Time evolution of dielectric parameters during the crosslink of epoxy resins

The d.c. conductivity and the dielectric constant of an epoxy resin cured with a diamine were examined in a frequency interval extended up to 10¹⁰ Hz. The analysis of the dielectric behavior has permitted gaining a better knowledge of the relationships between dielectric parameters and the physical and chemical modifications of the systems. The results indicate that the chemical kinetics of the crosslink process is closely paralleled by the change in time of the dielectric parameters so that dielectrometry provides valuable information on conversion, relaxation times, glass transition temperature and gelation.     

Thermal and mechanical characterization of high performance epoxy systems with extended cure times

Five epoxy resins of different chemistry and functionality were cured with DDS (4,4-diaminodiphenyl sulfone) using 2, 8 and 14 h curecycles. Both Differential Scanning Calorimetry (DSC) and Thermomechanical Analysis (TMA) were used to characterize reaction behavior and cured properties of the resin systems. In addition, static mechanical tests and density measurements were integrated with the thermal characterization methods to correlate resin properties with process time. Flexural three-point bending experiments showed that the resins tended to have higher yield stress and toughness values at extended cure times. The improved mechanical properties could be attributed to the full development of the epoxy molecular structure, in the form of cross-linked networks and molecular rearrangement. These results suggest that extended cure times or high temperature post-curing may be required to obtain the resin's ultimate mechanical properties for high performance composites.The authors would like to thank Dr. Andri Filippov of Shell Development Company for his interest in this work. Financial assistance and material support for this research were provided by Shell Development Company while instrument support was provided by TA Instruments through project support to the Polymeric Composites Laboratory of the University of Washington.     

Impedance spectroscopy of reactive polymers. 2. Multifunctional epoxy/amine formulations

Dielectric measurements were utilized to follow the advancement of cure in a bifunctional and a tetrafunctional epoxy/amine formulation. In deferance to earlier dielectric studies of cure, complex impedance was measured and used to calculate ionic resistivity. By using complex impedance we were able to separate, according to their frequency dependence, the contributions to overall polarization from electrode blocking layers, mobile charge carriers, and dipole relaxations. At any stage of cure, there is a unique frequency at which ionic resistivity can be singularly measured. Our approach does not involve trial-and-error frequency search, it measures dielectric response in real time, and is conducive to the development of phenomenological models based on equivalent circuits. Values of ionic resistivity measured at different cure time and temperature were used to quantify the progress of cure. Excellent agreement was reported between the calculated values of normalized degree of cure obtained by dielectric and calorimetric measurements. It was suggested that apart from the extrinsic conductivity by ionic impurities, an intrinsic mechanism which involves the reactive molecules contributes to the overall ionic conductivity. © 1995 John Wiley & Sons, Inc.     

Dielectric in situ sensor monitoring of phase separation and changes in the state of each phase

Frequency dependent dielectric measurements have been used to monitor and characterize the phase separation process and changes in state of each phase. The measurements are made in situ using a micro planar sensor. They can be made both in the laboratory as well as in an industrial production or use environment. Two examples are presented. The first is monitoring the onset of phase separation, the buildup in Tg and change in composition of each phase during “reactive processing” of a high performance thermoplastic (TP) PPI, thermoset precursors (TS) DGEBA-MCDEA intially homogeneous blend. The second example involves monitoring the stability, onset of phase separation, as a function of temperature on a mineral oil, stearyl alcohol, water, sufactant emulsion used in the cosmetic industry.     

DSC study of cure kinetics of DGEBA-based epoxy resin with poly(oxypropylene) diamine

Summary A kinetic study of cure kinetics of epoxy resin based on a diglycidyl ether of bisphenol A (DGEBA), with poly(oxypropylene) diamine (Jeffamine D230) as a curing agent, was performed by means of differential scanning calorimetry (DSC). Isothermal and dynamic DSC characterizations of stoichiometric and sub-stoichiometric mixtures were performed. The kinetics of cure was described successfully by empirical models in wide temperature range. System with sub-stoichiometric content of amine showed evidence of two separate reactions, second of which was presumed to be etherification reaction. Catalytic influence of hydroxyl groups formed by epoxy-amine addition was determined.     

Comparison of the effectiveness of epoxy cure accelerators using a fluorescent molecular probe

A simple optical method for quantitative comparison of the effectiveness of epoxy cure accelerators, used for speeding up the crosslinking process of epoxy resins with cyclic anhydrides, is described. Fluorescent molecular probes and a miniature fiber optic spectrometer have been applied for measurement of the cure kinetics of a model epoxy resin/anhydride composition in the presence of various cure accelerators. A quantitative index of accelerator performance has been determined for several of the most common accelerators.     

Effect of aromatic substitution on the cure reaction and network properties of anhydride cured triphenyl ether tetraglycidyl epoxy resins

A systemic study of the impact of aromatic substitution on the reaction rate and network properties of the isomers of a tetraglycidylaniline triphenyl ether epoxy resin cured with anhydride hardeners is presented here. The epoxy resins synthesized in this work were based upon N,N,N,N‐tetraglycidyl bis(aminophenoxy)benzene (TGAPB), where the glycidyl aniline and ether groups change from being all meta (133 TGAPB), to meta and para (134 TGAPB), and finally to an all para substituted epoxy resin (144 TGAPB). Increasing para substitution increased reaction rate, promoted the onset of vitrification and increased epoxide conversion. Thermal properties such as glass transition temperatures (T_g) and coefficients of thermal expansion (CTE) both increased consistently with increasing para substitution, although thermal stability as measured via thermogravimetric analysis decreased. Mechanical properties also varied systematically with flexural strength and ductility increasing with increased para substitution, while the modulus decreased. Indeed, the ductility almost doubled, as measured by the work of fracture and displacement at failure highlighting the importance of substitution on properties.     

Phase separation,porous structure,and cure kinetics in aliphatic epoxy resin containing hyperbranched polyester

Thermosetting blends of an aliphatic epoxy resin and a hydroxyl‐functionalized hyperbranched polymer (HBP), aliphatic hyperbranched polyester Boltorn H40, were prepared using 4,4′‐diaminodiphenylmethane (DDM) as the curing agent. The phase behavior and morphology of the DDM‐cured epoxy/HBP blends with HBP content up to 40 wt % were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and scanning electron microscopy (SEM). The cured epoxy/HBP blends are immiscible and exhibit two separate glass transitions, as revealed by DMA. The SEM observation showed that there exist two phases in the cured blends, which is an epoxy‐rich phase and an HBP‐rich phase, which is responsible for the two separate glass transitions. The phase morphology was observed to be dependent on the blend composition. For the blends with HBP content up to 10 wt %, discrete HBP domains are dispersed in the continuous cured epoxy matrix, whereas the cured blend with 40 wt % HBP exhibits a combined morphology of connected globules and bicontinuous phase structure. Porous epoxy thermosets with continuous open structures on the order of 100–300 nm were formed after the HBP‐rich phase was extracted with solvent from the cured blend with 40 wt % HBP. The DSC study showed that the curing rate is not obviously affected in the epoxy/HBP blends with HBP content up to 40 wt %. The activation energy values obtained are not remarkably changed in the blends; the addition of HBP to epoxy resin thus does not change the mechanism of cure reaction of epoxy resin with DDM. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 889–899, 2006     

Synthesis of an adhesion‐enhancing polysiloxane containing epoxy groups for addition‐cure silicone light emitting diodes encapsulant

Addition‐cure silicone resin is considered as a good choice for light emitting diodes (LEDs); however, it has very poor adhesion to the substrate, which limits its practical application. A novel polysiloxane with self‐adhesion ability and higher refractive index for the encapsulating of high‐power LEDs is prepared and characterized. This polysiloxane containing vinyl groups, phenyl groups, and epoxy groups was synthesized by a sol‐gel condensation process from methacryloxy propyl trimethoxyl silane, γ‐(2,3‐epoxypropoxy)propytrimethoxysilane, and diphenylsilanediol under the catalysis of an anion exchange resin. Then, the resin‐type encapsulation material was prepared by hydrosilylation of methylphenyl hydrogen‐containing silicone resin and the newly synthesized polysiloxane material. The novel polysiloxane was characterized by ¹H‐NMR and Fourier transform infrared spectroscopy. On the basis of higher refractive index, higher transparency, excellent thermal stability, and appropriate hardness, as well as good adhesive strength between the encapsulating material and the LED lead frame (polyphthalamide), the curable silicone resin‐type encapsulation material can be used as an encapsulant for LEDs. Copyright © 2014 John Wiley & Sons, Ltd.     

A new ultrasonic measurement system for the cure monitoring of thermosetting resins and composites

Measurements of the ultrasonic sound speed of thermosetting resins and composites can be used as an in-process cure monitoring technique. Ultrasonic measurements have an advantage over other in-process techniques in that ultrasonic sensors do not make contact with the part (thus leaving no imbedded sensor or witness mark) and can make true bulk measurements of the part. A new commercially available ultrasonic cure monitoring system has been developed which easily enables ultrasonic measurements to be made in compression molding, resin transfer molding, and autoclave processes. Advancements in ultrasonic sensor technology enable the sensor to maintain good coupling to the part during thermal cycling to 260C. Data is presented showing the change in ultrasonic sound speed during the compression molding of a graphite-epoxy prepreg. The data shows a good relationship to the ionic conductivity and resistivity data collected via dielectric cure monitoring.This effort was sponsored by the Manufacturing Technology Directorate, Wright Laboratory (WL/MTX), Air Force Material Command, USAF, under cooperative agreement award(s) to NCMS. The U. S. Government is authorized to reproduce and distribute reprints for Governmental purposes notwithstanding any copyright notation thereon. The views and conclusions contained herein are those of the authors and should not be interpreted as necessarily representing the official policies or endorsements, either expressed or implied, of Wright Laboratory or the U.S. Government.     

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     

Cure kinetics of epoxy resin-natural zeolite composites

The cure kinetics of epoxy resin and epoxy resin containing 10 mass% of natural zeolite were investigated using differential scanning calorimetry (DSC). The conformity of the cure kinetic data of epoxy and epoxy-zeolite system was checked with the auto-catalytic cure rate model. The results indicated that the hydroxyl group on the zeolite surface played a significant role in the autocatalytic reaction mechanism. This group was able to form a new transition state between anhydride hardener and epoxide group. The natural zeolite particles acted as catalyst for the epoxy system by promoting its curing rate.     

Effects of water on epoxy cure kinetics and glass transition temperature utilizing molecular dynamics simulations

Effects of water on epoxy cure kinetics are investigated. Experimental tests show that absorbed water in an uncured bisphenol‐F/diethyl‐toluene‐diamine epoxy system causes an increase in cure rate at low degrees of cure and a decrease in cure rate at high degrees of cure. Molecular simulations of the same epoxy system indicate that the initial increase in cure rate is due to an increase in molecular self‐diffusion of the epoxy molecules in the presence of water. Effects of water on the glass transition temperature (T_g) of the crosslinked thermoset are also studied. Both experiments and simulations show that water decreases T_g. Both types of results indicate that T_g effects are small below 1% water by weight, but that T_g depression occurs much quickly with increasing water content above 1%. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1150–1159     

Curing reaction of biphenyl epoxy resin with different phenolic functional hardeners

The investigation of cure kinetics and relationships between glass transition temperature and conversion of biphenyl epoxy resin (4,4′-diglycidyloxy-3,3′,5,5′-tetramethyl biphenyl) with different phenolic hardeners was performed by differential scanning calorimeter using an isothermal approach over the temperature range 120–150°C. All kinetic parameters of the curing reaction including the reaction order, activation energy, and rate constant were calculated and reported. The results indicate that the curing reaction of formulations using xylok and dicyclopentadiene type phenolic resins (DCPDP) as hardeners proceeds through a first-order kinetic mechanism, whereas the curing reaction of formulations using phenol novolac as a hardener goes through an autocatalytic kinetic mechanism. The differences of curing reaction with the change of hardener in biphenyl epoxy resin systems were explained with the relationships between T_g and reaction conversion using the DiBenedetto equation. A detailed cure mechanism in biphenyl-type epoxy resin with the different hardeners has been suggested. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 773–783, 1998     

Isothermal cure kinetics of epoxy/phenol‐novolac resin blend system initiated by cationic latent thermal catalyst

The investigation of the cure kinetics of a diglycidyl ether of bisphenol A (DGEBA)/phenol‐novolac blend system with different phenolic contents initiated by a cationic latent thermal catalyst [N‐benzylpyrazinium hexafluoroantimonate (BPH)] was performed by means of the analysis of isothermal experiments using a differential scanning calorimetry (DSC). Latent properties were investigated by measuring the conversion as a function of curing temperature using a dynamic DSC method. The results indicated that the BPH in this system for cure is a significant thermal latent initiator and has good latent thermal properties. The cure reaction of the blend system using BPH as a curing agent was strongly dependent on the cure temperature and proceeded through an autocatalytic kinetic mechanism that was accelerated by the hydroxyl group produced through the reaction between DGEBA and BPH. At a specific conversion region, once vitrification took place, the cure reaction of the epoxy/phenol‐novolac/BPH blend system was controlled by a diffusion‐control cure reaction rather than by an autocatalytic reaction. The kinetic constants k₁ and k₂ and the cure activation energies E₁ and E₂ obtained by the Arrhenius temperature dependence equation of the epoxy/phenol‐novolac/BPH blend system were mainly discussed as increasing the content of the phenol‐novolac resin to the epoxy neat resin. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2945–2956, 2000     

Isobaric cure shrinkage behaviors of epoxy molding compound in isothermal state

The warpage of plastic‐encapsulated IC packages after molding is believed to be induced by thermal and cure shrinkage of epoxy molding compound (EMC). To study the warpage behaviors of EMC, the amount of cure‐induced shrinkage needs to be understood. Volume shrinkage behaviors induced by cure reaction of EMC in isothermal and isobaric states were studied with a differential scanning calorimeter (DSC) and a pressure–temperature‐controlled dilatometer. The results show that higher pressure induce more volume shrinkage under fixed temperature but the difference of volume shrinkage under different pressure levels doesn't obey the principle of linearity. It is observed that the amount of chemical volume shrinkage at 145 °C is higher than those under three other temperatures: 160, 175, and 190 °C. The chemical volume shrinkage of EMC is found to be very process dependent. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2392–2398, 2005     

Miscibility and cure kinetics studies on blends of bisphenol-A polycarbonate and tetraglycidyl-4,4′-diaminodiphenylmethane epoxy cured with an amine

Differential scanning calorimetry (DSC) has been applied to characterize the glass transition behavior of the blends formed by bisphenol-A polycarbonate (PC) with a tetrafunctional epoxy (tetraglycidyl-4,4′-diaminodiphenyl methane, TGDDM) cured with 4,4′-diaminodiphenylsulphone (DDS). A rare miscibility in the complete composition range has been demonstrated in these blends. Additionally, the blend morphology was examined using scanning electron microscopy (SEM) and a homogeneous single-phase PC/epoxy network has been observed in the blends of all compositions. Moreover, polycarbonate incorporation has been found to exert a distinct effect on the cure behavior of the epoxy blends. The cure reaction rates for the epoxy-PC blends were significantly higher due to the presence of PC. In addition, the cure mechanism of the epoxy blends was no longer autocatalytic. An n-th order reaction mechanism with n = 1.2 to 1.5 has been observed for the blends of DDS-cured epoxy with PC of various compositions studied using DSC. The proposed n-th order kinetic model has been found to describe well the cure behavior of the epoxy/PC blends up to the vitrification point. © 1995 John Wiley & Sons, Inc.