Influence of cure system concentration on crosslink structure in SBR sulphur vulcanizates

A series of pure gum styrene-butadiene copolymer mixes, compounded with a $\text{sulphur}\text{N-}\text{cyclohexyl}\text{-2-}\text{benzothiazyl}$ sulphenamide (CBS) curing system and vulcanized for various times at 150°C has been subjected to extraction and chemical probe treatments to cleave polysulphidic and disulphidic crosslinks. The changes in the value of C₁ of the Mooney-Rivlin equation, obtained from stress-strain data, and the degree of swelling in n-heptane are reported. The weight losses occurring during these treatments have also been determined. If the proportion of vulcanizing ingredients is varied with the ratio of sulphur to CBS held constant, the ratio of monosulphidic to disulphidic crosslinks varies considerably at cure times from 45 to 120 min; no polysulphidic crosslinks were present in the vulcanizates examined. The paper contains values of C₂ (Mooney-Rivlin equation) and of χ, the polymer-liquid interaction constant; the latter varies with the cure system and is altered by the chemical probe treatments.     

Effect of post-cure on the glass transition temperature and mechanical properties of epoxy adhesives

The effects of post-curing and cure temperature on the glass transition temperature, T _g, and the mechanical properties of epoxy adhesives were studied. T _g was measured by a dynamic mechanical analysis apparatus developed in-house and the mechanical properties of the adhesives (yield strength, Young’s modulus and failure strain) were measured by a tensile machine. The relationships between T _g and mechanical performance under various post-cure conditions were investigated. The curing process was the same for all tests, consisting of an initial stage performed at different temperatures followed by cooling at room temperature. Three sets of specimens were considered, sharing the same initial cure process, but with a different post-curing procedure. In the first set, the specimens were only subjected to a curing process; in the second set, the specimens were subjected to a curing process followed by a post-cure performed at a temperature below the T _g of the fully cured network, T _g∞; and in the third set, the specimens were subjected to a curing process followed by a post-cure performed at a temperature above the T _g∞. When post-cured at a temperature above T _g∞, the mechanical and physical properties tend to have a constant value for any cure temperature.     

Cure characterization of Cycom 977‐2A carbon/epoxy composites for quickstep processing

In this effort, Quickstep, a relatively a new technique, have been employed for manufacturing of composite materials. The cure schedule provided by a prepreg manufacturer is usually designed for autoclave or other traditional processing techniques and thermosetting resin systems are formulated for ramp rate curing 2–3 K min^?1. While in case of Quickstep processing, ramp rates of 15 K min^?1 can be achieved, thus changing the chemorheology of resin. The cure process of 977‐2A carbon/epoxy composites was evaluated for Quickstep processing using differential scanning calorimetry (DSC), dynamic mechanical and thermal analysis, and Fourier transformed infrared and results were compared with cure cycle employed for autoclave curing. Optimum hold time for Quickstep processing at upper curing temperature (180°C) was determined using DSC. The hold time of 120 min at 180°C was found to be suitable for Quickstep cure cycle, producing a panel of similar degree of cure to that achieved through autoclave processing schedule. Final degree of cure was dependent on time spent at upper cure temperature and slightly on initial steps of the cure cycle which was used to control the resin flow, fiber wetting, and void removal. Quickstep processed samples exhibited higher T_g and crosslink density and similar molecular network structure to the autoclave cured samples. POLYM. ENG. SCI., 54:887–898, 2014. © 2013 Society of Plastics Engineers     

Bisphenol-A bimodal epoxy resins. Part I: The dynamic mechanical characterization of a 6300 (340/22,500) weight average molecular weight system

By using an advanced epoxy resin of 22,500 weight average molecular weight two bimodal systems of 6300 weight average molecular weights were prepared. By altering the curing procedure normally used to cure epoxy resins and high molecular weight resins we have succeeded in minimizing the difficulty associated with preparing bimodal epoxy resin systems. The ultimate T_g of these bimodal systems is associated with the phase morphology and controlled by the curing conditions employed. For the completely phase separated bimodal system a T_g of 473 K is reported and for the partially phase separated system a T_g of 466 K is reported. Equations were developed for predicting the equilibrium shear modulus of these bimodal systems. Theoretical predictions based on these equations were found to be consistent with experimental results.     

Addition‐cure‐type phenolic resin based on alder‐ene reaction: Synthesis and laminate composite properties

A maleimide‐functional phenolic resin was reactively blended with an allyl‐functional novolac in varying proportions. The two polymers were coreacted by an addition mechanism through Alder‐ene and Wagner–Jauregg reactions to form a crosslinked network system. The cure characterization was done by differential scanning calorimetry and dynamic mechanical analysis. The system underwent a multistep curing process over a temperature range of 110–270°C. Although the cure profiles were independent of the composition, the presence of maleimide led to a reduced isothermal gel time of the blend. Increasing the allylphenol content decreased the crosslinking in the cured matrix, leading to enhanced toughness and improved resin‐dominant mechanical properties of the resultant silica laminate composites. Changing the reinforcement from silica to glass resulted in further amelioration of the resin‐reinforcement interaction, but the resin‐dominant properties of the composite remained unaltered. Increasing the maleimide content resulted in enhanced thermal stability. Integrating both the reactive groups in a single polymer and its curing led to enhanced thermal stability and T_g, but to decreased mechanical properties of the laminate composites. This can be attributed to a brittle matrix resulting from enhanced crosslinking facilitated by interaction of the reactive groups located on the polymer of an identical backbone structure. The cured polymers showed a T_g in the range of 170–190°C. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 737–749, 2001     

Investigation of cure kinetics in epoxy/multiwalled carbon nanotube nanocomposites

With the increased interest in thermoset resin nanocomposites, it is important to understand the effects of the material on nanoscale characteristics. In this study, a curing reaction of an epoxy resin, which contained 0.25, 0.50, or 1.00 wt % of multiwalled carbon nanotubes (MWCNTs), at different heating rates was monitored by differential scanning calorimetry; cure kinetics were also evaluated to establish a relationship between crosslinking (network formation) and mechanical properties. MWCNT concentrations above 0.25 wt % favored crosslinking formation and decreased the activation energy (E_a) in the curing reaction. Examination of the kinetic mechanism suggests that the MWCNT locally restricted the spatial volume and favored the formation of nodular morphology in the resin, especially for high MWCNT concentrations. The MWCNT exhibited some entanglement in the matrix, which hindered a more pronounced effect on the mechanical properties. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39857.     

Influence of the Stoichiometric Ratio on the Curing Kinetics and Mechanical Properties of Epoxy Resin Cured with a Rosin-Based Anhydride

Bio-based alternatives for petroleum-based epoxy resin curing agents, such as maleopimaric acid (MPA), are indispensable for sustainable fiber reinforced polymer composites with thermosetting matrices. However, previous investigations disregarded the importance of choosing the right stoichiometric ratio R between the anhydride groups in the rosin-based curing agent and the epoxy groups in the resin. Therefore, the influence of R on the curing kinetics and mechanical properties of an epoxy resin cured with a rosin-based anhydride is studied. Here, Fourier-transform infrared spectroscopy (FT–IR) indicates that for R ⩾ 0.9 unreacted anhydride groups are present in the thermoset. Consequently, the network density decreases and the glass transition temperature T_g drops by about 40 °C. On the other hand, the steric hindrance of unreacted functional groups for R ⩾ 0.9, increases the flexural modulus and the reduced network density improves fracture toughness. The results indicate that the best R for overall high mechanical performance and good processability is preferably low (R ⩽ 0.7). Here, a low R results in a high T_g and good processability due to a low viscosity. However, the latency of the mixtures is low and therefore, the mixtures are not fit for processing via prepreg technology.     

The influence of precure dilation on the stress–strain properties of ethylene–propylene terpolymer networks

A study has been made of the influence of a dilating liquid, present during vulcanization, on the stress–strain behavior of EPT vulcanizates. Stress–strain measurements performed on the vulcanizates after extraction of the dilating liquid, taken over a range of strain rates, indicate the effective absence of time-dependent behavior and suggest that a close approach to equilibrium has been achieved. From the experimental data, values of the C₁ and C₂ constants of the empirical Mooney-Rivlin equation were derived. It was found that both C₁ and C₂ decreased with increased precure dilation, C₂ decreasing more rapidly than C₁. The observed decrease in C₁ is less than would be predicted by simple analogy with the Gaussian modulus; it is suggested that this difference might be explained by changes in network configuration and topology associated with the precure dilation.     

Effect of curing method on mechanical and morphological properties of carbon fiber epoxy composites for solid rocket motor

Microwave (MW) curing and conventional thermal curing techniques were utilized to cure carbon fiber epoxy composites for solid rocket motor to investigate the effect of curing method on their mechanical and morphological properties. In this work, tensile and inplane shear strength properties together with morphological properties were compared between MW cured and thermally cured composites, and the mechanism for MW curing was analyzed. The study shows that 83% cure cycle time reduction is achieved through MW curing. Mechanism analysis for MW curing indicates the resin at the surface layer and interior parts of the composites is cured with different forms. Temperature monitoring during MW processing indicates the uneven electric field distribution in the domestic MW oven. Fourier transform infrared spectrum measurements reveal that MWs do not initiate any new chemical reactions during the curing process of the composites. Thermal analysis using differential scanning calorimeter reveals higher glass transition temperature (T_g) of MW cured composites compared with thermally cured counterparts. Moreover, the MW cured composites show 17% lower tensile strength than thermally cured composites, whereas a 3% increase of the inplane shear strength is observed for MW cured composites, which is also confirmed via scanning electron microscope by means of better coating the fibers with resin, increased fiber wetting and less fiber pullout. POLYM. COMPOS., 36:1703–1711, 2015. © 2014 Society of Plastics Engineers     

Gelation and fusion of vinyl plastisols

The gelation of vinyl plastisols at constant temperature has been found to follow the equation ln [(C ? C_e)/(U ? C_e)] = (? π²/a²)D_τ + ln (8/π²), where C is the resin phase concentration, C_e the equilibrium resin phase concentration, U the critical resin phase concentration, a the average particle size, D the diffusion constant, and τ the time required for the onsent of gelation. A light reflectance apparatus capable of measuring the gelation process is described. The effect that various resin–plasticizer parameters have on the gelation and fusion process is discussed. The light-reflectance apparatus is also useful for estimating various resin and formulating parameters.     

Synthesis and properties of urethane elastomer-modified epoxy resin having hydroxymethyl group

Synthesis and properties of urethane elastomer-modified epoxy resins were studied. The urethane elastomer-modified epoxy resins were synthesized by the reaction of a 4-cresol type epoxy compound having hydroxymethyl groups (EPCDA) with isocyanate prepolymer. The structure was identified by IR, ¹H NMR and GPC. These epoxy resins (EPCDATDI) were mixed with a commercial epoxy resin (DGEBA) in various ratios. The mixed epoxy resins were cured with a mixture of 4,4′-diaminodiphenylmethane and 3-phenylenediamine (molar ratio 6:4) as a hardener. The curing behaviour of these epoxy resins was studied by DSC. The higher the concentration of EPCDATDI, the higher the onset temperature and the smaller the rate constant (k) of the exothermic cure reaction were. It was considered that the ratio of hydroxymethyl group to epoxide group was very small and the molecular weight of EPCDATDI was large. Therefore, the accelerating effect of the hydroxymethyl group on the epoxide–amine reaction was cancelled by the retardant effect of increased molecular weight and viscosity, and decreased molecular motion. Toughness was estimated by Izod impact strength and fracture toughness (K_1C). On addition of 10 wt% EPCDATDI with low molecular weight (M?_n 6710, estimated by GPC using polystyrene standard samples), Izod impact strength and K_1C increased by 70% and 60%, respectively, compared with unmodified epoxy resin. Glass transition temperatures (T_g) for the cured epoxy resins mixed with EPCDATDI measured by dynamic mechanical spectrometry were the same as those of unmodified epoxy resin. The storage modulus (E′) at room temperature decreased with increasing concentration of EPCDATDI. Toughness and dynamic mechnical behaviour of cured epoxy resin systems were studied based on the morphology.     

Enhanced film forming ability of benzoxazine–urethane hybrid polymer network by sequential cure method

Uniform copolymer films of benzoxazine resin (BA‐a) and urethane prepolymer (PU) were prepared at various BA‐a/PU mass ratios (100/0, 80/20, 60/40, 40/60, 20/80, and 0/100) via sequential cure method comprising of moisture cure and thermal cure steps. In the moisture cure step, Fourier Transform Infrared (FT‐IR) spectra revealed the network formation between NCO‐terminated group and moisture to firstly produce PU solid film. Then in the thermal cure step, the change of tri‐substituted benzene ring to tetra‐substituted benzene ring was observed suggesting polybenzoxazine network formation in this step. Moreover, the spectra reveal that isocyanate groups in polyurethane structure could react with phenolic hydroxyl groups of BA‐a to form biuret and allophanate groups. Dynamic mechanical analysis (DMA) confirms a synergistic behavior in glass transition temperature (T_g) of the alloys with the highest T_g value of 275°C which is uniquely observed in these alloys obtained from traditionally thermal cure method. The proposed sequential cure method above is found to be highly useful for uniform coating or film casting process which lacks in traditional, low A‐stage viscosity, benzoxazine resin. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40502.     

The effect of curing of unsaturated polyester resin on the dynamic relaxation time

The effect of hot curing of unsaturated polyester resin on the dynamic relaxation time was studied using dielectric measurements along with two dynamic mechanical measurement methods. It was found that the dynamic response during cure was a material frequency dependent property and did not depend on the measurement method. All relaxation times, measured during cure, by all three measurement methods used, converged to a single equation: τ(t)_av=at^b where t= curing time, a, b=constants. The increase of the relaxation time during cure followed the same trend as a friction factor, which was found to increase with conversion. The crosslinking density was found to increase slowly with conversion, while the relaxation time increased exponentially. These two different modes of behavior during cure explain the high resolution of dynamic measurements as a cure monitoring tool, which can easily detect small curing changes. This behavior of the relaxation time was explained by the sharp rise of activation energy due to a parallel decrease of free volume at high conversion.     

The effect of resin chemistry on the curing behavior and chemorheology of unsaturated polyester resins

The effect of the structure of unsaturated polyester resin on its curing and rheological behavior during isothermal cure has been investigated, using three different grades of resin. In the investigation, the structure of the resins was determined, using nuclear magnetic resonance spectrometry (NMR), together with chemical analysis. Both a differential scanning calorimeter (DSC) and an infrared (IR) spectrometer were used to determine the curing kinetics, and a cone-and-plate rheometer was used to determine the variation of rheological properties during isothermal cure. On the basis of the experimental study, we have concluded: (1) at the same styrene-to-fumarate mole ratio, the resin having isophthalates cures slower than the one having none; (2) everything else being equal, the resin having a high styrene-to-fumarate mole ratio cures faster than the resin having a low one; (3) the higher the concentration of initiator, the faster a resin cures. It has been found that a resin that cures faster does not necessarily achieve a higher final degree of cure than one that cures slowly. We have found that a mechanistic kinetic model developed in our previous investigation is very useful for investigating the reactivity of unsaturated polyester resin, by determining the rate constant and activation energy of the propagation reaction. On the basis of rheological investigation, we have concluded that both t_η∞ determined from steady shearing flow measurement and t_{tan δ = 1} determined from oscillatory shearing flow measurement may be used as a measure of gel time.     

The curing of UF resins studied by low‐resolution 1H‐NMR

A series of UF resins and one MUF resin were studied by low‐resolution ¹H‐NMR. The mobility of the resin during curing could be followed by measuring the spin‐spin relaxation time (T₂) with curing time. The relative curing behavior was similar to that found by traditional gel time measurements. In addition, extra features in the T₂ plots with curing time showed at what point the bulk of the condensation reactions took place. The speed of cure was also related to the chemical groups in the liquid resin, and it was found that the linear methylol groups were mainly responsible for the curing speed of the resins. By studying the curing with different hardener levels and glue concentrations it was found that a UF resin is more sensitive to the glue mix concentration than an MUF resin. A cured resin was also studied after curing to investigate postcuring effects. Water seemed to play the biggest role in the postcure, with substantial amounts present immediately after cure, which decreased with curing time and aging. For the low mol ratio resins studied here further curing reactions did not seem to play a major role in the post curing phenomenon. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 754–765, 2000     

Curing kinetics and mechanical properties of fast curing epoxy resins with isophorone diamine and N-(3-aminopropyl)-imidazole

Fast curing epoxy resins were prepared by the reactions of diglycidyl ether of bisphenol A with isophorone diamine (IPD) and N-(3-aminopropyl)-imidazole (API), and their curing kinetics and mechanical properties influenced by IPD content were also investigated. The analysis of curing kinetics was based on the nonisothermal differential scanning calorimetry (DSC) data with the typical Kissinger, Ozawa, and Flynn–Wall–Ozawa models, respectively. The glass-transition temperature was also measured by the same technique. Additionally, the mechanical properties including flexural, impact, and tensile performances were tested, and the curing time was estimated by isothermal DSC. The degree of cure (α) dependency of activation energy (E_a ) revealed the complexity of curing reaction. Detailed analysis of the curing kinetics at the molecular level indicated that the dependence of E_a on the α was a combined effect of addition reaction, autocatalytic reaction, viscosity, and steric hindrance. From the nonisothermal curves, the curing reaction mechanism could be proposed according to the increasingly obvious low temperature peaks generated by the addition reaction of epoxy group with the primary amines in API and IPD molecules. Using the preferred resin formulation, the resin system could be cured within 10 min at 120 °C with a relatively good mechanical performance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47950.     

Water vapor transport in an epoxy resin based on TGMDA and DICY

Water uptake has been measured in an epoxy resin based on tetraglycidylmethylenedianiline curved with dicyanidamide. The curing behavior of this system as elucidated by differential scanning calorimetry and Fourier transform infrared is complex. Based upon this information we selected curing temperatures and times in addition to the “standard” cure. The kinetics of the sorption of water by the materials which have undergone the standard cure indicate that the two modes of sorption are involved at high humidity and only a single mode at lower humidity (as seen by changes in the slope of the log M_t vs log t plots). The kinetics of the sorption in the resins which have undergone post cure at higher temperatures also indicate two or more modes of sorption at high humidities. However the slopes of the log M_t vs log t plots differ from those for the resin with standard cure. Subsequent sorption/desorption cycles on the standard cure resin showed marked increases in the initial sorption rate as well as changes in mode, suggesting that irreversible changes in the resin had occurred.     

Effect of NBR on epoxy/glass prepregs properties

Solid acrylonitrile‐butadiene rubber (NBR) was used in epoxy resin for toughening and also for increasing the tack of epoxy/glass prepregs. The NBR used in this study was a rubber with 33% acrylonitrile content. The changes in thermal and mechanical properties such as glass transition temperature (T_g), curing characteristics and lap‐shear strength have been studied. For this purpose, three types of prepregs with two levels of NBR content of 3 and 5%, were prepared. Prepregs were made by solvent type impregnation apparatus. In this method, resin impregnates satin textile glass fiber under the controlled and constant condition of line speed and oven temperature. Prepregs were B‐staged for about 3%. The cure characterization, T_g and flow behavior were evaluated using differential scanning calorimetry and rheological analysis. Results showed that increasing the rubber content caused the following effects: (a) delay in gel time of prepregs, (b) increase in activation energy of prepregs, and (c) decrease in total heat of curing reaction. It is interesting that NBR increased the tack of epoxy/glass prepreg but, had no effect on its resin flow behavior. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Curing characteristics of urea–formaldehyde resin in the presence of various amounts of wood extracts and catalysts

The characteristics of urea–formaldehyde (UF) resin curing in the presence of wood extracts and a catalyst [ammonium chloride (NH₄Cl)] were investigated by differential scanning calorimetry (DSC). The effects of extracts from 16 wood species on resin curing behaviors were evaluated. A model developed in this study, T_p = 53.296 exp(?9.72C) + 93.104, could be used to predict the resin curing rate in terms of the DSC peak temperature (T_p) as influenced by the NH₄Cl content (C). The results indicated that the curing rate of UF resin increased as the catalyst content increased and reached a maximum when the catalyst content ranged from 0.5 to 1.0% (solid basis over liquid UF resin weight). Further increases in the catalyst content had no effect on the resin curing rate. The curing rates of UF resin in the presence of wood extracts increased with decreased pH values or increased base buffer capacities. It was also discovered that the activation energy could not fully explain the resin curing behavior when some species of wood extracts were present, and therefore, the pre‐exponential factor had to be taken into account. The concept of the equivalent catalyst content (ECC) of wood extracts to the NH₄Cl content was introduced in this study; ECCs ranged from 0.0022 to 0.0331% among the 16 wood species. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008