Thermal behavior of aromatic polyamic acids and polyimides containing oxadiazole rings

Two aromatic polyimides and the corresponding poly(amic acid)s, with oxadiazole and para/meta phenoxyphenylene rings in the backbone, were synthesized and the structure — thermal properties correlation was followed by dynamic mechanical analysis. Concerning the poly(amic acid)s, the glass transition domain was emphasized only for the compound with meta-oriented rings because the process of imidization takes place with increasing temperature. A multiplex experiment was performed to calculate the activation energy of the transition localized under 200°C. Consecutive heating-cooling-heating cycles were accomplished. All phenomena are discussed by cross-examination of the storage modulus (E′), loss modulus (E″) and loss factor tanδ variation with temperature.     

Dynamic Mechanical Thermal Analysis of Polyamide 6/Biopol Blends

The temperature dependence investigated by means of DMTA of dynamic storage modulusE′, dynamic loss modulus E″ and loss tangent tgδ of blends obtained from polyamide 6 and poly(β-hydroxybutyrate-co-β-hydroxyvalerate) (Biopol D600G) indicated, that the dynamic mechanical properties of the blends containing up to 40% Biopol D600G are governed by the properties of polyamide 6. First at the 50% Biopol D600G content in the blend the transitions of the Biopol phase become visible and dominant. The shifts of the loss modulus maxima of the blends might indicate some interactions between the blend components in the amorphous phase. This revised version was published online in August 2006 with corrections to the Cover Date.     

Dynamic mechanical analysis on modified bismaleimide resins

Polyaminobismaleimides (PAMBI) with diphenyl methane, diphenyl ether and hexamethylene segments were synthesized according to Michael type addition reaction. The modification of PAMBIs with 2-glycidyl-phenyl-ether (GPE) was performed in order to ameliorate the toughness of the products. Dynamic mechanical analysis allowed the study of the processes that concur in the material through curing by tracking the storage modulus (E′) and loss factor (tanδ) changes. The small drop of E′ with increasing temperature in the glass transition region argues for crosslinked structures. The viscoelastic behavior revealed complex processes, i.e., overlapping of glass transition temperature range with intra-and inter-crosslinking.     

Thermal properties of anhydride-cured bio-based epoxy blends

Epoxidized palm oil (EPO) (0–12 wt%) was added into petrochemical-based epoxy blends (diglycidyl ether of bisphenol-A (DGEBA)/cycloaliphatic epoxide resin/epoxy novolac resin) to develop a thermal curable bio-based epoxy system. The thermal behaviors of the EPO, epoxy blends (EB), and bio-based epoxy blends (EB/EPO) were characterized using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMT) and thermo-mechanical analysis (TM). The glass transition temperature (T _g) and storage modulus (E′) of the EB/EPO system was reduced with the increasing of the EPO loading. This is attributed to the plasticizing effect of the EPO. It was found that epoxy blends with higher loading of EPO possessed higher coefficient of thermal expansion (CTE) and tanδ value. This is due to the increase of the free volume and chain flexibility in the three-dimensional network of the epoxy blends. The internal thermal stresses of the EB/EPO were decreased as the increasing loading of EPO, owing to the reduction of crosslink density, modulus of elasticity, and T _g in the epoxy blends.     

Correlations between the morphology and the thermo-mechanical properties in poly(vinyl acetate)/epoxy thermosets

The mechanical properties of poly(vinyl acetate) (PVAc)/epoxy thermosets as a function of the PVAc content were investigated through dynamic mechanical thermal analysis from −100 to 220 °C and through tensile tests at room temperature. The morphology of the thermosets was examined by scanning electron microscopy. Cured PVAc/epoxy blends are phase separated, arising two phases that correspond to a PVAc-rich phase and to the epoxy rich-phase. The morphology evolves from nodular to inverted as the PVAc content increases. Intermediate compositions present combined morphologies, in which nodular and inverted regions are detected. The tensile properties at room temperature reveal that combined morphologies present the most ductile behaviour. The glass transition temperatures (T _g) of PVAc and of epoxy phases in the blends are different from those of the neat polymers. The profile of the loss modulus (E″)–temperature curves are correlated with the change in morphology that appears increasing the PVAc content. The storage modulus (E′)–temperature curves are highly dependent on the morphology of the samples. The E′-composition dependence is predicted using several models for two-phase composites. The low-temperature β-relaxation of the epoxy is slightly modified by the presence of PVAc. The activation energies of the α and β-relaxations are not dependent on the blend morphology.     

Toughening of cyanate ester resin by carboxyl terminated nitrile rubber

The carboxyl terminated butadiene‐acrylonitrile (CTBN) rubber was used to improve the toughness of the cyanate ester (CE) resin. The toughness of the modified blends depended on the CTBN content. The addition of 10 phr (g/100gCE) CTBN in CE resin led to a 200% increase in the impact strength with a loss of storage modulus. The transmission electron microscopy result showed the existence of rubber particles, inferring that phase separation had occured after curing. The thermogravimetric analysis curve of CTBN indicated the presence of cavities which also can be observed on the fractured surface in the scanning electron microscopy pictures using high magnification. Thus, phase‐separation and cavities toughening mechanisms function together to improve the toughness. Copyright © 2004 John Wiley & Sons, Ltd.     

Determination of Activation Energy for Glass Transition of an Epoxy Adhesive Using Dynamic Mechanical Analysis

The activation energy associated with the glass transition relaxation of an epoxy system has been determined by using the three-point bending clamp provided in the recently introduced TA Instruments DMA 2980 dynamic mechanical analyzer. A mathematical expression showing the dependency of modulus measurements on the sample properties and test conditions has also been derived. The experimental results showed that the evaluation of activation energy is affected by the heating rate and test frequency, as well as the criterion by which the glass transition temperature (T _g) is established. It has been found that the activation energy based on the loss tangent (tanδ) peak is more reliable than on the loss modulus (E ₂) peak, as long as the dynamic test conditions do not cause excessive thermal lags. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermal analysis of hydrolysis and degradation of biodegradable polymer and bio-composites

The purpose of this study was to conduct a thermal analysis of the hydrolysis and degradation behavior of biodegradable polymers and bio-composites at 50°C and 90% relative humidity (RH). With increasing hydrolysis time, the thermal stability and degradation temperature of polybutylene succinate (PBS) slightly decreased. The glass transition temperature (T _g) and melting temperature (T _m) of PBS and the anti-hydrolysis agent treated PBS did not vary significantly with increasing hydrolysis time, whereas those of the trimethylolpropane triacrylate (TMPTA)-treated PBS slightly increased. With increasing hydrolysis time, the storage modulus (E’) values of the bio-composites decreased, whereas those of the TMPTA treated bio-composites slightly increased. Also, the tan values of the anti-hydrolysis agent and TMPTA treated PBS-BF bio-composites were slightly lower than those of the non-treated bio-composites, due to the reduction in their degree of hydrolysis. The tanδ_max peak temperature (T _g) of the anti-hydrolysis agent treated bio-composites was not significantly changed, whereas that of the TMPTA treated bio-composites was increased.     

Influence of carboxyl‐terminated (butadiene‐co‐acrylonitrile) loading on the mechanical and thermal properties of cured epoxy blends

A mixture of epoxy with liquid nitrile rubber, carboxyl‐terminated (butadiene‐co‐acrylonitrile) (CTBN) was cured under various temperatures. The cured resin was a two‐phase system, where spherical rubber domains were dispersed in the matrix of epoxy. The morphology development during cure was investigated by scanning electron microscope (SEM). There was slight reduction in the glass transition temperature of the epoxy matrix (T_g) on the addition of CTBN. It was observed that, for a particular CTBN content, T_g was found to be unaffected by the cure temperature. Bimodal distribution of particles was noted by SEM analysis. The increase in the size of rubber domains with CTBN content is due probably to the coalescence of the rubber particles. The mechanical properties of the cured resin were thoroughly investigated. Although there was a slight reduction in tensile strength and young's modulus, appreciable improvements in impact strength, fracture energy, and fracture toughness were observed. Addition of nitrile rubber above 20 parts per hundred parts of resin (phr) made the epoxy network more flexible. The volume fraction of dispersed rubbery phase and interfacial area were increased with the addition of more CTBN. A two‐phase morphology was further established by dynamic mechanical analysis (DMA). © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2531–2544, 2004     

Investigation on the gelation behavior of biodegradable poly(butylene succinate) during isothermal crystallization process

The early stage of polymer crystallization may be viewed as physical gelation process,i.e.,the phase transition of polymer from liquid to solid.Determination of the gel point is of significance in polymer processing.In this work,the gelation behavior of poly(butylene succinate)(PBS) at different temperatures has been investigated by rheological method.It was found that during the isothermal crystallization process of PBS,both the storage modulus(G′) and the loss modulus(G″) increase with time,and the rheological response of the system varies from viscous-dominated(G′G″),meaning the phase transition from liquid to solid.The physical gel point was determined by the intersection point of loss tangent curves measured under different frequencies.The gel time(t_c) for PBS was found to increase with increasing crystallization temperature.The relative crystallinity of PBS at the gel point is very low(2.5%-8.5%) and increases with increasing the crystallization temperature.The low crystallinity of PBS at the gel point suggests that only a few junctions are necessary to form a spanning network,indicating that the network is"loosely"connected,in another word,the critical gel is soft.Due to the elevated crystallinity at gel point under higher crystallization temperature,the gel strength S_g increases, while the relaxation exponent n decreases with increasing the crystallization temperature.These experimental results suggest that rheological method is an effective tool for verifying the gel point of biodegradable semi-crystalline polymers.     

Thermal stability and viscoelastic properties of MF/PVAc hybrid resins on the adhesion for engineered flooring in under heating system; ONDOL

The thermal properties of blends of melamine-formaldehyde (MF) resin and poly(vinyl acetate) (PVAc) for engineered flooring used on the Korean traditional ONDOL house floor heating system were investigated by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). The viscoelastic properties of the blends were also studied. Because MF resin is a thermosetting adhesive, the effect of MF rein was shown across all thermal behaviors. The addition of PVAc reduced the curing temperature. The TGA results showed that the DTG_max temperature and thermal stability of the blends increased with increasing PVAc content. The blends were examined in non-isothermal DSC experiments at a heating rate of 10 °C/min. There was an exothermic peak in all the heating scanning curves, with each blend displaying a single curing peak temperature (T_p), intermediate between those of the two pure components and varying with the blend composition. The DMTA thermogram of MF resin showed that the storage modulus (E′) increased as the temperature was further increased as a result of the cross-linking induced by the curing reaction of the resin. E′ of MF resin increased both as a function of increasing temperature and with increasing heating rate.     

Thermal and mechanical characteristics of polyurethane/curaua fiber composites

Polyurethane composites reinforced with curaua fiber at 5, 10 and 20% mass/mass proportions were prepared by using the conventional melt-mixing method. The influence of curaua fibers on the thermal behavior and polymer cohesiveness in polyurethane matrix was evaluated by dynamic mechanical thermal analysis (DMTA) and by differential scanning calorimetry (DSC). This specific interaction between the fibers and the hard segment domain was influenced by the behavior of the storage modulus E′ and the loss modulus E″ curves. The polyurethane PU80 is much stiffer and resistant than the other composites at low temperatures up to 70°C. All samples were thermoplastic and presented a rubbery plateau over a wide temperature range above the glass transition temperature and a thermoplastic flow around 170°C.     

Dielectric and optical properties of BaTiO<Subscript>3</Subscript> thin films prepared by low-temperature process

Barium titanate (BaTiO₃) thin films have been prepared by low temperature processing on Pt/Ti/SiO₂/Si substrates using sol-gel-hydrothermal (SGHT) technique, which combined the conventional sol-gel process and hydrothermal method. X-ray diffraction analysis showed that the barium titanate thin films are polycrystalline. As-reacted barium titanate films grown on Pt(111)/Ti/SiO₂/Si(100) substrates had a dielectric constant (ε) and loss tangent (tanδ) of 80 and 0.05 at 1 MHz, respectively. The optical constants including refractive index n, extinction coefficient k, and absorption coefficient α of the barium titanate thin films in the wavelength range of 2.5–12.6 μm were obtained by infrared spectroscopic ellipsometry.     

A new cerebrogalactoside from <Emphasis Type="Italic">Juglans mandshurica</Emphasis>

A new cerebrogalactoside, Juglans cerebroside A (1), together with five known compounds, quercetin-3-O-β-D-galactopyranoside (2), myricetin-3-O-β-D-galactopyranoside (3), 2″E-quercetin-3-O-β-D-(6″″-O-[3″(4′″-hydroxyphenyl) propylene acyl]) glucopyranoside (4), gallic acid (5), and 2-methyl-1-hexadecanol (6) were isolated from the leaves of Juglans mandshurica Maxim. The structures of these compounds were determined by 1D, 2D NMR, and MS techniques.     

Dynamic rheology studies of in situ polymerization process of polyacrylamide–cellulose nanocrystal composite hydrogels

A series of dynamic small-amplitude oscillatory shear experiments for in situ polymerization process of polyacrylamide–cellulose nanocrystal (PAM–CNC) nanocomposite hydrogels were performed to investigate the relationship between rheological properties and synthesis parameters including chemical cross-linker concentration, polymerization temperature, initiator concentration, and CNC aspect ratios. The results showed that CNCs accelerated the onset of gelation (t _onset) and acted as a multifunctional cross-linker during the gelation reaction. The composite hydrogels exhibited enhanced steady-state elastic modulus ( G_￥￠ ) \left( {G_\infty^\prime } \right) and plateau loss factor (tanδ) compared to these of the pure PAM hydrogels, indicating that adding CNCs not only reinforced but also toughened PAM hydrogels. ( G_￥￠ ) \left( {G_\infty^\prime } \right) and the effective network junction density (N) increased with increased cross-linker concentration, polymerization temperature, and CNC aspect ratios, but decreased with increased initiator concentration. The changes of plateau tanδ were opposite to that of G_￥￠ G_\infty^\prime . The sol–gel transition kinetics of PAM–CNC hydrogels accelerated with increased cross-linker concentration and polymerization temperature and, however, reached optimization at 0.25 wt% of initiator concentration. CNCs with lower aspect ratios promoted t _onset and the sol–gel transition of PAM–CNC hydrogels, suggesting the fact that CNCs with lower aspect ratios further facilitated the formation of network of PAM–CNC nanocomposite hydrogels.     

Studies on dynamic mechanical and mechanical properties of vinyloxyaminosilane grafted ethylene propylene diene terpolymer/linear low density polyethylene (EPDM-g-VOS/LLDPE) blends

The dynamic mechanical properties of vinyloxyaminosilane grafted ethylene propylene diene terpolymer/linear low density polyethylene (EPDM-g-VOS/LLDPE) blends have been evaluated with special reference to the effect of blend ratio. It has been found that increasing the proportion of LLDPE in the blends decreases the T_g values and increases the storage modulus (E^′) and loss modulus (E^′′) due to increase in crystallinity. A gradual increase in the values of tanδ_max is observed for the blends with increase in EPDM-g-VOS concentration, which indicates that no phase inversion occurs. But however the higher increase in tanδ_max after 50 wt.% of EPDM-g-VOS composition is due to small change in crystallinity and is ascertained by SEM micrographs. Mechanical properties such as tensile strength, Young’s modulus and hardness increase with increases in LLDPE concentration in the blends and with dicumyl peroxide (DCP) concentration whereas the values of elongation at break are decreased with increase in LLDPE and DCP concentration.     

Damping performance of Eucommia ulmoides gum

Eucommia ulmoides gum(EU gum),known as gutta percha in Southeast Asia,is a natural polymer with double characteristics of rubber and plastic.In present paper,tanδ-T curve and hysteresis loss(HL) were chosen to characterize its damping property.The results indicated that its tanδvalue would increase with rising of temperature when T>0℃and form another damping peak at 40-80℃besides T_g peak.This phenomenon resulted from meltage of crystals of EU gum could increase its damping property at ambient-high temperature.Its tanδvalue even exceeded those of conventional damping rubbers,such as nitrile-butadiene rubber(NBR) and chlorinated isobutene-isoprene rubber(CIIR).     

Thermophysical and thermoacoustical properties of benzaldehyde mixtures with ethylbenzene at 303.15, 308.15, and 313.15 K and a pressure of 0.1 MPa

Ultrasound velocity (u), density (ρ) and viscosity (η) measurements of benzaldehyde + ethylbenzene mixtures have been carried out at 303.15, 308.15, and 313.15 K. These values have been used to calculate the excess molar volume (V ^E), deviation in viscosity (δη), and deviation in isentropic compressibility (δβ_s), deviations in ultrasound velocity (δu), excess free volume (δV _f), excess intermolecular free length (δL _f) and excess Gibbs free energy of activation of viscous flow (δG ^E). McAllister’s three body interaction model is used for correlating kinematic viscosity of binary mixtures. The excess values were correlated using the Redlich-Kister polynomial equation to obtain their coefficients and standard deviations. The thermophysical properties under the study were fit to the Jouyban-Acree model. The observed variation of these parameters helps in understanding the nature of interactions in these mixtures. Further, theoretical values of the ultrasound speed were evaluated using theories and empirical relations.     

Chemical constituents from the leaves of <Emphasis Type="Italic">Cinnamomum reticulatum</Emphasis>

Reticuol, a novel Cinnamomum sesquiterpenoid, has been isolated from Cinnamomum reticulatum Hay (Lauraceae), together with eight known compounds, p-hydroxybenzoic acid, isoanwulignan, 2,6-dimethyl1,7-octadiene-3,6-diol, a-tocopheryl quinone, kaempferol-3-O-(2″,4″-di-E-p-coumaroyl)-α-L-rhamnopyranoside, kaempferol-3-O-(3″,4″-di-E-p-coumaroyl)-α-L-rhamnopyranoside, pheophorbide a, and aristophyll C. The structure of reticuol was determined on the basis of spectroscopic analysis.     

Thermal properties of microcrystalline cellulose-filled PET–PTT blend polymer composites

Polymer composite materials were prepared from poly(ethylene terephthalate)–poly(trimethylene terephthalate) blends as the matrix and different microcrystalline cellulose (MCC) filler levels (0–40 wt%) using melt compounding followed by compression molding. The composites were analyzed using dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC) and thermogravimetric analysis (TG). The DSC results indicated that there is no consistent or significant influence of the MCC addition on the glass transition (T _g), melting (T _m), and crystallization temperature of the composites. With increasing MCC content, dynamic mechanical properties improved because of the reinforcing effect of the MCC. The tan δ peak values from the DMTA were not significantly changed as the MCC content increased. TG indicated that the onset temperature of rapid thermal degradation decreased with increasing MCC content. It was also found that the thermal stability of the composites slightly decreased as the MCC content increased.