Toughening of semi-IPN structured epoxy using a new PEEK-type polymer via in situ azide–alkyne click polymerization

A new poly(ether ether ketone)-type polymer prepared from 1,4-bis(azidomethyl)benzene (p-BAB), 4,4′-bis(2-propynyloxy)benzophenone (PBP) or 4,4′-sulfonylbis(propynyloxy)-benzene (SBP) via azide–alkyne click polymerization was used as a toughening agent to improve the fracture toughness, thermal stability of the toughened epoxy and reduce its viscosity during processing. The epoxy was toughened by the polymer [poly(p-BAB/PBP)] via in situ polymerization during the curing process, which largely decreased viscosity during the epoxy mixing process compared to that of a neat epoxy. The fracture toughness of 5 wt % poly(p-BAB/PBP) toughened epoxy is two times higher than that of the neat epoxy, and even higher than that of the polyethersulfone-type [poly(p-BAB/SBP)] toughened epoxy using the same amount of toughening agents. In addition, the T _g of this toughened epoxy is higher than that of engineering plastic, which could be regarded as the evidence for the excellent thermal resistance. These phenomena might be attributed to the formation of semi-interpenetrating polymer networks composed by the epoxy network and the linear poly(p-BAB/PBP). In situ poly(p-BAB/PBP) has unique advantages such as decreased viscosity and improved thermal stability in comparison with in situ poly(p-BAB/SBP). These features are significant for the development of carbon-fiber-reinforced plastics as alternate materials to metals. Therefore, in situ poly(p-BAB/PBP) is a promising toughener for epoxy systems. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48178.     

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     

Toughening of epoxy resin systems using low‐viscosity additives

This study has evaluated three low‐viscosity epoxy additives as potential tougheners for two epoxy resin systems. The systems used were a lower‐reactive resin based upon the diglycidyl ether of bisphenol A (DGEBA) and the amine hardener diethyltoluene diamine, while the second epoxy resin was based upon tetraglycidyl methylene dianiline (TGDDM) and a cycloaliphatic diamine hardener. The additives evaluated as potential tougheners were an epoxy‐terminated aliphatic polyester hyperbranched polymer, a carboxy‐terminated butadiene rubber and an aminopropyl‐terminated siloxane. This work has shown that epoxy‐terminated hyperbranched polyesters can be used effectively to toughen the lower cross‐linked epoxy resins, i.e. the DGEBA‐based systems, with the main advantage being that they have minimal effect upon processing parameters such as viscosity and the gel time, while improving the fracture properties by about 54 % at a level of 15 wt% of additive and little effect upon the T_g. This result was attributed to the phase‐separation process producing a multi‐phase particulate morphology able to initiate particle cavitation with little residual epoxy resin dissolved in the continuous epoxy matrix remaining after cure. The rubber additive was found to impart similar levels of toughness improvement but was achieved with a 10–20 °C decrease in the T_g and a 30 % increase in initial viscosity. The siloxane additive was found not to improve toughness at all for the DGEBA‐based resin system due to the poor dispersion within the epoxy matrix. The TGDDM‐based resin systems were found not to be toughened by any of the additives due to the lack of plastic deformation of the highly cross‐linked epoxy network Copyright © 2003 Society of Chemical Industry     

Surface morphology,thermomechanical and barrier properties of poly(ether sulfone)‐toughened epoxy clay ternary nanocomposites

Poly(ether sulfone) (PES)‐toughened epoxy clay ternary nanocomposites were prepared by melt blending of PES with diglycidyl ether of bisphenol A epoxy resin along with Cloisite 30B followed by curing with 4,4′‐diaminodiphenylsulfone. The effect of organoclay and thermoplastic on the fracture toughness, permeability, viscoelasticity and thermomechanical properties of the epoxy system was investigated. A significant improvement in fracture toughness and modulus with reduced coefficient of thermal expansion (CTE) and gas permeability were observed with the addition of thermoplastic and clay to the epoxy system. Scanning electron microscopy of fracture‐failed specimens revealed crack path deflection and ductile fracture without phase separation. Oxygen gas permeability was reduced by 57% and fracture toughness was increased by 66% with the incorporation of 5 phr clay and 5 phr thermoplastic into the epoxy system. Optical transparency was retained even with high clay content. The addition of thermoplastic and organoclay to the epoxy system had a synergic effect on fracture toughness, modulus, CTE and barrier properties. Planetary ball‐milled samples gave exfoliated morphology with better thermomechanical properties compared to ultrasonicated samples with intercalated morphology. Copyright © 2010 Society of Chemical Industry     

Physicochemical properties and fracture behavior of soy‐based resin

A soy‐based resin was prepared by the process of transesterfication and epoxidation of regular food‐grade soybean oil. The soy‐based resin was used as a reactive diluent and also as a replacement of bisA epoxy resin in an anhydride‐cured polymer. The curing efficiency of soy epoxy resin was studied using differential scanning calorimetry. Physicochemical properties and fracture behavior of soy‐based resin polymers were studied using dynamic mechanical analysis and fracture toughness measurements, respectively. Toughness measurements were carried out using the compact tension geometry following the principles of linear elastic fracture mechanics. Tests showed that the addition of soy‐based epoxy resin to the base epon resin improved the toughness of the blend. Morphology of the fractured specimens has been analyzed by scanning electron microscopy. The soy‐based resins hold great potential for environmentally friendly, renewable resource based, and low cost materials for structural applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

Reactive Energetic Plasticizers for Energetic Polyurethane Binders Prepared via Simultaneous Huisgen Azide‐Alkyne Cycloaddition and Polyurethane Reaction

Reactive energetic plasticizers (REPs) for use in glycidyl azido polymer (GAP) based polyurethane (PU) energetic binders were investigated. These REPs consisted of an activated terminal alkyne group that was expected to give rise to Huisgen azide‐alkyne 1,3‐dipolar cycloaddition within the specific pot life for a PU formulation to prevent the migration of plasticizers, and with a gem‐dinitro group as an energy resource. A quantitative miscibility investigation between the plasticizers and uncured GAP showed that REPs exhibited better miscibility than conventional energetic plasticizers. The plasticization effect of the REPs on the GAP prepolymer with respect to the reduction of the viscosity illustrated REPs can effectively reduce the viscosity of the GAP prepolymer from 6,015 cP to 150–240 cP at the processing temperature when 50 wt‐% of REP was added. A comparison of the click reactivity and activation energies (E_a) of REPs and GAP prepolymer elucidated that the reactivity of azide‐alkyne cycloaddition depended on the dipolarophilicity of REPs which could be controlled by adjusting the length of methylene spacer between electron‐withdrawing groups (EWG) and neighboring alkynes in REPs. Thermogravimetric analysis manifested REP/GAP‐based PU binders maintained the thermal stability of the control GAP‐based PU binder. The mechanical properties and impact insensitivity of the GAP‐based PU binders were also improved by the incorporation of REPs.     

Novel phosphorus-modified polysulfone as a combined flame retardant and toughness modifier for epoxy resins

A novel phosphorus-modified polysulfone (P-PSu) was employed as a combined toughness modifier and a source of flame retardancy for a DGEBA/DDS thermosetting system. In comparison to the results of a commercially available polysulfone (PSu), commonly used as a toughness modifier, the chemorheological changes during curing measured by means of temperature-modulated DSC revealed an earlier occurrence of mobility restrictions in the P-PSu-modified epoxy. A higher viscosity and secondary epoxy-modifier reactions induced a sooner vitrification of the reacting mixture; effects that effectively prevented any phase separation and morphology development in the resulting material during cure. Thus, only about a 20% increase in fracture toughness was observed in the epoxy modified with 20 wt.% of P-PSu, cured under standard conditions at 180 °C for 2 h. Blends of the phosphorus-modified and the standard polysulfone (PSu) were also prepared in various mixing ratios and were used to modify the same thermosetting system. Again, no evidence for phase separation of the P-PSu was found in the epoxy modified with the P-PSu/PSu blends cured under the selected experimental conditions. The particular microstructures formed upon curing these novel materials are attributed to a separation of PSu from a miscible P-PSu-epoxy mixture. Nevertheless, the blends of P-PSu/PSu were found to be effective toughness/flame retardancy enhancers owing to the simultaneous microstructure development and polymer interpenetration.     

Specific influence of polyethersulfone functionalization on the delamination toughness of modified carbon fiber reinforced polymer processed by resin transfer molding

The specific influence of polyethersulfone (PES) end‐functionalization with chlorine or hydroxyl end groups at same molar mass on PES‐epoxy composites based on a high‐performance tetra‐epoxide with di‐amine hardener resin (RTM6) is investigated in terms of morphology, thermal behavior, and toughness. A model study on PES filaments embedded in epoxy precursor is first performed to compare the interdiffusion and resulting morphology upon curing. PES‐OH shows a larger interdiffusion distance compared to PES‐Cl in the model systems and the laminates. This effect is more pronounced at high heating rate. Cross sections and fracture surfaces of composite panels are analyzed by scanning electron microscopy (SEM) coupled with energy dispersive X‐ray (EDX) spectroscopy to establish the link between the microstructures and fracture mechanisms. The toughness of PES‐OH‐modified epoxy composites is doubled compared to unmodified reference panels, whereas the PES‐Cl shows no improvement. The favorable influence of PES‐OH is ascribed to enhanced miscibility, interfacial adhesion and morphology, resulting from the better affinity between hydroxyl‐terminated PES and the epoxy‐resin. POLYM. ENG. SCI., 59:996–1009, 2019. © 2019 Society of Plastics Engineers     

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     

刚性聚氨酯增韧改性环氧树脂的研究

在环氧树脂(EP)中加入以对苯二甲酸二甲酯为原料合成的端羟基芳香聚酯及2,4—甲苯二异氰酸酯(TDI),采用原位聚合法制备了刚性聚氨酯(PUR)增韧改性EP。用红外光谱表征了其反应,探讨了端羟基芳香聚酯含量、端羟基芳香聚酯与TDI摩尔比和固化剂用量对改性EP力学性能的影响,并用扫描电子显微镜观察了改性EP的冲击断面。结果表明,在提高EP韧性的同时,改性EP的其它力学性能都得以提高。     

聚醚砜/环氧树脂共混体系流变特性与固化性能的研究

环氧树脂是一种性能优良的热固性树脂,但是存在抗冲击性能差的缺点。聚醚砜(PES)是一种高性能热塑性树脂,与环氧树脂共混能够改善环氧树脂的韧性。系统研究了不同PES含量的PES/环氧树脂共混体系的流变特性和固化性能。通过对等温粘度曲线的数据拟合分析,建立了粘度模型,分析了PES对PES/环氧树脂共混体系粘度的影响机理,并通过DSC测试研究了PES对共混体系固化性能的影响。结果表明,PES在环氧树脂中的溶解过程可以引起共混体系粘度的波动,PES的引入缩短了PES/环氧树脂共混体系的凝胶时间,而且PES中的羟基对环氧树脂的固化具有促进作用。     

自修复聚合物材料用微胶囊

Microcapsules with dicyclopentadiene (DCPD) as core material and urea formaldehyde resin as wall material used for making self-healing polymer material were prepared with the in-situ polymerization method. The effect of microcapsules on the fracture toughness of epoxy resin was studied. The addition of microcapsules into epoxy resin results in the decrease of fracture toughness. When microcapsule content was kept constant, as the microcapsule size increased the fracture toughness of the epoxy resin decreased linearly and the percentage of decrease compared to the neat epoxy without microcapsules increased linearly. Moreover, the fracture toughness of the material decreases linearly with the increase of microcapsule content.     

填料对增韧环氧树脂断裂韧性等性能的影响

本文系统地研究了活性硅微粉、硅灰石等填料的加入对增韧环氧树脂的断裂韧性、力学性能、介电性能等的影响.结果表明填料的加入虽然对增韧环氧的电气性能和部分力学性能有所影响,但是不降低其断裂韧性.     

Adhesive and Mechanical Properties of Reactive Polysulfone Modified Epoxy Resins

The diglycidyl ether of bisphenol-A epoxy resin (EPON 828®) was cured with 4,4'-diaminodiphenylsulfone (DDS) and, optionally, an animophenyl functional reactive polyethersulfone (R-PES, 〈 M_n 〉=10k) as a co-curing agent. Commercial polysulfone, Udel® P-1700, was also utilized to afford epoxy-Udel® blends (or semi-IPNs). Cured epoxy polymers were subjected to T_g determinations, plane strain fracture toughness (K_IC) tests, adhesive bond strength measurements, tensile tests and chemical resistance studies. The morphologies of the fractured samples were studied by SEM and correlated to the property changes. Only the reactive polysulfone modification improved both fracture toughness and adhesive properties without detracting from the good mechanical properties and chemical resistance.     

A reactive polymer for toughening epoxy resin

Epoxy resins are hardly toughened by low weight content of tougheners. In this study, 5 wt % polyurea was adopted to significantly toughen piperidine‐cured epoxy, as fracture toughness improved from 0.78 to 1.98 MPa m^1/2. We focused on the reactions and morphology evolution of epoxy/polyurea mixture. The polyurea molecular weight was reduced by the exchange reactions of polyurea with epoxy during mixing, as evidenced by gel permeation chromatograph and Fourier transform infrared spectroscopy. As a result, epoxy molecules were chemically bonded with polyurea, improving particle content and interface thickness. Transmission electron microscope observation shows that (a) polyurea in situ formed nanoparticles in matrix which subsequently aggregate into micron‐sized particles of thick interface with matrix; and (b) the particles became less stainable with increasing the mixing time, because the reactions promoted high levels of crosslink density of the particles which were thus more resistant to the diffusion of staining chemicals. Longer mixing time improved, obviously, the fracture toughness of epoxy/polyurea composite. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Adhesive and Mechanical Properties of Reactive Polysulfone Modified Epoxy Resins

The diglycidyl ether of bisphenol-A epoxy resin (EPON 828®) was cured with 4,4′-diaminodiphenylsulfone (DDS) and, optionally, an animophenyl functional reactive polyethersulfone (R-PES, ? M_n ?=10k) as a co-curing agent. Commercial polysulfone, Udel® P-1700, was also utilized to afford epoxy-Udel® blends (or semi-IPNs). Cured epoxy polymers were subjected to T_g determinations, plane strain fracture toughness (K_IC) tests, adhesive bond strength measurements, tensile tests and chemical resistance studies. The morphologies of the fractured samples were studied by SEM and correlated to the property changes. Only the reactive polysulfone modification improved both fracture toughness and adhesive properties without detracting from the good mechanical properties and chemical resistance.     

Thermal and mechanical properties of PPO filled epoxy resins compatibilized by triallylisocyanurate

A series of blends has been prepared by adding a poly(phenylene oxide) (PPO), in varying proportions, to an epoxy resin cured with dicyandiamide. All the materials show two‐phase morphology when characterized by SEM and DMA. SEM and DMA indicate that partial mixing exists in all the blends especially with high PPO content. This implies that the epoxy oligomer or low crosslinking density epoxy exists in the PPO phase after curing. The tensile strength and modulus of these blends are nearly independent of the PPO content, while the fracture toughness (G_IC) is improved by PPO. However, the two‐phase particulate morphology is not uniform. In order to improve the uniformity and miscibility, triallylisocyanurate (TAIC) has been used as an in situ compatibilizer for the polymer blends of epoxy and PPO. SEM and DMA reveal improvement of miscibility and solvent resistance for this system. The fracture toughness of these TAIC‐modified systems are also improved by adding TAIC (0–20 phr). © 2000 Society of Chemical Industry     

Adhesive strength and mechanisms of epoxy resins toughened with pre-formed thermoplastic polymer particles

The aim of this study was to characterize the adhesive properties of epoxy resins toughened with pre-formed polyamide-12 particles in comparison to the conventional approach using core–shell rubber particles. Dicyandiamide-cured diglycidyl ether of bisphenol-A was used as the base epoxy resin. The T-peel adhesive strength of the toughened resin containing 20 phr polyamide-12 particles was about 3-times higher than that of the unmodified resin. In the case of rubber toughening, the improvement in adhesive strength tended to reach a plateau, even after improvement in the resin toughness itself. Besides, the polyamide particle toughening utilizes the bulk resin toughness for the peel adhesive strength, even in a thin adhesive layer between the substrates. The polyamide particles embedded in epoxy resin matrix were fractured after bridging cracks and stretching in the peel process. The crack-bridging mechanism by the pre-formed thermoplastic polymer particles was operative behind the crack-tip and would, therefore, experience a relatively small constraint by the presence of rigid metal substrates in comparison to conventional rubber toughening. The requirements for the polymer particles to work as a modifier using the bridging mechanism would be good adhesion to the epoxy matrix, high toughness and a relatively lower modulus of elasticity than that of matrix resin.     

Self‐healing and interfacially toughened carbon fibre‐epoxy composites based on electrospun core–shell nanofibres

Dual components of a self‐healing epoxy system comprising a low viscosity epoxy resin, along with its amine based curing agent, were separately encapsulated in a polyacrylonitrile shell via coaxial electrospinning. These nanofiber layers were then incorporated between sheets of carbon fiber fabric during the wet layup process followed by vacuum‐assisted resin transfer molding to fabricate self‐healing carbon fiber composites. Mechanical analysis of the nanofiber toughened composites demonstrated an 11% improvement in tensile strength, 19% increase in short beam shear strength, 14% greater flexural strength, and a 4% gain in impact energy absorption compared to the control composite without nanofibers. Three point bending tests affirmed the spontaneous, room temperature healing characteristics of the nanofiber containing composites, with a 96% recovery in flexural strength observed 24 h after the initial bending fracture, and a 102% recovery recorded 24 h after the successive bending fracture. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44956.