Stress relaxation behavior of starch powder‐epoxy resin composites

The purpose of the present study is to investigate the quasi‐static and the viscoelastic behavior of epoxy resin reinforced with starch powder. An increase in the elastic modulus on the order of 42% was achieved; a behavior that was predicted by the modulus prediction model (MPM). Next, the composite was subjected to flexural relaxation experiments, in order to determine the relaxation modulus, at different filler‐weight fractions and flexural deflections imposed. The viscoelastic models of the standard linear solid, the power law model and the residual property model (RPM) were applied in order to simulate/predict the stress relaxation curves. Predicted values derived from the application of the above models were compared to each‐other as well as to respective experimental findings. From the above comparison it was proved the superiority of the RPM model in predicting both the linear and the nonlinear viscoelastic response of the materials investigated. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41697.     

A polypropylene/high density polyethylene blend compatibilized with an ethylene‐propylene‐diene monomer block copolymer: Fitting dynamic rheological data by emulsion models with a physical scheme

The dynamic rheological behaviors at 210, 230, and 250 °C are measured by small amplitude oscillatory shear on a rotational rheometer for a polypropylene(PP)/ ethylene‐propylene‐diene monomer(EPDM) block copolymer/ high density polyethylene (HDPE)/blend. The scanning electron microscope (SEM) photomicrographs show the blend has a droplet/matrix, semi‐co‐continuous, co‐continuous morphology respectively at different weight ratios. The Cole–Cole (G″ vs. G′) data of the blends can be fitted by the simplified Palierne's model only for very narrow weight ratios. A physical scheme is proposed that the dispersed droplets are enclosed by EPDM, thus an equivalent dispersed phase is made up of “expanded” EPDM. With this physical scheme the G″ vs. G′ data of the HDPE‐rich blends at 210 °C can be fitted well by Palierne's model. Also with the physical scheme the G″ vs. G′ data of the PP‐rich blends at three temperatures can be fitted well by G–M's model with G* of interface equals to zero. This means the proposed physical scheme is reasonable. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43709.     

Rheological properties of neat epoxy exposed to in‐service aerospace contaminants

We present an experimental study on the rheological properties of a commonly used epoxy resin system (EPIKOTE‐862 resin and EPIKURE‐W curing agent), exposed to a variety of fluids typical of aerospace operations (jet fuel, hydraulic fluids, deicing, detergents, etc.), for a period of up to 6 months, at room temperature for most conditions, and with no concurrent mechanical loading or prior degradation. The specimens were subjected to stress and frequency sweeps with a shear rheometer, while a limited set received also a temperature sweep in a range consistent with aircraft operations. Results indicate that the treated resin samples are linear viscoelastic under these testing conditions. The resin has reasonable chemical resistance to most contaminants of this study, with the exception of two commonly used detergents: an aircraft surface cleaning compound, Penair C5572, and a nonionic detergent, Methyl Ethyl Ketone (MEK). The durability change of the first compound appears triggered by high temperatures only, while the second compound causes a very drastic stiffness loss under several conditions. This drop of performance occurs within a 3‐months period, with no apparent color change or fracture that could prompt visual inspection and repair. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3961–3971, 2013     

A method based on the time–temperature superposition principle to predict pressurization time in compression molding

The quality of epoxy composites reinforced by glass fibers and manufactured by compression molding is affected by the pressurization time. Traditional methods, including differential scanning calorimetry and dynamic thermomechanical analysis, cannot be reliably used to predict pressurization time in the scenario of continuous production and inconstant circumstances seen in industry. In this paper, the rheological behaviors of epoxy under constant temperature were investigated and analyzed to verify if the time–temperature superposition (TTS) principle, which defines the relation between time and temperature in the deformation and relaxation response of a viscoelastic material, could be suitably applied to describe them. The results show that the TTS principle could indeed be used to predict resin viscosity by the horizontal shift factor. A new method based on the TTS principle and written into a program to forecast pressurization time in compression molding is proposed. The uniform surface color and the qualified thickness of the composite components using the program indicate that the program works well and that this method is feasible for predicting pressurization time during compression molding. The results of tensile and short‐beam shear strength tests show that pressurization time affects the mechanical properties of the final product. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45308.     

The nonlinear stress relaxation behavior after a step shear of star-shaped styrene-butadiene rubber filled with precipitated silica: Experiment and simulation

The nonlinear stress relaxation behavior after a step shear strain of star-shaped SSBR/silica compounds containing 21 vol% filler of various surface areas was measured and simulated using constitutive equations. A styrene-butadiene rubber (SBR) gum and SBR filled with silica having BET surface areas of 55, 135, 160, and 195 m²/g were used. Relaxation modulus behavior of the filled compounds was found to be dependent on surface area. Specifically, stress relaxation tests indicated that an increase in surface area led to increase in values of relaxation moduli in both the linear and nonlinear regimes. The time-dependent relaxation modulus exhibited a plateau at long times of relaxation in compounds containing silica of high surface area. Additionally, good time-strain superpositions were achieved for all samples at intermediate times of relaxation, and the strain-dependent damping function decreased with filler surface area. The constitutive equations proposed by Leonov and Simhambhatla and Leonov, modified to include multimodal relaxation of the particle network, were used to predict the time evolution of the relaxation modulus in the nonlinear regime for all samples. The simulations provided good results for the SBR gum for all tested strain levels. Also, in the compounds filled with silica, both models satisfactorily described the experimental observation in the nonlinear regime at low strain levels. However, at higher strain levels, due to a possible slip effect, the simulations overpredicted measured values of the relaxation moduli, thus leading to only qualitative predictions of the observed behavior. It is also possible that neither model accurately captured the floc rupture kinetics of these complex rubber compounds.     

Curing of phenol‐formaldehyde resin mixed with wood preservatives

The effects of preservatives used for glue‐line treatment on the curing of phenol‐formaldehyde resin (PF) were studied by dynamic mechanical analysis and differential scanning calorimetry. Storage modulus, G′, loss modulus, G″, and loss tangent, tan δ, of PF with and without preservatives were recorded as a function of time under isothermal heating. The time required for G′, G″, and tan δ to reach steady values increased with addition of preservative. The G′, G″, and tan δ curves of PF containing benzyl alcohol (used in the preservative as a diluent) were almost identical to those of PF containing preservative. However, the addition of antitermite and anti‐fungal compounds alone had no effect on the curing process. There were no differences in total reaction enthalpy or dependence of activation energy on degree of conversion between pure PF and mixtures. Our results indicate that benzyl alcohol in preservatives plasticizes the curing system for PF. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Acrylic‐based epoxy resin damping systems: Synthesis,characterization, and properties

Acrylate‐based epoxy resin (AE)/low molecular weight polyamine (LPA) composites were developed. The chemical structure, curing behavior, fracture morphology, damping properties, and mechanical properties were evaluated by Fourier transform infrared (FTIR), ¹H‐nuclear magnetic resonance (¹H‐NMR), gel permeation chromatography (GPC), Differential scanning calorimeter (DSC), scanning electron microscope (SEM), Dynamic mechanical thermal analysis (DMTA), and electro mechanical machine. Transmission electron microscope (TEM) and SEM pictures exhibited nanoscale micro‐phase separation between epoxy and acrylic segmers. DMTA results indicated that the loss factor of cured AE/LPA system could reach 1.84 and temperature range of tan δ > 0.5 was about 84 °C. Tensile strength and elongation at break of the cured AE samples can reach 6.5 MPa and 185%, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43654.     

Numerical and experimental investigations on polymer melt flow phenomenon in a vario‐thermal mold cavity

Mold temperature is one of the key factors affecting the morphology and quality of plastic parts. This article explores the melt flow phenomena in a vario‐thermal mold cavity. A coupled numerical method, considering the conjugate heat transfer between the mold and melt, is developed for the melt flow simulation. Mold temperature variations and melt flow phenomena for short shot injection in an electrical heated mold cavity are numerically studied and verified by experiments. The results indicate that the melt flow length and cavity filling ratio increase significantly with the elongation of the preheating time before injection. Melt filling ratio increased nearly linearly with the increasing of electric heating time. The smaller the injection pressure is, the bigger the relative filling ratio increment is. Therefore, polymer melt can flow much longer or the mold cavity can be filled up with a smaller injection pressure when the cavity is preheated. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45193.     

Probing the viscoelastic moduli of thin,soft films with a quartz crystal resonator

Coating biomaterials with thin, soft films can alter properties, such as the biocompatibility of the materials, whereas it remains a great challenge to probe the properties of such films. In this article, we show a method that allows for the determination of the viscoelastic moduli of thin, soft films deposited on the surface of a quartz crystal through the measurement of resonance frequency shifts and the broadening of the acoustic resonance of the crystal as a resonator. The method is based on transcendental equations, which describe the mechanical response of the quartz resonator with the deposited films. It differs from the currently widely used ones, which use a thin film approximation numerically through the solution of transcendental equations to determine the viscoelasticity of the films. We estimated the glass‐transition temperature of a thin poly(vinyl butyral) film by measuring the change in the viscoelastic moduli of the film with increasing temperature, and the results agree well with the temperature obtained from other techniques. The method was not constrained to the range of the elastic moduli of the film, except where the acoustic film resonance occurred, and thus, could be applied to the study of a wide variety of thin, soft layers under different conditions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44532.     

Neural network modeling of the preparation process of a siloxane‐organic polyazomethine

Although apparently simple, the polycondensation reaction leading to polyazomethine is difficult to control because of its equilibrium character, the conversion degree being influenced by a series of parameters. The reaction between a siloxanediamine, 1,3‐bis(3‐aminopropyl)tetramethyldisiloxane, and terephthalaldehyde was performed here in solution (in tetrahydrofuran) without by‐products removal and in absence of any catalyst or pH modifier. Different conditions (co‐monomers ratio, dilution, and temperature), considered as input parameters for the process modeling, were varied according to a pre‐established experimental program. The viscosity of the reaction mixture was chosen as output parameter, being monitored with a Haake Viscotester 7 Plus‐L. The process modeling was performed using a hybrid combination of artificial neural networks and differential evolution algorithm, the last one having the role of developing the neural model in an optimal form. The simulation results showed that the methodology provides accurate results, the model predictions being in close correlation with the experimental data. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42552.     

Viscoelastic properties of polyaniline–emeraldine base nanostructured films: Experimental results and molecular dynamics simulations

Comprehensive exploration of the viscoelastic properties of polyaniline–emeraldine base (PANI–EB) nanostructured films is presented from two viewpoints of experimental study associated with dynamic mechanical thermal analysis and thermogravimetric measurements and of computational simulations by molecular dynamics (MD) approach. The results are expressed in storage and loss modulus components (E′ and E″). The role of drying temperature, time, and residual solvent content were studied on the E′ and E″ of prepared PANI–EB films. Using the principle of time–temperature superposition, E′ and E″ at different temperatures and frequencies can be plotted on master curves. The relationship between the modulus components with the solvation level of PANI–EB film is also studied. MD simulation is applied to study the viscoelasticity of simulated PANI structures with different monomeric aniline chains. The temperature dependence of viscoelastic properties provides good information for fractional free volume, cavity size distribution, and activation energy of PANI structures. Simulation outcomes provide a fairly good compatibility with the experimental results. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41858.     

The Cole–Cole plot for cure: The cure and reversion of natural rubber

Cure rheometry is routinely used in the rubber industry for processability assessment and cure‐time determination. This article examines these rheological outputs in Cole–Cole format to explore what new insights can be gained from this alternative data plot. It differs from the conventional Cole–Cole treatment in its application to a reacting system. The plots described here are therefore of G″(t) vs. G′(t). Initially some attention is directed to the basics of the Cole–Cole treatment and the likely features to be expected when applied to systems undergoing both cure and reversion. This article goes on to consider examples of both by studying a natural rubber vulcanization at temperatures of 160 °C and above. Through the Cole–Cole approach, it is thought possible to identify the competition between intermolecular and intramolecular sulfurization, and between crosslink and main‐chain scission. The approach offers considerable potential to expand the capabilities of cure rheometry. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44085.     

Quantitative relation between the relaxation time and the strain rate for polymeric solids under quasi‐static conditions

Relaxation time is an essential physical quantity reflecting the hysteresis of the microstructure of materials. To associate the relaxation time with the strain rate, the stress–strain curves of six types of polymers at low strain rate were normalized, and a nondimensional generalized Maxwell model incorporating strain‐rate‐dependent relaxation times was obtained by the internal variable theory of irreversible thermodynamics. The results indicate that the constitutive equation may capture well the normalized stress–strain behaviors that are not related to the strain rate. The ratio of the initial modulus to the secant modulus at the maximum stress was also found to not rely on the strain rate anymore. Furthermore, strain‐rate independence occurred only when the relaxation time was proportional to the time interval for stress from zero to the maximum stress. The relaxation time varied in a power law with the strain rate. The explicit relation is helpful for providing a concise and promising solution for predicting the quasi‐static mechanical response of viscoelastic solids. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44114.     

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

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

Gelation mechanism and rheological properties of polyacrylamide crosslinking with polyethyleneimine and its plugging performance in air‐foam displacement

Gels based on polyacrylamide crosslinking with polyethyleneimine have attracted attention because of their resulting high strength and good thermal stability. This study investigated the gelation mechanism of the polymeric gel and its plugging performance in air‐foam flooding. An optic microrheology analyzer was used to monitor the gelation process. The crosslinking reaction occurred in two steps, as determined from the elasticity factor curves, and the polymeric gels adopted a semisolid state from solution, as determined from the solid liquid balance curves. The elastic modulus values were higher than the viscous modulus values, indicating that mature gels were elastic‐based materials. The yield stress increased gradually with increasing polymer dosage, which was consistent with the breakthrough pressure and the trend of displacement pressure. The mature gels showed significant thixotropy. In the core displacement test, the preferred injection volume of the gel was 0.1 pore volume, and the stable pressure of the foam flooding was increased by about three times after the core was plugged. The blocking effect for cores with small original permeability was better than that with large permeability. The best blocking resulted from simultaneous treatment of both ends of the cores, followed by front‐end treatment and rear‐end treatment. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45778.     

Nanoclay dispersion into a thermosetting binder using sonication and intensive mixing methods

Suspensions of epoxy with 10% by weight of organomodified montmorillonite clay [Cloisite 30B], prepared by two different methods, viz. intensive batch mixing and sonication, were investigated. The characterization of linear viscoelastic material functions of the suspension using small‐amplitude oscillatory shear during processing enabled the assessments of the dispersion capabilities of the two mixing methods. Thermal imaging was used to monitor the temperature distributions generated during mixing. Sonication was determined to be more effective in the dispersion of the clay into the epoxy resin than the intensive batch mixing process, as revealed by the significant increase of the dynamic properties upon sonication, which suggested that some degree of intercalation and exfoliation had taken place during sonication. The use of the linear viscoelastic material functions thus provided a relatively easy to implement method for the analysis of the dispersion effectiveness of the different processing methods and operating conditions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Numerical simulation on residual wall thickness of tubes with dimensional transitions and curved sections in water‐assisted injection molding

Residual wall thickness is an important indicator which aims at measuring the quality of water‐assisted injection molding (WAIM) parts. The changes of residual wall thickness around dimensional transitions and curved sections are particularly significant. Free interface of the water/melt two‐phase was tracked by volume of fluid (VOF) method. Computational fluid dynamics (CFD) method was used to simulate the residual wall thickness, and the results corresponded with that of experiments. The results showed that the penetration of water at the long straight sections was steady, and the distribution of the residual wall thickness was uniform. However, there was melt accumulation phenomenon at the dimensional transitions, and the distribution of the residual wall thickness wasn't uniform. Adding fillet at the dimensional transitions could improve the uniformity of the residual wall thickness distribution, and effectively reduce water fingering. Additionally, at the curved sections, the residual wall thickness of the outer wall was always greater than that of the inner wall, and the fluctuations of the residual wall thickness difference were small. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structure and properties of a low viscosity acrylate based flexible epoxy resin

A series of low viscosity acrylate‐based epoxy resin (AE)/glycol diglycidyl ether (GDE) systems were prepared. The effect of GDE and low molecular weight polyamide (LPA) content on the rheological behavior, phase structure, damping, and mechanical properties were studied by differential scanning calorimeter (DSC), viscometer, scanning electron microscopy (SEM), dynamic mechanical thermal analysis (DMTA), and electro mechanical machine. The viscosity of the uncured AE systems decreased significantly after the incorporation of GDE. The damping properties were found to decrease slightly with the increasing GDE and LPA content. The tensile strength of the cured AE/GDE samples enhanced significantly after the incorporation of GDE with at least 150% improvement for all the samples while it decreased slightly with increasing LPA content. The AE/GDE cured systems were intended for future use as structural damping materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42959.     

Curing kinetics of a “green” thiol‐containing resin: Oligo(ethylene‐2‐mercaptosuccinate)

This work focuses on examining the curing process of neat oligo(ethylene‐2‐mercaptosuccinate) using differential scanning calorimetry (DSC), rheology, and Fourier transform infrared (FTIR) spectroscopy. The thiol‐containing resin offers much promise as a bioabsorbable polymer in medical field and as a reusable thermoset in sustainable applications. Although curing between thiol groups has been investigated in solutions, studies of neat materials without solvent are rare. Here, the evolution of glass transition temperature (T_g), complex shear modulus (G*), gelation, and chemical structure are monitored as a function of isothermal curing time and temperature. Both T_g and G* increase with curing, indicating the formation of polymer networks. The conversion of the cure is determined from the DiBenedetto equation and is found to follow a second‐order plus second‐order autocatalytic reaction model. Importantly, the intensity of the S–H bond absorption decreases with the extent of curing, which confirms the curing mechanism, i.e., disulfide formation between the thiol groups. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43205.