigate the glass transition temperatures (T_g). Mechanical properties were based on tensile characteristics (Young's modulus), impact strength, and fracture toughness. The measured moduli were compared to theoretical predictions. Scanning electron microscopy was used to study the morphological structure of the fracture surfaces of impacted specimens. It was found that at a low content of 2 phr (1.2 wt %) of nanoclays, the impact strength and the fracture toughness were improved by 77 and 90% respectively, comparatively to the neat epoxy, whereas DSC revealed a reduction of the T_g of nanocomposites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

含氟聚醚醚酮增韧环氧树脂相形貌与性能研究

采用SEM观察了热塑性含氟结构聚醚醚酮(6FPEEK)共混增韧环氧树脂的浇铸体脆断断口相形貌,测试了浇铸体的力学性能及动态机械性能,通过统计和数学分析建立了冲击韧性(αk)、热塑颗粒粒径(d)和粒间距(D)间的半定量关系。结果表明,该体系可得到连续相为环氧树脂而分散相为热塑颗粒的相结构,热塑相颗粒尺寸较为统一,且随热塑性树脂含量的增加而增大;6FPEEK含量增加对拉伸强度的影响不大,环氧树脂和热塑性塑料的结合界面差导致了冲击韧性在6FPEEK质量分数达到9.09%时出现峰值而后下降;该增韧体系的增韧机理可能为刚性粒子增韧。     

Improved thermosets obtained from diglycidyl ether of bisphenol A/4,4′‐diaminodiphenylsulfone based on a new epoxy‐terminated hyperbranched polymer

A new hyperbranched polymer (HBP) with a flexible aromatic skeleton and terminal epoxy groups was synthesized to improve the toughness of diglycidyl ether of bisphenol A. The HBP was characterized using nuclear magnetic resonance, Fourier transfer infrared spectroscopy and gel permeation chromatography. The effect of HBP on the thermomechanical and mechanical properties of modified epoxy systems was studied. For evaluating the efficiency of the modified epoxy systems, composite samples using glass fiber cloth were molded and tested. Using dynamic mechanical analysis, a slight reduction in glass transition temperature (T_g) with increasing HBP content was observed. Analysis of fracture surfaces revealed a possible effect of HBP as a toughener and showed no phase separation in the modified resin systems. The results showed that the addition of 15 phr HBP maximized the toughness of the modified resin systems with 215 and 40% increases in impact and flexural strengths, respectively. T_g and heat resistance of cured modified resin systems decreased slightly with an increase in HBP content and, at 15 phr HBP, only a 2.6% decrease in thermomechanical properties was observed. Meanwhile, a molded composite with HBP showed improved mechanical properties and retention rate at 150 °C as compared to that made with neat resin. © 2015 Society of Chemical Industry     

Control of morphologies and mechanical properties of thermoplastic‐modified epoxy matrices by addition of a second thermoplastic

Ternary mixtures based on stoichiometric mixtures of the diglycidyl ether of bisphenol‐A (DGEBA) and 4,4′‐diaminodiphenyl sulfone (DDS) and two miscible thermoplastics, poly(methyl methacrylate) (PMMA) and the poly(hydroxy ether of bisphenol‐A) (phenoxy), were investigated by optical microscopy (OM), atomic force microscopy (AFM) and dynamic mechanical analysis (DMA). Mechanical testing was used to study the ultimate behavior. All the modified epoxy mixtures were heterogeneous. DMA has been shown to be an excellent technique for detecting the morphologies generated after curing when the loss modulus is used for analysis. Morphology varied with the thermoplastic content on the mixtures. The addition of a second thermoplastic in small amounts changed the morphological features from particulated to co‐continuous and from that to phase‐inverted morphologies. A significant increase in fracture toughness was observed above all for the mixtures with some level of co‐continuity within the epoxy‐rich matrix. Phase inversion led to poor strength and also fracture toughness. Copyright © 2003 Society of Chemical Industry     

Study on phenolphthalein poly(ether sulfone)‐modified cyanate ester resin and epoxy resin blends

In this work, the phenolphthalein poly(ether sulfone) (PES‐C)‐modified cyanate ester (CE) and epoxy (EP) blends were prepared. This work mainly discusses the curing behaviors, fracture toughness, dynamic mechanical properties, and thermal and mechanical properties of the blends. The Fourier transform infrared and differential scanning calorimetric analyses are used to confirm the curing behaviors, demonstrating that the main reaction pathways are not varied with the addition of PES‐C, but the reaction rate could be evidently accelerated. The fracture morphologies of the blends are observed by Scanning electron microscope (SEM) and the fracture causes of the failed surface are also analyzed. With the addition of PES‐C, the modified blends display higher fracture toughness (K_Ic) and impact strength when compared with neat CE. Domain sizes of the blends first increase then decrease with the addition of PES‐C. The results of dynamic mechanical analysis and thermogravimetric analysis show that the T_g, storage modulus, and thermal stability of the crosslink network slightly decreases with the addition of PES‐C. The mechanical strength of blends with the addition of PES‐C is far better than that of the blends without PES‐C both at ambient temperature and elevated temperature. POLYM. ENG. SCI., 55:2591–2602, 2015. © 2015 Society of Plastics Engineers     

Continuous reactor preparation of thermoplastic modified epoxy‐amine prepolymers

This paper describes a new continuous reactor method to prepare thermoplastic modified epoxy prepolymers for aerospace prepregs with the aim of replacing traditional batch reactors. Compared with batch reactors, the continuous reactor is capable of producing epoxy prepolymers through simultaneous dissolution of polyethersulfone (PES) and 4,4′‐diaminodiphenylsulfone in tetraglycidyl‐4,4′‐ diaminodiphenylmethane (TGDDM). In addition, concurrent chain extension reactions advance prepolymer molecular weights to desired viscosities in less than 2 min of mean residence time. Optical micrographs were used to define how process temperature influences PES dissolution in TGDDM in a continuous reactor. Kinetic studies confirmed that the chain extension reaction in a continuous reactor is similar to that in a batch reactor, and the molecular weights and viscosities of prepolymers were readily controlled through reaction kinetics. Atomic force microscopy was used to confirm similar cured network morphologies for formulations prepared from batch and continuous reactors. Additionally tensile strength, tensile modulus and fracture toughness analyses concluded that mechanical properties of cured epoxy matrices produced from the two reactors were equivalent. © 2014 Society of Chemical Industry     

Structural and material properties of a rapidly cured thermoplastic‐toughened epoxy system

Thermoplastic‐toughened epoxy resins are widely used as matrices in modern composite prepreg systems. Rapid curing of thermoplastic‐toughened epoxy matrix composites results in different mechanical properties. To investigate the structure–property relationship, we investigated a poly(ether sulfone)‐modified triglycidylaminophenol/4,4′‐diamino diphenyl sulfone system that was cured at different heating rates. An intermediate dwell was also applied during the rapid heating of the thermoplastic‐modified epoxy system. We found that a higher heating rate led to a larger domain size of the phase‐separated macrostructure and also facilitated more complete phase separation. The intermediate dwell helped phase separation to proceed even further, leading to an even larger domain size of the macrostructure. A carbon‐fiber‐reinforced polymer matrix composite prepreg based on the poly(ether sulfone)‐modified multifunctional epoxy system was cured with the same schedule. The rapidly heated composite laminates exhibited higher mode I delamination fracture toughness than the slowly heated material. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Curing and toughening of a styrene‐modified epoxy resin

A commercially available epoxy resin (E907) formulated with a viscosity‐reducing styrene monomer and several additives was subjected to thermal cure studies and mechanical property measurements. Thermoplastic poly(arylene ether sulfone) (PES) and poly(arylene ether phosphine oxide) (PEPO) with reactive amine or hydroxyl end groups were utilized to toughen and co‐cure with the system. The cure cycle was optimized and the networks were analyzed via differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analyzer, scanning electron microscopy, sol–gel extractions, and fracture toughness. A model epoxy resin was prepared from a tetrafunctional epoxy, e.g., MY722, difunctional EPON828, styrene monomer, and benzoyl peroxide initiator (BPO), and was evaluated as a control to assess the possible role of the styrene monomer. The optimized cure cycle for E907 was 6 h at 93°C, followed by a postcure of 2 h at 204°C. The fracture toughness of E907 was increased only marginally with PES and PEPO. In contrast, the model epoxy resin demonstrated a positive effect due to the styrene monomer and BPO and exhibited significantly increased fracture toughness with PES modification. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1504–1513, 2001