Modification of a two‐component system by introducing an epoxy‐reactive diluent: Construction of a time–temperature–transformation (TTT) diagram

Curing reactions of a three‐component system consisting of an epoxy resin diglycidyl ether of bisphenol A (DGEBA n = 0), 1,2‐diaminecyclohexane as curing agent, and vinylcyclohexene dioxide as a reactive diluent were studied to calculate a time–temperature–transformation isothermal cure diagram for this system. Differential scanning calorimetry (DSC) was used to calculate the vitrification times. DSC data show a one‐to‐one relationship between T_g and fractional conversion α, independent of cure temperature. As a consequence, T_g can be used as a measure of conversion. The activation energy for the polymerization overall reaction was calculated from the gel times obtained using the solubility test (58.5 ± 1.3 kJ/mol). This value was similar to the results obtained for other similar epoxy systems. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1190–1198, 2004     

Chitin derivatives. II. Time–temperature–transformation cure diagrams of the chitosan amidization process

The transformation of the salts of chitosan with acetic and propionic acid, chitosonium acetate and chitosonium propionate, into chitin or the respective homolog of amidized chitosan has been described on the basis of time–temperature–transformation (TTT) cure diagrams. The time to vitrification at various isothermal cure temperatures (T_c) was determined using dynamic mechanical thermal analysis. The time to full cure was derived using a T_g–T_c cure time relationship according to the method of Peng and Gillham, as well as by an extrapolation procedure. Consequently, TTT cure diagrams describing the temperature-driven regeneration process include full cure and vitrification curves. As in thermosets, this transformation displays an S-shaped vitrification curve, and the time to full cure increases with decreasing cure temperature. The time to full cure is very remote from the time to vitrification, and this is attributed to the tendency of vitrification to prevent full cure from being attained. The activation energies for vitrification of chitosonium acetate and chitosonium propionate derived from an Arrhenius equation are similar. This suggests that the same mechanism governs glass formation in the N-acetyl and N-propionyl-glucosamine derivatives. Additionally, the morphology of amidized chitosan and native chitin was examined using X-ray diffraction and FTIR analysis. X-ray diffraction results indicate that amidized chitosan is an amorphous material, whereas native chitin is crystalline. FTIR suggests the existence of hydrogen-bonded amide groups in native chitin but not in amidized chitosan. This difference in morphology between amidized chitosan and native chitin is accounted for in terms of the influence of glass formation in the former. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1879–1889, 1999     

New thermosets obtained by cationic copolymerization of DGEBA with γ‐caprolactone with improvement in the shrinkage. II. Time–temperature–transformation (TTT) cure diagram

Mixtures of diglycidylether of bisphenol A (DGEBA) with different proportions of γ‐caprolactone (γ‐CL) were cured with ytterbium triflate as initiator. The curing was studied with differential scanning calorimetry (DSC) and thermo mechanical analysis (TMA). The results are presented in the form of a time–temperature–transformation diagram. The kinetic analysis was performed by means of the isoconversional integral procedure and the kinetic model was also determined using the Coats–Redfern method. Gelation was determined by means of combined experiences of DSC and TMA. The relationship between the glass transition temperature (T_g) and the degree of conversion α was determined by DSC. Using the isoconversional lines and the T_g‐α relationship, the vitrificacion curve was obtained. The methodology developed makes it possible to obtain the TTT diagram using only no‐isothermal experiments with equivalent results to those using classical isothermal procedures. The addition of γ‐CL accelerates the curing and reduces the shrinkage after gelation and consequently the internal stresses in the material. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

New soybean oil–styrene–divinylbenzene thermosetting copolymers. VI. Time–temperature–transformation cure diagram and the effect of curing conditions on the thermoset properties

A new class of thermosetting resins has been developed that is based on the cationic copolymerization of regular soybean oil (SOY), low saturation soybean oil (LSS), or conjugated LSS (CLS) with various alkene comonomers initiated by boron trifluoride diethyl etherate (BFE) or related modified initiators. The activation energy for the gelation process for these thermosets ranges from 95 to 122 kJ/mol. A time‐temperature‐transformation (TTT) isothermal cure diagram has been established for the model system LSS45–ST32–DVB15–(NFO5–BFE3) ie 45 wt% low saturation soybean oil, 32 wt% styrene, 15 wt% divinylbenzene, and 5 wt% Norway fish oil ethyl ester plus 3 wt% boron trifluoride diethyl etherate. The effect of curing conditions on the thermophysical and mechanical properties, including the mechanical damping and shape memory properties, has been subsequently investigated using this model thermoset. These findings allow the efficient optimization of desired properties for specific applications. © 2003 Society of Chemical Industry     

In situ formation and compounding of polyamide 12 by reactive extrusion

The anionic polymerization of lauryllactam was initiated at 270°C using sodium hydride as an initiator and N,N′‐ethylene‐bisstearamide (EBS) as an activator (NaH:EBS molar ratio of 2). Polymerization occurred in less than 2 min and was successfully performed in an internal mixer and a twin‐screw extruder with corotating intermeshing screws (Werner & Pfleiderer ZSK 25). The content of residual monomer, as determined by thermogravimetric analysis, was lower than 0.5 wt %. Molecular weight, as measured by size exclusion chromatography, was governed by the lauryllactam:NaH molar ratio calculated on a M_n of 25 kg/mol at a constant NaH:EBS molar ratio of 2. Blends were prepared in situ by polymerization of lauryllactam solutions of various polymers. When poly(ethylene‐co‐butylacrylate) (Lotryl®; Atofina) was dissolved in lauryllactam, rubber‐toughened polyamide 12 blends were obtained. Mechanical properties of the injection‐molded polymers were examined by stress–strain as well as notched Charpy impact tests at different temperatures. Blend morphologies were imaged by scanning electron microscopy (SEM). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 344–351, 2003     

Isothermal Cure of an Epoxy System Containing Tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM), a Multifunctional Novolac Glycidyl Ether and 4,4′-Diaminodiphenylsulphone (DDS): Vitrification and Gelation

Times to gelation and vitrification have been determined at different isothermal curing temperatures between 200 and 240°C for an epoxy/amine system containing both tetraglycidyl-4,4′-diaminodiphenylmethane (TGDDM) and a multifunctional Novolac glycidyl ether with 4,4′-diaminodiphenylsulphone (DDS). The mixture was rich in epoxy, with an amine/epoxide ratio of 0·64. Gelation occurred around 44% conversion. Vitrification was determined from data curves of glass transition temperature, T_g, versus curing time obtained from differential scanning calorimetry experiments. The minimum and maximum values T_g determined for this epoxy system were T_g0=12°C and T_gmax=242°C. Values of activation energy for the cure reaction were obtained from T_g versus time shift factors, a_T, and gel time measurements. These values were, respectively, 76·2kJmol^-1 and 61·0kJmol^-1. The isothermal time–temperature–transformation (TTT) diagram for this system has been established. Vitrification and gelation curves cross at a cure temperature of 102°C, which corresponds to glass transition temperature of the gel. © of SCI.     

Time–temperature–transformation (TTT) cure diagram: Modeling the cure behavior of thermosets

The times to gelation and to vitrification for the isothermal cure of an amine-cured epoxy (Epon 828/PACM-20) have been measured on macroscopic and molecular levels by dynamic mechanical spectrometry (torsional braid analysis and Rheometrics dynamic spectrometer), infrared spectroscopy, and gel fraction experiments. The relationships between the extents of conversion at gelation and at vitrification and the isothermal cure temperature form the basis of a theoretical model of the time–temperature–transformation (TTT) cure diagram, in which the times to gelation and to vitrification during isothermal cure versus temperature are predicted. The model demonstrates that the “S” shape of the vitrification curve depends on the reaction kinetics, as well as on the physical parameters of the system, i.e., the glass transition temperatures of the uncured resin (T_g0), the fully cured resin (T_g∞), and the gel (_gelT_g). The bulk viscosity of a reactive system prior to gelation and/or vitrification is also described.     

Master curve and time–temperature–transformation cure diagram of a polyfunctional epoxy acrylic resin

The curing reaction of a well‐defined glycidyl methacrylate‐co‐butyl acrylate statistical copolymer, prepared by atom transfer radical polymerization, and a commercial linear diamine (Jeffamine D‐230) was studied with the objectives of constructing and discussing a time–temperature–transformation isothermal curing for this system. Thermal and rheological analyses were used to obtain the gelation and vitrification times. Differential scanning calorimetry data showed a one‐to‐one relationship between the glass‐transition temperature (T_g) and fractional conversion independent of the cure temperature. As a result, T_g was used as a measurement of conversion. We obtained a kinetically controlled master curve for isothermal curing temperatures from 50 to 100°C by shifting T_g versus the natural logarithm time data to a reference temperature of 80°C. We calculated the apparent activation energy by applying two different methods, gel time measurements versus shift factors, suggesting a good agreement between them. Isoconversion contours were calculated by the numerical integration of the kinetic model. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Master curve and time–temperature–transformation cure diagram of lignin–phenolic and phenolic resol resins

The aim of this work is to generate both a master curve of resol resins based on the time–temperature superposition principle and their TTT cure diagrams. The samples used for this purpose were lignin–phenolic and phenol–formaldehyde resol resins. A TMA technique was employed to study the gelation of resol resins. In addition, a DSC technique was employed to determine the kinetic parameters through the Ozawa method, which allowed us to obtain isoconversional curves from the data fit to the Arrhenius expression. Establishing the relationship between the glass‐transition temperature and curing degree allowed the determination of the vitrification lines of the resol resins. Thus, using the experimental data obtained by TMA and DSC, we generated a TTT cure diagram for each of resins studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3362–3369, 2007     

Mechanical behavior of tetrafunctional/phenol novolac epoxy mixtures cured with a diamine

An amine‐cured epoxy system based on tetraglycidyldiaminodiphenylmethane and a novolac glycidyl ether resin was studied. Epoxies were prepared by varying the cure schedules and using the isothermal time–temperature–transformation diagram of the system. The materials were characterized using dynamic‐mechanical analysis (DMA), tensile stress–strain tests over a range of temperatures and testing speeds, impact, and hardness tests. Optical microscopy was used to study the fracture surfaces of the samples. Some interrelations between the behavior and the microstructure of the system are discussed. In addition, the effect of thermal aging on the mechanical properties has been studied. DMA analysis seemed to reveal a structure that tended to be less heterogeneous with increasing the crosslink density. The advance in the etherification reactions or the thermal aging has reduced the mechanical properties related with the consumption of energy to break. The optimal cure schedule according to the global properties has been established. The morphology of fractured surfaces by optical microscopy showed a clear correlation with the variation of the tensile properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2305–2313, 2000     

Structure–property relations of nylon‐6 and polytetramethylene glycol based multiblock copolymers with microphase separation prepared through reactive processing

A series of poly(urethane‐urea‐amide) thermoplastic elastomers (PUUAs) based on polytetrahydrofuran (polytetramethylene glycol, PTMG), nylon‐6 and 4,4′‐diphenylmethane diisocyanate were synthesized through reactive processing. This method solved the incompatibility of nylon‐6 and PTMG, and these model elastomers were used to gain insight into the structure–property relations of block polymers. The target products were solvent resistant, transparent and melting‐processable. Fourier transform infrared spectroscopy, XRD, DSC, TEM, dynamic mechanical analysis, tensile testing and TGA were used to study the structure, crystallization, morphology, mechanical properties and thermostability of the PUUAs. The Fourier transform infrared results proved the successful preparation of PUUAs from nylon‐6 and PTMG. TEM examination showed that all samples exhibit microphase separated morphology with the nylon‐6 domain dispersed in the PTMG phase. The results of tensile testing indicated that the elastomers exhibit excellent mechanical properties with stress at break and strain at break exceeding 40 MPa and 600% respectively. The TGA results implied that the PUUAs can be fabricated by transitional processing at proper temperature without any thermodegradation. These favorable features were related to the microphase separated structure of the PUUAs. © 2016 Society of Chemical Industry     

Investigation on particular morphology of immiscible polyamide 12/polystyrene blends

In this article, a particular phase morphology of immiscible polyamide 12/polystyrene (PA12/PS) blends prepared via in situ anionic ring-opening polymerization of Laurolactam (LL) in the presence of PS was investigated. SEM and FTIR were used to analyze the morphology of the blends. The results showed that PS is dispersed as small droplets in the continuous matrix of PA12 when PS content is less than 5 wt %. When the PS content is higher than 10 wt %, two particular phase morphologies appeared. First, dispersed PS-rich particles with the spherical inclusions of PA12 can be found when PS content is between 10 wt % and 15 wt %. Then, the phase inversion (the phase morphology of the PA12/PS blends changes from the PS dispersed/PA12 matrix to PA12 dispersed/PS matrix system) occurred when PS content is higher than 20 wt %, which is completely different from traditional polymer blends prepared by melt blending. The possible reason for the particular morphology development was illuminated through phase inversion mechanism. Furthermore, the stability of the phase morphologies of the PA12/PS blends was also investigated. SEM showed that the particular morphology is instability, and it will be changed upon annealing at 230°C for 30 min. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A study on the cure characteristics of epoxy/diaminodiphenylmethane system prepared at room temperature

The curing behavior and kinetics of epoxy resin with diaminodiphenylmethane (DDM) as the curing agent was studied by many researchers, however all of them prepared the system at a high‐temperature condition (i.e., T ≥ 80°C). In this study, a mixture of epoxy/DDM was prepared at ambient temperature and its curing characteristics were studied by using differential scanning calorimetry (DSC). The autocatalytic model was used to calculate the kinetic factors in the dynamic experiments. The kinetics of the curing reaction was also evaluated by two different isoconversional models; namely Friedman method and the Advanced Isoconversional method proposed by Vyazovkin to investigate the activation energy behavior during the curing reaction. The activation energy of the curing reaction was found to be in the range of 48 ± 2 kJ/mol and might be considered to be constant during the curing. In fact, our findings were different from the result reported by other researchers for the system which was prepared at elevated temperature. Therefore, it seems that the preparation temperature of the samples influenced considerably on the curing behavior of epoxy with DDM. Finally, a time–temperature–transformation (TTT) diagram was established to determine the cure process and glass transition properties of the system. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thermal polymerization of thiol–ene network‐forming systems

The thermal polymerization of a tetrafunctional thiol (PETMP) and divinyl ether (TEGDVE) was monitored by temperature‐ramping differential scanning calorimetry (DSC) and the effects of inhibitor type and concentration, oxygen inhibition and initiator type were studied. The incorporation of inhibitors was required to produce a stable system at room temperature. Butylated hydroxytoluene (BHT) inhibited polymerization at low temperatures, but was inefficient at high temperatures and polymerization rates, and hence BHT is an ideal stabilizer. In contrast, a nitroxide inhibitor (NO‐67) was a very effective inhibitor and no polymerization occurred until all of the nitroxide was depleted. The presence of oxygen retarded the onset of polymerization but did not change the final conversion significantly. Polymerization with initiators having higher half‐life temperatures shifted the DSC peak to higher temperature because the rate of initiator decomposition and thus initiation was slower. Rheological investigations of the cure at different temperatures revealed that the gel time decreased significantly with increasing cure temperature, and the calculated apparent activation energy for PETMP/TEGDVE was 54 kJ mol^?1. Dynamical mechanical thermal analysis of the cured material was undertaken and frequency‐superposed results revealed that the glass transition region of PETMP/TEGDVE/azobisisobutyronitrile was much narrower than that of free‐radically cured dimethacrylate, but was similar to that of an epoxy resin cured with an aromatic diamine. This behaviour could be attributed to PETMP/TEGDVE network homogeneity, or to the less constrained crosslinks in the PETMP/TEGDVE network. Copyright © 2007 Society of Chemical Industry     

Preparation and properties of core–shell nanosilica/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) latex

A core–shell nanosilica (nano‐SiO₂)/fluorinated acrylic copolymer latex, where nano‐SiO₂ served as the core and a copolymer of butyl acrylate, methyl methacrylate, and 2,2,2‐trifluoroethyl methacrylate (TFEMA) served as the shell, was synthesized in this study by seed emulsion polymerization. The compatibility between the core and shell was enhanced by the introduction of vinyl trimethoxysilane on the surface of nano‐SiO₂. The morphology and particle size of the nano‐SiO₂/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) [P(MMA–BA–TFEMA)] core–shell latex were characterized by transmission electron microscopy. The properties and surface energy of films formed by the nano‐SiO₂/P(MMA–BA–TFEMA) latex were analyzed by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, and static contact angle measurement. The analyzed results indicate that the nano‐SiO₂/P(MMA–BA–TFEMA) latex presented uniform spherical core–shell particles about 45 nm in diameter. Favorable characteristics in the latex film and the lowest surface energy were obtained with 30 wt % TFEMA; this was due to the optimal migration of fluorine to the surface during film formation. The mechanical properties of the films were significantly improved by 1.0–1.5 wt % modified nano‐SiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Time–temperature–transformation cure diagrams of phenol–formaldehyde and lignin–phenol–formaldehyde novolac resins

In this study, the time–temperature– transformation (TTT) cure diagrams of the curing processes of several novolac resins were determined. Each diagram corresponded to a mixture of commercial phenol–formaldehyde novolac, lignin–phenol–formaldehyde novolac, and methylolated lignin–phenol–formaldehyde novolac resins with hexamethylenetetramine as a curing agent. Thermomechanical analysis and differential scanning calorimetry techniques were applied to study the resin gelation and the kinetics of the curing process to obtain the isoconversional curves. The temperature at which the material gelled and vitrified [the glass‐transition temperature at the gel point (_gelT_g)], the glass‐transition temperature of the uncured material (without crosslinking; T_g0), and the glass‐transition temperature with full crosslinking were also obtained. On the basis of the measured of conversion degree at gelation, the approximate glass‐transition temperature/conversion relationship, and the thermokinetic results of the curing process of the resins, TTT cure diagrams of the novolac samples were constructed. The TTT diagrams showed that the lignin–novolac and methylolated lignin–novolac resins presented lower T_g0 and _gelT_g values than the commercial resin. The TTT diagram is a suitable tool for understanding novolac resin behavior during the isothermal curing process. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Stress relaxation of woodfiber–thermoplastic composites

Woodfiber–polypropylene and woodfiber–waste polyethylene composites have been produced by injection molding and by hot pressing the thermoplastic between woodfiber mats. The stress relaxation under constant strain in these composites has been studied at 25, 50, and 80°C. The results have been compared with similar experiments performed on neat thermoplastics. It is interesting to note that the presence of woodfibers as reinforcement in the composites restricts the stress relaxation, but their effectiveness decrease with the increase in ambient temperature. Composites made by hot pressing the woodfiber mat and the thermoplastic are found to exhibit a lesser amount of relaxation than those made by injection molding the same combination. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 401–407, 2006     

Synthesis of core–shell type microsphere with reactive seed microspheres

Monodispersed poly(methyl methacrylate) (PMMA) particles (seed microspheres) were synthesized with the living radical initiators, tetramethylthiuram disulfide, or p-xylene dimethyldithiocarbamate by suspension polymerization in water media with and without divinyl benzene as a crosslinker. Monodispersed spherical microspheres with PMMA core–polyacrylamide shells were synthesized by UV irradiation to the seed microsphere–acrylamide aqueous solution. The content and the molecular weight of the polyacrylamide shell chain were controlled by changing the acrylamide feed and irradiation time of the UV light. The microspheres became dispersible to water after the UV irradiation. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 211–216, 1998     

Melt processing of polyamide 12 and cellulose nanocrystals nanocomposites

The fabrication of nanocomposites of polyamide 12 (PA12) and cellulose nanocrystals (CNCs) isolated from cotton and tunicates is reported. Through a comparative study that involved solution‐cast (SC) and melt‐processed materials, it was shown that PA12/CNC nanocomposites can be prepared in a process that appears to be readily scalable to an industrial level. The results demonstrate that CNCs isolated from the biomass by phosphoric acid hydrolysis display both a sufficiently high thermal stability to permit melt processing with PA12, and a high compatibility with this polymer to allow the formation of nanocomposites in which the CNCs are well dispersed. Thus, PA12/CNC nanocomposites prepared by melt‐mixing the two components in a co‐rotating roller blade mixer and subsequent compression molding display mechanical properties that are comparable to those of SC reference materials. Young's modulus and maximum stress could be doubled in comparison to the neat PA12 by introduction of 10% (CNCs from tunicates) or 15% w/w (CNCs from cotton) CNCs. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42752.     

增容剂对动态硫化氯化丁基橡胶/尼龙12热塑性弹性体性能的影响

分别以聚丙烯接枝马来酸酐( PP -g - MAH)、苯乙烯-乙烯-丁二烯-苯乙烯共聚物接枝马来酸酐(SEBS-g- MAH)以及新型改性剂苯乙烯-共轭二烯烃嵌段共聚物选择加氢物(SEPS)作为增容剂,考察了不同增容剂对动态硫化氯化丁基橡胶/尼龙12热塑性弹性体(PA 12/CIIR TPV)物理机械性能的影响,并研...