Thermal characterization of carbon‐nanofiber‐reinforced tetraglycidyl‐4,4′‐diaminodiphenylmethane/4,4′‐diaminodiphenylsulfone epoxy composites

The thermal properties of carbon nanofibers (CNF)/epoxy composites, composed of tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM) resin and 4,4′‐diaminodiphenylsulfone (DDS) as a curing agent, were investigated with differential scanning calorimetry (DSC), thermogravimetric analysis, and dynamic mechanical thermal analysis. DSC results showed that the presence of CNF had no pronounced influence on the heat of the cure reaction. However, the incorporation of CNF slightly improved the thermal stability of the epoxy. Furthermore, the storage modulus of the TGDDM/DDS epoxy was significantly enhanced, whereas the glass‐transition temperature was not significantly affected, upon the incorporation of CNFs. The storage modulus of 5 wt % CNF/epoxy composites at 25°C was increased by 35% in comparison with that of the pure epoxy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 295–298, 2006     

Synthesis,characterization, and properties of low viscosity tetra‐functional epoxy resin N,N,N′,N′‐ tetraglycidyl‐3,3′‐diethyl‐4,4′‐diaminodiphenylmethane

Tetra‐functional epoxy resin N,N,N′,N′‐tetraglycidyl‐3,3′‐diethyl‐4,4′‐diaminodiphenylmethane (TGDEDDM) was synthesized and characterized. The viscosity of TGDEDDM at 25°C was 7.2 Pa·s, much lower than that of N,N,N′,N′‐tetraglycidyl‐4,4′‐diaminodiphenylmethane (TGDDM). DSC analysis revealed that the reactivity of TGDEDDM with curing agent 4,4′‐diamino diphenylsulfone (DDS) was significantly lower than that of TGDDM. Owing to its lower viscosity and reactivity, TGDEDDM/DDS exhibited a much wider processing temperature window compared to TGDDM/DDS. Trifluoroborane ethylamine complex (BF₃‐MEA) was used to promote the curing of TGDEDDM/DDS to achieve a full cure, and the thermal and mechanical properties of the cured TGDEDDM were investigated and compared with those of the cured TGDDM. It transpired that, due to the introduction of ethyl groups, the heat resistance and flexural strength were reduced, while the modulus was enhanced. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2014 , 131, 40009.     

Miscibility and mechanical properties of tetrafunctional epoxy resin/phenolphthalein poly(ether ether ketone) blends

Phenolphthalein poly(ether ether ketone) (PEK‐C) was found to be miscible with uncured tetraglycidyl 4,4′‐diaminodiphenylmethane (TGDDM), which is a type of tetrafunctional epoxy resin (ER), as shown by the existence of a single glass transition temperature (T_g) within the whole composition range. The miscibility between PEK‐C and TGDDM is considered to be due mainly to entropy contribution. Furthermore, blends of PEK‐C and TGDDM cured with 4,4′‐diaminodiphenylmethane (DDM) were studied using dynamic mechanical analysis (DMA), Fourier‐transform infrared (FTIR) spectroscopy, and scanning electron microscopy (SEM). DMA studies show that the DDM‐cured TGDDM/PEK‐C blends have only one T_g. SEM observation also confirmed that the blends were homogeneous. FTIR studies showed that the curing reaction is incomplete due to the high viscosity of PEK‐C. As the PEK‐C content increased, the tensile properties of the blends decreased slightly and the fracture toughness factor also showed a slight decreasing tendency, presumably due to the reduced crosslink density of the epoxy network. SEM observation of the fracture surfaces of fracture toughness test specimens showed the brittle nature of the fracture for the pure ER and its blends with PEK‐C. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 598–607, 2001     

Characterization of the cure of TGDDM/DDS epoxy resins by chemiluminescence I. Spectral and thermal analysis

The emission of weak visible chemiluminescence (CL) during the cure of a tetraglycidyl 4,4′-diaminodiphenyl methane (TGDDM)-based epoxy resin, with three different concentrations of 4,4′-diaminodiphenylsulfone (DDS) has been studied at 135°C. Spectral analysis indicates that the CL originates from trace oxidation of the TGDDM resin and the emission intensity is sensitive to the viscosity changes during cure. From thermal analysis data, sharp discontinuities in CL intensity are shown to occur at the gel point. The temperature dependence of CL from a cured resin also shows a sharp discontinuity at T_g. These results indicate that CL provides a sensitive monitor of both the kinetics of gelation and the network formation in this epoxy resin.     

Curing behavior and thermal and mechanical properties enhancement of tetraglycidyl‐4,4′‐diaminodiphenylmethane/4,4′‐diaminodiphenylsulfone using a liquid crystalline epoxy

A thermosetting resin system, based on tetraglycidyl‐4,4′‐diaminodiphenylmethane, has been developed via copolymerization with 4,4′‐diaminodiphenylsulfone in the presence of a newly synthesized liquid crystalline epoxy (LCE). The curing behavior of LCE‐containing resin system was evaluated using curing kinetics method and Fourier transform infrared spectroscopy. The effect of LCE on the thermal and mechanical properties of modified epoxy systems was studied. Thermogravimetric analysis indicated that the modified resin systems displayed a high T_0.05 and char yield at lower concentrations of LCE (≤5 wt%), suggesting an improved thermal stability. As determined using dynamic mechanical analysis and differential scanning calorimetry, the glass transition value increased by 9.7% compared to that of the neat resin when the LCE content was 5 wt%. Meanwhile, the addition of 5 wt% of LCE maximized the toughness with a 175% increase in impact strength. The analysis of fracture surfaces revealed a possible effect of LCE as a toughener and showed no phase separation in the modified resin system, which was also confirmed by dynamic mechanical analysis. © 2016 Society of Chemical Industry     

Preparation and properties of high performance phthalide‐containing bismaleimide modified epoxy matrices

A series of intercrosslinked networks formed by diglycidyl ether of bisphenol A epoxy resin (DGEBA) and novel bismaleimide containing phthalide cardo structure (BMIPP), with 4,4′‐diamino diphenyl sulfone (DDS) as hardener, have been investigated in detail. The curing behavior, thermal, mechanical and physical properties and compatibility of the blends were characterized using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), notched Izod impact test, scanning electron microscopy (SEM) and water absorption test. DSC investigations showed that the exothermic transition temperature (T_p) of the blend systems shifted slightly to the higher temperature with increasing BMIPP content and there appeared a shoulder on the high‐temperature side of the exothermic peak when BMIPP content was above 15 wt %. TGA and DMA results indicated that the introduction of BMIPP into epoxy resin improved the thermal stability and the storage modulus (G′) in the glassy region while glass transition temperature (T_g) decreased. Compared with the unmodified epoxy resin, there was a moderate increase in the fracture toughness for modified resins and the blend containing 5 wt % of BMIPP had the maximum of impact strength. SEM suggested the formation of homogeneous networks and rougher fracture surface with an increase in BMIPP content. In addition, the equilibrium water uptake of the modified resins was reduced as BMIPP content increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

An investigation of epoxy/thermoplastic blends based on addition of a novel copoly(aryl ether nitrile) containing phthalazinone and biphenyl moieties

In this paper, a novel soluble copoly(aryl ether nitrile) containing phthalazinone and biphenyl moieties (PPBEN) was synthesized for the first time to improve the impact resistance of tetraglycidyl 4,4'‐diaminodiphenylmethane epoxy resin cured with 4,4‐diaminodiphenylsulfone. Then a series of blends were prepared via solution blending with different contents of PPBEN. The thermal and mechanical properties and the micromorphology of the cured blends were investigated by differential scanning calorimetry, dynamic mechanical analysis (DMA), parallel plate rheometry, mechanical property tests and SEM analysis, respectively. The results indicated that the incorporation of thermoplastic PPBEN delayed the epoxy curing reaction, and the crosslinking density of epoxies was also reduced. The no‐notch impact strength of the cured blend with 15% PPBEN was up to 16.7 kJ m^?2, higher by about 104% than that of pure epoxy resin without sacrificing the modulus due to a specific sea‐island structure. All the blends showed two‐phase morphology characterized by DMA and SEM. The size of the thermoplastic morphology was only 70?80 nm, much less than that of commonly used thermoplastics, due to the special segment structure of PPBEN. © 2015 Society of Chemical Industry     

Toughening of epoxy resins with thermoplastics. Ii. Tetrafunctional epoxy resin-polyetherimide blends

A series of blends has been prepared by adding a polyetherimide (PEI), in varying proportions, to a tetrafunctional epoxy resin, tetraglycidyl-diaminodiphenylmethane (TGDDM), cured with 4,4′-diaminodiphenylsulphone (DDS). All the materials exhibited two-phase morphologies which were characterised by dynamic mechanical thermal analysis and scanning electron microscopy. Addition of the thermoplastic gave a modest improvement in fracture properties (K_1c and G_1c), as determined by three-point bending experiments, although no obvious correlation with the marked morphological changes was observed.     

Effect of SiO2 on rheology,morphology, thermal,and mechanical properties of high thermal stable epoxy foam

A series of highly thermostable epoxy foams with diglycidyl ether of bisphenol‐A and bisphenol‐S epoxy resin (DGEBA/DGEBS), 4,4′‐diaminodiphenyl sulfone (DDS) as curing agent have been successfully prepared through a two‐step process. Dynamic and steady shear rheological measurements of the DGEBA/DGEBS/DDS reacting mixture are performed. The results indicate all samples present an extremely rapid increase in viscosities after a critical time. The gel time measured by the crossover of tan δ is independent of frequency. The influence of SiO₂ content on morphology, thermal, and mechanical properties of epoxy foams has also been investigated. Due to the heterogeneous nucleation of SiO₂, the pore morphology with a bimodal size distribution is observed when the content of SiO₂ is above 5 wt %. Dynamic mechanical analysis (DMA) reveals that pure epoxy foam possesses a high glass transition temperature (206°C). The maximum of specific compressive strength can be up to 0.0253 MPa m³ kg^?1 at around 1.0 wt % SiO₂. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40068.     

Studies of the properties of a thermosetting epoxy modified with block copolymers

Poly[(n‐butyl acrylate)‐block‐poly(methyl methacrylate)‐co‐(glycidyl methacrylate)] (BMG) diblock copolymers incorporating an epoxy‐reactive functionality in one block have been synthesized and used as modifiers for the model epoxy resin E‐51 cured with 4,4′‐diaminodiphenyl methane (DDM). The properties and morphologies of the modified epoxy thermosets were investigated by dynamic mechanical analysis (DMA), impact testing and scanning electron microscopy (SEM). The results reveal that addition of the block copolymers leaves the glass transition temperatures of the blends relatively unchanged, with small decreases in the storage moduli at room temperature. The toughening effect is dependent on the chemical structures of the block copolymers and an increase in the impact strength by a factor of two was obtained by the addition of ‘relatively symmetrical’ block copolymers. Moreover, the impact test results are consistent with the morphologies of the fracture surfaces as evidenced by SEM. Copyright © 2005 Society of Chemical Industry     

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     

Preparation and characterization of an epoxy resin modified by a combination of MDI‐based polyurethane and montmorillonite

The present work investigates the modification of epoxy resin by using a combination of nanoclay (montmorillonite—Cloisite 30B) and a liquid polymeric modifier (polyurethane). Polyurethane was obtained from 4,4′‐diphenylmethane diisocyanate and polydiols with different molecular weight: polyethylene glycol (PEG 400) and polyoxypropylene diols with molecular weight 1000 g/mol and 2000 g/mol. The impact strength, the critical stress intensity factor as well as the flexural strength were evaluated as functions of modifiers content. The obtained results showed that hybrid composites exhibit enhanced mechanical properties without significant changes of the glass transition temperature. FTIR analysis showed that chemical reactions took place between the hydroxyl groups of epoxy resin and the isocyanate groups of polyurethane, explaining an improvement of the mechanical properties of epoxy resin. However, XRD results demonstrated the formation of an exfoliated structure for the hybrid compositions with both polyurethane and montmorillonite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermo mechanical behaviour of unsaturated polyester toughened epoxy–clay hybrid nanocomposites

The intercrosslinked networks of unsaturated polyester (UP) toughened epoxy–clay hybrid nanocomposites have been developed. Epoxy resin (DGEBA) was toughened with 5, 10 and 15% (by wt) of unsaturated polyester using benzoyl peroxide as radical initiator and 4,4′-diaminodiphenylmethane as a curing agent at appropriate conditions. The chemical reaction of unsaturated polyester with the epoxy resin was carried out thermally in presence of benzoyl peroxide-radical initiator and the resulting product was analyzed by FT-IR spectra. Epoxy and unsaturated polyester toughened epoxy systems were further modified with 1, 3 and 5% (by wt) of organophilic montmorillonite (MMT) clay. Clay filled hybrid UP-epoxy matrices, developed in the form of castings were characterized for their thermal and mechanical properties. Thermal behaviour of the matrices was characterized by differential scanning calorimetry (DSC), thermo gravimetric analysis (TGA) and dynamic mechanical analysis (DMA). Mechanical properties were studied as per ASTM standards. Data resulted from mechanical and thermal studies indicated that the introduction of unsaturated polyester into epoxy resin improved the thermal stability and impact strength to an appreciable extent. The impact strength of 3% clay filled epoxy system was increased by 19.2% compared to that of unmodified epoxy resin system. However, the introduction of both UP and organophilic MMT clay into epoxy resin enhanced the values of mechanical properties and thermal stability according to their percentage content. The impact strength of 3% clay filled 10% UP toughened epoxy system was increased by 26.3% compared to that of unmodified epoxy system. The intercalated nanocomposites exhibited higher dynamic modulus (from 3,072 to 3,820 MPa) than unmodified epoxy resin. From the X-ray diffraction (XRD) analysis, it was observed that the presence of d ₀₀₁ reflections of the organophilic MMT clay in the cured product indicated the development of intercalated clay structure which in turn confirmed the formation of intercalated nanocomposites. The homogeneous morphologies of the UP toughened epoxy and UP toughened epoxy–clay hybrid systems were ascertained from scanning electron microscope (SEM).     

Maleimido-functionalized spirobislactone having enhanced volumetric expansion on polymerization

An approach to enhancing the volumetric expansion on polymerization of spirobislactone is proposed. This approach suggests a molecular modification of spirobislactone through attaching a rigid pendant segment bearing maleimido group to its aromatic ring. An additional volumetric expansion is achieved from loose molecular packing in cured resins due to the steric hindrance effect among rigid pendent segments. Thus a new monomer, maleimido-functionalized spirobislactone (MFS), is prepared. In order to evaluate the volumetric expansion of MFS during curing, tetraglycidyl 4,4′-diamino diphenyl methane (TGDDM) is employed to cure with MFS. The volumetric expansion of MFS on curing is measured to be 12.3%, higher than that of net spirobislactone monomer. The existence of loose molecular packing in MFS/epoxy cured resins is demonstrated by morphology observation of the cured resin stained by the phosphotungstic acid (PTA), and the stained regions are observed to be nanoparticles. Such a cured resin, prepared from 20 mol% of MFS and 80 mol% of TGDDM epoxy resin, shows excellent toughness (Charpy impact strength 13,000 J/m²) and good mechanical strength (flexural strength 120 MPa, storage flexural modulus 4.2 GPa). Its glass transition temperature by dynamic mechanical thermal analysis (DMA) attains 227 °C, much higher than that of the cured resin from net spirobislactone and epoxy resin.     

Internal stress analysis of epoxy adhesively-boned joints based on their thermomechanical properties at cryogenic temperature

Internal stress analysis is essential to structural design of materials applied in cryogenic engineering. In this contribution, thermomechanical properties including dynamic thermomechanical properties and thermal expansion behavior of four epoxy resins, namely the polyurethane modified epoxy resin (PUE), diglycidyl ether of bisphenol A (DGEBA), tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) and triglycidyl-p-aminophenol (TGPAP) were studied by dynamic thermomechanical analysis. Internal stress of the epoxy layer in the bonded joint was calculated based on the thermomechanical properties. Meanwhile, the structure-cryogenic property relationship of epoxy resins were investigated. Results demonstrate that internal stress in the four epoxies bonded joints is 6 ~ 21 MPa at −150°C, and is positively correlated with the average thermal expansion coefficient (CTE) of epoxy resins. TGDDM and TGPAP showed higher retention of lap shear strength both at −196°C and after temperature cycling due to their lower CTE. Morphology of the fractured surface of bonded joints demonstrated that internal stress is responsible for the severe interface failure at −196°C. It reveals that selection of epoxy resins with low CTE is beneficial for designing high-performance epoxy adhesive systems served at cryogenic temperature.     

Phthalonitrile‐epoxy blends: Cure behavior and copolymer properties

Binary blends composed of 4,4′‐bis(3,4‐dicyanophenoxy)biphenyl (biphenyl PN) and diglycidyl ether of bisphenol A (epoxy resin) and oligomeric n = 4 phthalonitrile (n = 4 PN) and epoxy resin were prepared. The cure behavior of the blends was studied under dynamic and isothermal curing conditions using differential scanning calorimetry, simultaneous thermogravimetric/differential thermal analysis, infrared spectroscopy, and rheological analysis. The studies revealed that phthalonitrile‐epoxy blends exhibited good processability and that they copolymerized with or without the addition of curing additive. In the absence of curing additive, the blends required higher temperatures and longer cure times. The thermal and dynamic viscoelastic properties of amine‐cured phthalonitrile‐epoxy copolymers were examined and compared with those of the neat epoxy resin. The properties of the epoxy resin improved with increasing biphenyl PN content and with n = 4 PN addition. Specifically, the copolymers exhibited higher glass transition temperatures, increased thermal and thermo‐oxidative stabililty, and enhanced dynamic mechanical properties relative to the commercially available epoxy resin. The results showed that the phthalonitrile‐epoxy blends and copolymers have an attractive combination of processability and high temperature properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Studies on mechanical,thermal, and morphology of diglycidylether‐terminated polydimethylsiloxane‐modified epoxy–bismaleimide matrices

An epoxy matrix system modified by diglycidylether‐terminated polydimethylsiloxane (DGETPDMS) and bismaleimide (BMI) was developed. Epoxy systems modified with 4, 8, and 12% (by wt) of DGETPDMS were made using epoxy resin and DGETPDMS, with diaminodiphenylmethane as the curing agent. The DGETPDMS‐toughened epoxy systems were further modified with 4, 8, and 12% (by wt) of BMI, namely (N,N′‐bismaleimido‐4,4′‐diphenylmethane). DGETPDMS/BMI/epoxy matrices were characterized using differential scanning calorimetry, thermogravimetric analysis, and heat deflection temperature analysis. The matrices, in the form of castings, were characterized for their mechanical properties, viz. tensile strength, flexural strength, and impact test, as per ASTM methods. Mechanical studies indicate that the introduction of DGETPDMS into epoxy resin improves the impact strength, with reduction in tensile strength, flexural strength, and glass transition temperature, whereas the incorporation of BMI into epoxy resin enhances the mechanical and thermal properties according to its percentage content. However, the introduction of both DGETPDMS and BMI enhances the values of thermomechanical properties according to their percentage content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 668–674, 2006     

Dynamics and thermal properties of epoxy resin cured by new diamino disiloxanes

Two disiloxane compounds, 3,3′‐(1,3‐dimethyl‐1,3‐diphenyl‐1,3‐disiloxanediyl)bis(benzenamine) ( C1 ) and 4,4′‐(1,3‐dimethyl‐1,3‐diphenyl‐1,3‐disiloxanediyl)bis(benzenamine) ( C2 ) were synthesized and used as new curing agents of DGEBA epoxy resin with an epoxy value of 0.51 ( E‐51 ). The curing kinetics of E‐51/C1 and E‐51/C2 systems was investigated by non‐isothermal differential scanning calorimetry (DSC) analyses. The activation energy (ΔE) and the characteristic cure temperatures of the two systems were determined. The two systems have the similar activation energy. The reactivity of E‐51/C1 is higher than that of E‐51/C2 . The reaction orders of E‐51/C1 and E‐51/C2 are 0.88 and 0.87, respectively, illustrating that curing reaction between the epoxy resin and curing agent ( C1 or C2 ) is complicated. The DSC result shows that E51 cured by C2 has higher Tg; whereas thermogravimetric analysis results indicate that E51 cured by C1 has higher thermal stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42385.     

Novel amine terminated elastomeric oligomers and their effects on properties of epoxy resins as a toughener

The objective of this study was to investigate the effects of amine terminated elastomeric epoxy tougheners on the mechanical and thermal properties of diglycidyl ether of bisphenol A based epoxy resin. The amine terminated polycaprolactone (PCL) (1) and PCL‐PDMS‐PCL (2) based oligomers were synthesized and characterized by FTIR spectroscopy. The stoichiometrical amount of the reactive oligomers as toughener, reactive epoxy resin and the curing agent, 4,4′‐diaminodiphenyl sulfone (DDS) were mixed and degassed. The homogenous mixtures were cured at 120°C into the preheated molds. The mechanical and thermal characterizations of toughened epoxy resin system were evaluated. It has been shown that the mechanical and thermal properties of toughened epoxy system vary as a function of the chemical structure and the concentration of rective oligomers. Higher mechanical properties were obtained for epoxy resin toughened by PCL‐PDMS‐PCL (2) based oligomer. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of a bifunctional epoxy monomer containing biphenyl moiety and properties of its cured polymer with phenol novolac

A new type of epoxy resin containing a 4,4′‐biphenylene moiety in the backbone (Bis‐EBP) is synthesized and confirmed by elemental analysis, infrared spectroscopy, and ¹H‐nuclear magnetic resonance spectroscopy. In addition, to evaluate the influence of the 4,4′‐biphenylene group in the structure, an epoxy resin having a 1,4‐phenylene group in place of the 4,4′‐biphenylene moiety (Bis‐EP) is synthesized. The cured polymer obtained through the curing reaction between the new biphenyl‐containing epoxy resin and phenol novolac is used for making a comparison of its thermal and physical properties with those obtained from Bis‐EP and bisphenol‐A (4,4′‐isopropylidenediphenyl)‐type epoxy resin (Bis‐EA). The cured polymer obtained from Bis‐EBP shows markedly higher fracture toughness of 1.32 MPa m^1/2, higher glass transition temperature, lower moisture absorption, and higher thermal decomposition temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 690–698, 1999