Modeling the curing kinetics for a modified bismaleimide resin

The kinetics of curing for a modified bismaleimide (BMI) has been investigated to ascertain a suitable cure model for the material. The experimental data for characterizing the curing kinetics for a modified bismaleimide resin were determined using a DSC isothermal scan method and indicated a curing mechanism involving multiple reactions. The reaction process was shown to be dominated by a different mechanism at different stages of the cure process, with an initial autocatalytic reaction shifting into an nth order reaction as the reaction proceeded. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 907–913, 2000     

Curing characteristics of o-cresol novolac epoxy resin modified by bismaleimide

Curing characteristics of o-cresol novolac epoxy resin modified by 4,4-diaminodiphenylmethane bismaleimide (DDM-BMI) using FTIR were investigated and the glass transition temperature was measured. With the addition of DDM as hardener, the relative curing reaction conversion of DDM-BMI increased with equivalent weight ratio [R₁ = (equiv wt summation of epoxy and DDM-BMI)/equiv wt of DDM] and weight ratio of epoxy and DDM-BMI (R₂ = wt of epoxy resin/wt of DDM-BMI). Using phenol novolac resin (PN) as hardener, the curing reaction conversion of DDM-BMI was hardly changed, but the variation of that in the epoxy resin was observed with R₂ change. © 1996 John Wiley & Sons, Inc.     

BMD/UP体系非等温固化动力学研究

不饱和聚酯是最常用的一种热固性材料,其力学性能和耐热性是较受关注的两个方面,利用双马来酰亚胺作为第二组分对不饱和聚酯进行耐热改性的工作取得了较好的效果。研究其动力学过程对于固化反应温度、时间等工艺合理优化控制,制备高性能复合材料具有重要意义。考虑到BMD／UP体系中反应的复杂性,本文采用n级动力学模型,进行了非等温动力学研究。     

Mechanical,thermal and morphological behavior of bismaleimide modified polyurethane‐epoxy IPN matrices

An intercrosslinked network of bismaleimide modified polyurethane‐epoxy systems were prepared from the bismaleimide having ester linkages, polyurethane modified epoxy and cured in the presence of 4,4′‐diaminodiphenylmethane. Infrared spectral analysis was used to confirm the grafting of polyurethane into the epoxy skeleton. The prepared matrices were characterized by mechanical, thermal and morphological studies. The results obtained from the mechanical and thermal studies reveal that the incorporation of polyurethane into the epoxy skeleton increases the mechanical strength and decreases the glass transition temperature, thermal stability and heat distortion temperature. Whereas, the incorporation of bismaleimide having ester linkages into polyurethane modified epoxy systems increases the thermal stability, tensile and flexural properties and decreases the impact strength, glass transition temperature and heat distortion temperature. Surface morphology of polyurethane modified epoxy and bismaleimide modified polyurethane‐epoxy systems were studied using scanning electron microscopy. Copyright © 2003 John Wiley & Sons, Ltd.     

Preparation and properties of modified bismaleimide resins by novel bismaleimide containing 1,3,4‐oxadiazole

Bismaleimide (BMI) resin is a high‐performance thermosetting polymer, but its inherent brittleness hinder a broader range of application. Therefore, it has aroused wide concern to improve the toughness of BMI resins without scarification of their thermal stability. This paper reported some studies on modified BMI resins based on diallyl bisphenol A, novel BMI monomers, e.g. 2‐[3‐(4‐maleimidophenoxy)phenyl]‐5‐(4‐maleimidophenyl)‐1,3,4‐oxadiazole (m‐Mioxd) or 2‐[4‐(4‐maleimidophenoxy)phenyl]‐5‐(4‐maleimidophenyl)‐1,3,4‐ oxadiazole (p‐Mioxd) in different proportions (0.87:1, 1:1, 1.2:1; mol/mol). The curing mechanism and kinetics of the copolymerized systems were investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy. Thermogravimetric analysis was applied to study the thermal properties of the cured resins, and the results indicated that the modified resins had excellent thermal stability with high residual weight percentage at 700°C (>50%), temperatures for 5% weight loss around 400°C. Besides, N,N′‐4,4′‐bismaleimidodiphenylmethylene and O,O′‐diallyl bisphenol A resin blends were modified by m‐Mioxd and p‐Mioxd, respectively. We investigated the effects of mole concentration of m‐Mioxd or p‐Mioxd on the curing process, mechanical properties, fracture toughness, and heat resistance of the modified resins. The results revealed that the introduction of m‐Mioxd and p‐Mioxd could improve the impact property of the modified BMI resins. When their proportion was 0.07, the impact strength increased 123.8% and 108.3%, respectively. The novel chain‐extended BMIs could reduce the crosslink density of cured resins and improve the brittleness effectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of organoclay on the curing reactions in bismaleimide/diallyl bisphenol a resin

4,4′‐Bismaleimidodiphenyl methane (BMPM)/2,2′‐diallyl bisphenol A (DBA)/organoclay nanocomposites were synthesized. The effects of organoclays on the curing reactions in the BMPM/DBA system at low temperatures (ene reaction) and high temperatures (Diels–Alder reaction, homopolymerization of BMPM, and alternative copolymerization) were investigated with differential scanning calorimetry and Fourier transform infrared techniques. The results showed that these reactions were affected to different extents in the presence of organoclays. The ene reaction was accelerated to different degrees depending on the acidity of the modifier and the accessibility of the organoclays used. The exfoliation degree of organoclays in the prepolymers showed great effects on the curing behavior of BMPM/DBA. When an organoclay was less intercalated, the curing behavior of the system was different from that of neat BMPM/DBA. On the other hand, when the organoclay was better exfoliated in prepolymers, the curing behavior of the system was similar to that of the neat BMPM/DBA system. However, even in this case, the reactions at high temperatures occurred in different ways in the presence of an organoclay. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 994–1006, 2005     

Rheological and dielectric changes during isothermal epoxy-amine cure

Dynamic viscosity and ionic conductivity were measured simultaneously during the cure of a digylcidyl ether of bisphenol-A (DGEBA) epoxy resin with diamino-diphenyl sulfone (DDS) by mounting a microdielectric sensor into the plates of a rheometer. Two different cure temperatures were examined. Periodically, throughout the cure, samples were removed from the plates of the rheometer, quenched, and analyzed for the glass transition temperature and epoxide conversion. The relationship between conductivity and viscosity appeared to be independent of cure temperature. A linear relation with a slope of ?1 was observed between the natural logarithms of conductivity and viscosity during the cure up to approximately 85% cure conversion. It was hypothesized that the reaction rate was hindered by diffusion at this stage in the polymerization. A free volume relationship was used to successfully correlate conductivity with viscosity up to the diffusion limited region. ©1995 John Wiley & Sons, Inc.     

Allyl ether of aralkyl phenolic resin with low melt viscosity and its Alder‐ene blends with bismaleimide: synthesis,curing, and laminate properties

This paper outlines the synthesis and characterization of O‐allyl aralkyl phenolic (O‐allyl Xylok, OAX) resins having low melt viscosity and its Alder‐ene blends with 2, 2′‐bis 4‐[(4′‐maleimido phenoxy) phenyl] propane. The blends manifested a three‐stage curing pattern that converged to a two‐stage pattern on enhancing the maleimide content. The polymerization kinetics of typical allyl and maleimide rich resin systems showed apparent activation energy increasing and pre‐exponential factor decreasing from ene to the Diels–Alder step. Increased allyl content improved mechanical and impact properties of the composites at ambient temperature, although it diminished the retention of interlaminar shear strength at elevated temperature. Increased maleimide content of the resin was conducive for the higher rigidity for the composite and its retention at elevated temperature. A substantial increase in T_g (from 153°C to 280°C) and thermal stability was observed with an increase in maleimide content. High allyl content resulted in improved mechanical properties thanks to better resin–reinforcement interaction as revealed from morphological analysis. Copyright © 2014 John Wiley & Sons, Ltd.     

Dielectric properties of self‐catalytic interpenetrating polymer network based on modified bismaleimide and cyanate ester resins

Bismaleimide (BMI) resins with good thermal stability, fire resistance, low water absorption, and good retention of mechanical properties at elevated temperatures, especially in hot/wet environments, have attracted more attention in the electronic and aerospace industries. However, their relatively high dielectric constant limits their application in the aforementioned fields. In this work, a new promising approach is presented that consists of the formation of a self‐catalytic thermoset/thermoset interpenetrating polymer network. Interpenetrating polymer networks (IPNs) based on modified BMI resin (BMI/DBA) and cyanate ester (b10) were synthesized via prepolymerization followed by thermal curing. The self‐catalytic curing mechanism of BMI/DBA‐CE IPN resin systems was examined by differential scanning calorimetry. The dielectric properties of the cured BMI/DBA‐CE IPN resin systems were evaluated by a dielectric analyzer and shown in dielectric properties‐temperature‐log frequency three‐dimensional plots. The effect of temperature and frequency on the dielectric constant of the cured BMI/DBA‐CE IPN resin systems is discussed. The composition effect on the dielectric constant of the cured IPN resin systems was analyzed on the basis of Maxwell's equation and rule of mixture. The obtained BMI/DBA‐CE IPN resin systems have the combined advantages of low dielectric constant and loss, high‐temperature resistance, and good processability, which have many applications in the microelectronic and aerospace industries. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1123–1134, 2003     

Surface characterization and barrier properties of plasma‐modified polyethersulfone/layered silicate nanocomposites

This study describes the preparation of polyethersulfone (PES)/layered silicate nanocomposites (PLSNs) by mixing PES polymer chain into organically‐modified layered silicate in 1‐methyl‐2‐pyrrolidinone (NMP) solution. Both X‐ray diffraction data and transmission electron microscopy images of PLSNs indicate that the silicate layers were almost exfoliated and randomly distributed into the PES matrix. The mechanical and barrier properties of PLSNs show remarkable enhancement in the storage modulus and water/oxygen permeability when compared with that of neat PES matrix. Surfaces modification of PES and PLSN films with various treated times, system pressures, and radio frequency (RF) powers were performed using a mixture of oxygen (O₂) and nitrogen (N₂) plasmas. The topographical and physical properties of plasma‐modified PES and PLSN surfaces were investigated using scanning probe microscopy (SPM), contact‐angle measurements, and X‐ray photoelectron spectroscopy (XPS). These results indicate that the surface roughness of PLSNs with the same condition of plasma modification is lower than that of neat PES matrix and is probably due to the increase of stiffness with the presence of inorganic layered silicates in PES matrix. The surface properties of the PES and PLSNs are also changed from hydrophobic to hydrophilic. The XPS spectra suggest that the exposure of the PES and PLSNs to the plasmas led to the combination of etching reactions of polymer surface initiated by plasma and the following addition reactions of new oxygen‐ and nitrogen‐containing functional groups onto polymer surfaces to change their surface properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3185–3194, 2006     

Influence of glass transition temperature of crosslinked unsaturated polyester resin/styrene formulations on the final conversion after an isothermal curing at 100°C

SMC (sheet molding compound) is a composite based on fibers‐reinforced unsaturated polyester (UP) resin molded usually at 140°C to 170°C under a pressure of 60 to 100 bars. In order to develop new SMC formulations that can be molded at lower temperature (100°C) for economic and environmental reasons, the formulation of the composite had to be completely modified, both to allow a rapid reaction at 100°C, but also to avoid a vitrification phenomenon due to the fact that the glass transition temperature (Tg) of the SMC parts becomes, during the molding process, higher than the mold temperature. In this paper, the relation between the molding temperature, the glass transition temperature, and the final conversion of UP resin/styrene formulations has been underlined. The Tg of the cured resin was decreased by two different ways. The first way involved the reduction of the crosslinking density of the UP resin by using a blend of two resins, a pure maleic and a more flexible one. This blend allows to adjust the Tg over a temperature range from 197°C (Tg of the pure UP resin) to 75°C (Tg of the pure flexible resin). The second way consisted in the addition of butyl methacrylate (BuMA), a reactive plasticizer, to the formulation, allowing a decrease of the final material's Tg from 197°C to 130°C by replacing 35 wt% of styrene by BuMA. These two methods allow to obtain a final conversion of 99% after 8 minutes of molding at 100°C.     

Some comments on nature of the structural relaxation and glass transition

We report on an experiment and new formula revealing dynamic and structural heterogeneity observed in liquids and polymeric systems. The formula applied to data obtained by mechanical spectroscopy reveals the glass-forming system behaviour giving the parameters previously postulated. The presented results are compared with data obtained for liquids (oligomers) confined to nanoporous media. To explain the behaviour of the polymeric systems the three-phase model is considered.     

Rheological and thermal study of delayed crystallization in poly(butylene terephthalate)/ethylene‐co‐ethyl acrylate blends

The effects of the composition and resulting morphology on the crystallization and rheology of blends containing poly(butylene terephthalate) (PBT) and an ethylene‐co‐ethyl acrylate (EEA) copolymer, two immiscible polymers, were studied over the entire range of volume fractions. Differential scanning calorimetry (DSC) thermograms recorded during cooling showed important differences, mainly in terms of the PBT crystallization temperatures, depending on the blend composition. In addition to the classical crystallization peaks of PBT and EEA, a third crystallization peak appeared for blends containing less than 60% PBT. This peak was attributed to a delayed crystallization of PBT. This phenomenon was examined in terms of homogeneous crystallization. Linear viscoelastic measurements allowed the delayed crystallization behavior in these polymer blends to be displayed. Indeed, the variation of the storage modulus with the temperature showed increasing steps during cooling. These sudden increases appeared at temperatures very close to those at which the crystallization peaks were observed in the DSC experiments. This behavior was verified for different blend compositions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 714–721, 2004     

Synthesis and properties of bismaleimide‐modified novolak resin/silsesquioxane nanocomposites

Bismaleimide‐modified novolak resin/silsesquioxane (BMI‐PN/SiO_3/2) nanocomposites were prepared by the sol–gel process. The reactions in the sol–gel synthesis were characterized by Fourier transform infrared spectroscopy. It was found by field emission scanning electron microscopy and atomic force microscopy studies that the particle size of the dispersed phase was about 100 nm, and there existed particle aggregates. The proportion of bismaleimide in the BMI‐PN/SiO_3/2 nanocomposites showed an important effect on the thermal properties of the composites, as demonstrated by thermogravimetric analysis and dynamical mechanical analysis. Major improvements in the glass‐transition temperature and the heat resistance of the material were achieved by the introduction of the nanosized SiO_3/2 inorganic phase, and the modulus at high temperatures was improved too. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2599–2606, 2003     

Dielectric and rheological study of the molecular dynamics during the cure of an epoxy resin

Composite manufacturing is currently one of the most challenging processes for industrial lightweight applications. To date, the process conditions for polymer‐based composite manufacturing are evaluated by laboratory measurements: usually, the flow behavior and the curing of the polymer matrix material are characterized by rheology and quality assurance is performed by thermo‐physical analysis in postprocess measurements. In contrast a dielectric in‐mold sensor offers the possibility to measure the real‐time behavior of the polymer during processing. This study focuses on the correlation of simultaneous rheological and dielectric measurements on Hexcel RTM6 using a coupled setup of both techniques. For dielectric measurements a reusable in‐mold sensor was used and a calibration, taking into account the cable response, was performed. The results show good agreement with respect to glass‐transition temperature and the gel‐point. This can be understood by the fluctuation–dissipation theorem that explicitly relates molecular dynamics to the macromolecular mechanical properties under dynamic time‐dependent load. Furthermore, it was found that the dynamic viscosity can directly be related to the electrical conductivity. This proves the high potential of dielectric analysis as online‐capable technique for material characterization during composite manufacturing. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 907–913     

Time‐resolved wide‐angle X‐ray scattering measurements during the isothermal crystallization and ferroelectric phase‐transition processes of a vinylidene fluoride/trifluoroethylene copolymer

The time‐resolved measurement of wide‐angle X‐ray scattering was performed with a synchrotron radiation source during the processes of the isothermal crystallization and ferroelectric phase transition of a vinylidene fluoride/trifluoroethylene copolymer with 73 mol % vinylidene fluoride. When the sample was cooled rapidly from the melt to the temperature region of the paraelectric high‐temperature phase, the peak position of the 200/110 reflection shifted toward the higher angle side and the half‐width became narrower. This indicated an increase in the crystallite size with a more compact chain‐packing mode. Even when the temperature jump was made from the melt into the region of the ferroelectric or low‐temperature phase, the crystallization of the high‐temperature phase was first observed before the appearance of the low‐temperature phase. This was consistent with a prediction based on the so‐called Ostwald state rule: the thermodynamically unstable but kinetically preferable high‐temperature phase can appear first even when the thermodynamically more stable low‐temperature phase should be created. The time‐dependent intensity changes were analyzed with the Avrami kinetic equation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4175–4181, 2004     

Theoretical study on dependence of hyperpolarizability of one‐dimensional ring system on the delocalization transition

We calculate the optical properties such as the polarization, the (hyper)polarizabilities, the critical vector potential, etc., in terms of the non‐Hermitian Anderson model of a 6‐site ring model. The dependence of the optical properties on the delocalization transition is investigated. It is found that all the total optical properties nonlinearly increase with the increase of the delocalization. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Thermal curing behavior of MWCNT modified vinyl ester‐polyester resin suspensions prepared with 3‐roll milling technique

This study aims to investigate the curing behavior of a vinyl ester‐polyester resin suspensions containing 0.3 wt % of multiwalled carbon nanotubes with and without amine functional groups (MWCNTs and MWCNT‐NH₂). For this purpose, various analytical techniques, including Differential Scanning Calorimetry (DSC), Fourier infrared spectroscopy (FTIR), Raman Spectroscopy, and Thermo Gravimetric Analyzer (TGA) were conducted. The resin suspensions with carbon nanotubes (CNTs) were prepared via 3‐roll milling technique. DSC measurements showed that resin suspensions containing CNTs exhibited higher heat of cure (Q), besides lower activation energy (E_a) when compared with neat resin. For the sake of simplicity of interpretation, FTIR investigations were performed on neat vinyl ester resin suspensions containing the same amount of CNTs as resin. As a result, the individual fractional conversion rates of styrene and vinyl ester were interestingly found to be altered dependent on MWCNTs and MWCNT‐NH₂. The findings obtained from RS measurements of the cured samples are highly proportional to those obtained from FTIR measurements. TGA measurements revealed that CNT modified nanocomposites have higher activation energy of degradation (E_d) compared with the cured polymer. The findings obtained revealed that CNTs with and without amine functional groups alter overall thermal curing response of the surrounding matrix resin, which may probably impart distinctive characteristics to mechanical behavior of the corresponding nanocomposites achieved. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1511–1522, 2009     

Efficient gel‐type electrolyte with bismaleimide via in situ low temperature polymerization in dye‐sensitized solar cells

This study reports the characteristics of gel‐type dye‐sensitized solar cells (DSSCs), fabricated with gel‐type electrolyte containing poly‐1,1′‐(methylenedi‐4,1‐phenylene)bismaleimide (PBMI), or poly‐1,1′‐(3,3′‐dimethyl‐1,1′‐biphenyl‐4,4′‐diyl)bismaleimide (PDBBMI), or poly‐N,N′‐(4‐methyl‐1,3‐phenylene)bismaleimide (PMPBMI), prepared by in situ polymerization of the corresponding monomer without an initiator at 30 °C. Incorporating 0.3 wt % content of exfoliated alkyl‐modified nanomica (EAMNM) into PBMI‐gelled electrolyte leads to higher short‐circuit current density (J_sc = 17.14 mA cm^?2) and efficiency (η = 7.02%) than that of neat PBMI‐gel electrolyte (J_sc = 15.32 mA cm^?2, η = 6.41%). Incorporating 0.3 wt % EAMNM into PBMI‐gelled electrolyte results in remarkably stable device performance under continuous light soaking under one sun (100 mW cm^?2) at 55 °C. The efficiency of DSSCs based on PBMI/0.3 wt % EAMNM‐gelled electrolyte drops by only 1.7% (η = 6.93%) after 500 h of continuous light soaking. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Calorimetric studies on an anhydride‐cured epoxy resin from diglycidyl ether of bisphenol‐A and diglycidyl ether of poly(propylene glycol). I. Onset of diffusion control during isothermal polymerization

Calorimetric studies on a series of anhydride‐cured epoxy resins, in which the epoxy oligomer is a mixture of diglycidyl ether of bisphenol‐A (DGEBA) and diglycidyl ether of poly(propylene glycol) (DGEPPG) in different mole ratios, were carried out. DGEPPG is a flexible epoxy oligomer that was used to tune glass transition temperature for the fully reacted epoxy resin. Conversion versus time curves for the systems with different DGEBA/DGEPPG mole ratios (not including the neat DGEPPG system) were found to overlap with each other in mass‐controlled reaction regime, indicating similar reactivities of epoxy groups in both epoxy oligomers. Onset of diffusion‐controlled reaction regime for different systems was estimated by fitting the conversion versus time data using a phenomenological kinetic equation, as well as from direct comparison of the conversion versus time curves. For the systems (i.e., 0, 10, and 30% DGEPPG) that vitrify during reaction, the crossover from mass‐controlled to diffusion‐controlled reaction occurs close to the onset of the vitrification, where T_g is about 25–30 K below the reaction temperature. For the system (i.e., 50% DGEPPG system) that does not vitrify during the reaction, such crossover still occurs when the T_g of the mixture reaches a value about 25 K below the reaction temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2155–2165, 2008