Comparison of thermal techniques for glass transition measurements of polystyrene and cross-linked acrylic polyurethane films

There are few quantitative comparisons in the literature between glass transitions (T_g) measured by differential scanning calorimetry (DSC) and by dynamic mechanical analysis (DMA). Also, in the case of DMA, two different operational definitions have been used to obtain the glass transition, namely, the loss modulus (E″) and damping (tan δ) peak temperatures. We propose a new DMA definition of T_g and demonstrate that it agrees with DSC T_g measurements within ±2°C for both thermoplastic polystyrene and thermoset cross-linked acrylic polyurethane films with measurable tan δ peaks. The glass transitions for a single polystyrene standard and several cross-linked acrylic polyurethane films were measured by DSC. Additionally, E″ and tan δ peak temperatures were measured by DMA as a function of frequency and temperature. Empirically, it was determined that the average of the E″ and tan δ peak temperatures measured at 1 rad/s oscillation frequency corresponds to the glass transition measured by the ASTM E1356 DSC test method. © 1994 John Wiley & Sons, Inc.     

Block copolyetheresters. V. Low-temperature properties of thermotropic block copolyetheresters

The low-temperature properties of block copolyetheresters with hard segments of poly(alkylene p,p′-bibenzoate) and soft segments of poly(tetramethylene ether) were investigated by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). In the temperature range of −100 to 60°C, two transition temperatures, a glass transition temperature (T_g) and a melting temperature (T_m), were found by DSC and are attributed to the polyether segments. The T_g monitored by DSC of the polyether segments of the block copolyetheresters is around −68°C and independent of the composition and the type of polyester segment. Thus, the amorphous parts of the polyether segments should be immiscible with the amorphous parts of the polyester segments. The polyether segments of the block copolyetheresters exhibit a lower T_m and a lower crystallinity than those of the poly(tetramethylene ether)glycol due to the presence of the polyester segments. The crystallizability of the polyether segments is dependent on the composition to some extent. The DMA data show that the dynamic modulus drops more abruptly around −10 to 15°C, indicating that the mechanical properties may change significantly due to the melting of the polyether segments. © 1996 John Wiley & Sons, Inc.     

Deeper insights into the thermal properties of epoxy thermoset resins using torsion measurements

The glass transition temperature (T_g) of epoxy thermosets is a critical material property that depends on the component chemistry, the final cross-link density, and processing conditions. This study incorporates dynamic mechanical analysis (DMA) testing with a torsion clamp geometry on a TA Instruments DHR-2 and differential scanning calorimetry (DSC) to characterize five different two-component epoxy-amine systems. Investigation of the T_g dependence on DMA frequency and heating shows that lowering the frequency from 1 to 0.01 Hz results in a T_g very similar to that measured using DSC, while a heating rate of 0.3°C/min using DMA gives a T_g comparable to the DSC measured value at 30°C/min. The DMA technique reveals secondary relaxation transitions and peak broadening in the tan(δ) plots of poorly mixed epoxy blends, quantified using full width at half maximum (FWHM) of tan(δ) peaks, and are indicative of a non-homogeneous cross-linked network and off-ratio blending, respectively. The increase in the FWHM due to poor mixing ranges from 8% to 96%. These parameters are easily measurable and quantifiable in DMA, but are not observed in DSC. The additional DMA insights are valuable for process development and failure analysis, and can improve the understanding of epoxies.     

Anomalies,influencing factors,and guidelines for DMA testing of fiber reinforced composites

This study systematically assessed the measurement of dynamic properties of a range of fiber reinforced composite materials using dynamic mechanical analysis (DMA) instrument. The discrepancy in the moduli from DMA to ASTM tests was investigated. The study showed that proper specimen preparation, maintaining appropriate aspect ratio (span to thickness ratio) to reduce the transverse shear deformation, and sufficient loading are critical to measure correct properties from DMA test. The guidelines on aspect ratio and loading for plastics to high-modulus carbon fiber composites are presented as a design chart and equations, respectively. The study also found that the glass transition temperature (T_g) was independent of specimen aspect ratio and T_g is lower for multidirectional composites when compared with its unidirectional composites. The particle interleaved T800H/3900-2 composite showed two glass transition temperatures (140 and 198°C), the lower value is due to the effect of interleaving by thermoplastic particles, and the higher value is the T_g of its base matrix. This lowering of T_g would have significant effect on the application temperature of the material. This phenomenon was not observed here to fore in the literature. POLYM. COMPOS., 2009. © 2009 Society of Plastics Engineers     

Glass transition temperatures of hydrocarbon blends: Adhesives measured by differential scanning calorimetry and dynamic mechanical analysis

A comparison of calculated and measured glass transition temperatures of a series of three‐component hydrocarbon blends was performed. The blends were prepared as mixtures of an elastomer with different proportions of tackifying resin and oil. Glass transition temperature, T_g, was measured by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) at four measurement frequencies. Most of these blends had pressure‐sensitive adhesive (PSA) properties, and were used to prepare a series of PSA tapes. The adhesion of the PSA tapes was shown to be strongly dependent on T_g. Tack of PSA tapes was measured at two different temperatures, and shown to be directly correlated to the blend T_g. Several predictive methods for blend T_g that are based on individual component T_gs were evaluated. The prediction of blend T_g is far more accurate if the individual component T_g values are determined by DMA instead of DSC. In addition, the Gordon‐Taylor equation gave a significant improvement on predicted blend T_g when compared to the Fox equation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 826–832, 2000     

Thermal analysis of styrene–alkyl methacrylate polymers. I. Glass transition temperatures

The glass transition temperatures (T_g's) of several polystyrenes and styrene–alkyl methacrylate copolymers and terpolymers were measured using thermomechanical analysis (TMA) and differential scanning calorimetry (DSC). The polymers studied had number-average molecular weights from 3000 to 250,000 g/mole. The results indicate that the composition dependence of the T_g's for the copolymers and terpolymers can be satisfactorily described by a general Fox equation. In general, the measured T_g's of the copolymer and terpolymer samples depend more on the steric effects of the constituent pendent groups than on their molecular weights. The chain flexibility rather than the size of the pendent group is the determining factor in the glass transition properties of the styrene polymers.     

Characterization of epoxies cured with bimodal blends of polyetheramines

DGEBA was cured with bimodal blends of polyetheramines as well as with single molecular weight amines while maintaining stoichiometry. Glass transition temperatures (T_gs) and moduli were measured using dynamic mechanical analysis (DMA). Fracture properties were measured using the compact tension geometry and testing was performed at both ambient and non‐ambient temperatures, investigating toughness changes as a function of temperature. For constant amine average molecular weights, the addition of high molecular weight amines caused increased glassy moduli at a constant T ? T_g and decreased densities while broadening the glass transition without changing the fracture toughness. The fracture behavior, specifically the slip‐stick to brittle transition, was affected by the broadened transitions. T_g, breadth of T_g, and total damping were found to be proportional to the volume fraction of amine in the system. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1621–1631, 2013     

Super-crosslinked ionic liquid-intercalated montmorillonite/epoxy nanocomposites: Cure kinetics,viscoelastic behavior and thermal degradation mechanism

Super-crosslinked epoxy nanocomposites containing N-octadecyl-N′-octadecyl imidazolium iodide (IM)-functionalized montmorillonite (MMT-IM) nanoplatelets were developed and examined for cure kinetics, viscoelastic behavior and thermal degradation kinetics. The structure and morphology of MMT-IM were characterized by FTIR, XRD, TEM, and TGA. Synthesized MMT-IM revealed synergistic effects on the network formation, the glass transition temperature (T_g) and thermal stability of epoxy. Cure and viscoelastic behaviors of epoxy nanocomposites containing 0.1 wt% MMT and MMT-IM were compared based on DSC and DMA, respectively. Activation energy profile as a function of the extent of cure was obtained. DMA results indicated a strong interface between imidazole groups of MMT-IM and epoxy, which caused a significant improvement in storage modulus and the T_g of epoxy. Network degradation kinetics of epoxy containing 0.5, 2.0, and 5.0 wt% MMT and MMT-IM were compared by using Friedman, Kissinger-Akahira-Sunose (KAS), Flynn-Wall-Ozawa (FWO) and the modified Coats-Redfern methods. Although addition of MMT to epoxy was detrimental to the T_g value, as featured by a fall from 94.1°C to 89.7°C detected by DMA method, and from 103.3°C to 97.9°C by DSC method, respectively. By contrast, meaningful increase in such values were observed in the same order from 94.1°C to 94.7°C and from 103.3°C to 104.7°C for super-crosslinked epoxy/MMT-IM systems.     

Investigation on the interpenetrating polymer networks (ipns) of polyvinyl alcohol and poly(N-vinyl pyrrolidone) hydrogel and its in vitro bioassessment

Poly(vinyl alcohol) (PVA) and poly(N-vinyl pyrrolidone) (PVP) composite hydrogel with interpenetrating polymer networks (IPNs) was prepared by in situ polymerization and compared with pure PVA hydrogel. The prepared IPN hydrogel was characterized by infrared spectroscopy (IR), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. The mechanical property and cell culture were also tested. The results show that PVP can chemically bond with PVA and form uniform blend hydrogel. The content of PVP can affect the structure, crystallinity, glass transition temperature (T_g), and mechanical property of the hydrogel. The T_g of the PVA hydrogel is 2.7°C while the T_g of the IPN hydrogel is −37°C. The IPN hydrogel has lower glass transition temperature, corresponding to better elastic properties, and has better mechanical performance on stretch and compression than PVA hydrogel. The crystallinity (X_c) of PVA hydrogel and IPN hydrogel is 65.3 and 26.3%, respectively. The DMA curves and XPS analysis suggest that PVA and PVP are well miscible on a molecular level in the IPN hydrogel. The cell proliferation trend demonstrates that the addition of PVP has a positive influence on the cell growth and the IPN hydrogel may be used as a promising biomaterial for artificial cartilage substitute. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A relationship between the glass transition temperature (Tg) and fractional conversion for thermosetting systems

An equation, based on thermodynamic considerations to relate the glass transition temperature, T_g, to compositional variation of a polymer system, is adapted in this article for modeling the T_g vs. fractional conversion (x) relationship of reactive thermosetting systems. Agreement between the adapted equation and experimental T_g vs. x data is found for several thermosetting crosslinking systems (i.e., epoxies and cyanate ester/polycyanurate) as well as for reactive thermosetting linear polymer systems (i.e., polyamic acid and esters to polyimides). The equation models the experimentally obtained T_g vs. x behavior of thermosetting systems which include competing reactions. Agreement for widely varying molecular structures demonstrates the generality of the equation. The entire T_g vs. x relationship can be predicted for a thermosetting material by using the T_g vs. x equation and the values of the initial glass transition temperature, T_g0, the fully reacted system glass transition temperature, T_g∞, and the ratio of the change in specific heat from the liquid or rubbery state to the glassy state (Δc_p) at T_g0 and T_g∞, Δc_p∞/Δc_p0. The values of T_g0, T_g∞, and Δc_p∞/Δc_p0 can be measured generally from two differential scanning calorimetric experiments. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 3–14, 1997     

Studies on the thermal properties of poly(phenylene sulfide amide)

Thermal properties of poly(phenylene sulfide amide) (PPSA) prepared using sodium sulfide, sulfur, and thiourea as sulfur sources which reacted with dichlorobenzamide (DCBA) and alkali in polar organic solvent at the atmospheric pressure, were studied. The glass transition temperature (T_g), melting point temperature (T_m), and melting enthalpy (ΔH_m) of the related polymers were obtained by use of differential scanning calorimetry analysis. The results are: T_g = 103.4–104.5°C, T_m = 291.5–304.7°C, and ΔH_m = 104.4–115.4 J/g. Thermal properties such as thermal decomposition temperature and decomposition kinetics were investigated by thermogravimetric analysis under nitrogen. The initial and maximum rate temperatures of degradation were found to be 401.5–411.7°C and 437–477°C, respectively. The parameters of thermal decomposition kinetics of PPSAs were worked out to be: activation energy of degradation was 135 to 148 kJ/mol and the 60-s half-life temperature was 360 to 371°C. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1227–1230, 1997     

Polyester hot-melt adhesives. I. Factors affecting adhesion to epoxy resin coatings

The peel strength and tensile shear strength of polyester hot-melt adhesives on metals coated with epoxy resins are affected by four characteristics of the polyester: (1) inherent viscosity, (2) glass transition temperature (T_g), (3) degree of crystallinity, and (4) melting point. The inherent viscosity affects the strength, toughness, and crystallinity of the adhesive. The T_g and degree of crystallinity affect the low-temperature adhesive properties; the peel strength is relatively low when the T_g is appreciably above the use temperature. The T_g, degree of crystallinity, and melting point affect the high-temperature adhesive properties. A hot-melt adhesive with high peel and tensile shear strengths from 0° to 120°C is the polyester of 1,4-butanediol and trans-1,4-cyclohexanedicarboxylic acid.     

Properties of films obtained by UV-curing 4,4'-hexafluoroisopropylidenediphenoldihydroxyethylether diacrylate and its mixtures with the hydrogenated homologue

A new ultraviolet (UV)-curable acrylic monomer, 4,4'-hexafluoroisopropylidene-diphenoldihydroxyethylether diacrylate, was synthesized: it was cured as a film and its properties compared with those of its fully hydrogenated homologue. The introduction of two CF₃groups into the monomer did not change its reactivity in the UV-curing reaction, but increased the glass transition temperature (T_g) of the cured polymeric film, decreased its refractive index (n), and lowered its surface tension. The fluorinated and the hydrogenated monomers were completely miscible and give homogeneous films: the T_g and n values were found linearly dependent on the fluorinated monomer content. The surface properties were deeply influenced by the presence of fluorine; a surface enrichment of the fluorinated monomer was evidenced by X-ray photoelectron spectroscopy analyses on the surfaces of the films obtained from mixtures of the two monomers. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 979–983, 1997     

Characterization of N,N-dimethylacrylamide/2-methoxyethylacrylate copolymers and phase behaviour of their thermotropic aqueous solutions

Dimethylacrylamide (DMA) has been copolymerized with 2-methoxyethylacrylate (MOEA) and solutions of the products were analysed by FTIR to yield derived reactivity ratios r_DMA = 1.11 ± 0.13 and r_MOEA = 0.63 + 0.10. The measured glass transition temperatures T_g of PDMA and PMOEA were 395 K, and 242 K, respectively. These and the values of T_g for the copolymers accorded well with the Fox relationship. Cloud point curves for copolymers in water were established over a wide range of concentration, solubility decreasing with increase in temperature. For these reversibly thermotropic solutions, the lower critical solution temperature (LCST) increased from 9°C to 80°C with decrease in content of MOEA in the copolymer from 91.1 mol% to 38.6 mol%.     

Preparation and characterization of polyethylene–clay nanocomposites by using chlorosilane‐modified clay

Clay was modified by trimethylchlorosilane; after modification, hydroxyl groups at the edge of layers were reacted and CEC value was drastically decreased. Polyethylene–clay composites were prepared by melt compounding. Wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) showed that intercalated nanocomposites were formed using organoclay ion‐exchanged from chlorosilane‐modified clay, but conventional composites formed using organoclay directly ion‐exchanged from crude clay. Dynamic mechanical analysis (DMA) of PE and PE–clay composites was conducted; the results demonstrated that nanocomposites were more effective than conventional composites in reinforcement and addition of organoclay resulted in the increase of glass transition temperature (T_g), but crude clay had no effect on T_g of PE–clay composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 676–680, 2004     

Effects of polycaprolactone molecular weights on thermal and mechanical properties of polybenzoxazine

Polymer blends of polybenzoxazine (PBA‐a) and polycaprolactone (PCL) of different molecular weights (M_n = 10,000, 45,000, and 80,000 Da) were prepared at various PBA‐a/PCL mass ratios and their properties were characterized. The results from dynamic mechanical analyzer (DMA) revealed two glass transition temperatures implying phase separation of the two polymers in the studied range of the PCL contents. Moreover, a synergistic behavior in glass transition temperature (T_g) was evidently observed in these blends with a maximum T_g value of 281°C compared with the T_g value of 169°C of the PBA‐a and about ?50°C of the PCL used. The blends with higher M_n of PCL tended to provide greater T_g value than those with lower M_n of PCL. The modulus and hardness values of PBA‐a were decreased while the elongation at break and area under the stress?strain curve were increased with an increase of the content and M_n of PCL, suggesting an enhancement of toughness of the PBA‐a. Scanning electron micrographs (SEM) of the sample fracture surface are also used to confirm the improvement in toughness of the blends. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41915.     

Direct measurement of the carbon dioxide-induced glass transition depression in a family of substituted polycarbonates

We present a method for the direct measurement of the glass transition temperature of compressed gas–polymer systems. The technique utilizes a Setaram C80D microcalorimeter equipped with high-pressure cells. Pressurizing the cells and running in scanning mode allows direct determination of the glass transition temperature. To validate the method, T_g measurements of the CO₂–poly(methyl methacrylate) system as a function of gas phase pressure were made. The results compare favorably with literature values. However, the effects of foaming appear to interfere with T_g measurement at the highest gas pressures. The CO₂-induced T_g depression of a series of polycarbonates was also measured. The magnitude of the T_g depression increases with decreasing glass transition temperature, reflecting an increase in intrinsic chain mobility, as evidenced by the glass transition temperature. The data correlate well with the Chow model. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1441–1449, 1998     

Studies of the stability of thermoplastic-modified bismaleimide resin

The stability of bismaleimide—o,o′-diallyl bisphenol A (BMI—DABA) blends modified with high-performance amorphous thermoplastic bisphenol A polysulfone (PSF), polyether ketone (PEK-C), and polyether sulfone (PES-C) bearing a phthalidylidene group has been studied by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). The extent of stability of thermoplastic components has been compared with the area of the endothermic peak that appears within the glass transition region for thermoplastic component in cured blends aged at temperature below the glass transition temperature (T_g). The stability of thermoplastic can be improved by the formation of semi-interpenetrating polymer networks (semi-IPNs). The stability of thermoplastic with higher T_g is more easily controlled. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1965–1970, 1997     

The role of network architecture on the glass transition temperature of epoxy resins

A series of epoxy networks were synthesized in which the molecular weight between crosslinks (M_c) and crosslink functionality were controlled independent of the network chain backbone composition. The glass transition temperature (T_g) of these networks was found to increase as M_c decreased. However, the rate at which T_g increased depended on crosslink functionality. The dependency of M_c on T_g is well described by two models, one based on the concept of network free volume while the other model is based on the principle of corresponding states. Initially, neither model could quantitatively predict the effect of crosslink functionality in our networks. However, our tests indicated that both the glass transition and the rubbery moduli of our networks were dependent on M_c and crosslink functionality, while the glassy state moduli were independent of these structural variables. The effect of crosslink functionality on the rubbery modulus of a network has been addressed by the front factor in rubber elasticity theory. Incorporation of this factor into the glass transition temperature models allowed for a quantitative prediction of T_g as a function of M_c and crosslink functionality. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 387–395, 1997     

Compatibility study of chlorinated polyethylene/ethylene methacrylate copolymer blends using thermal,mechanical, and chemical analysis

Blends of chlorinated polyethylene (CPE) elastomer and ethylene methacrylate copolymer (EMA) in various compositions were studied for their compatibility using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and Fourier transform infrared (FTIR) spectroscopy techniques. Irrespective of measurement techniques used, all blends showed a single glass transition temperature (T_g) lying in between the T_g of control polymers in both DSC and DMA. Glass transition temperatures of blends obtained from DSC were in consistency with Couchman–Karasz equation. Also, the T_g obtained from both DSC and DMA are above the “rule of mixing” line of the two control polymers. These results from thermal analysis clearly indicate some compatibility between the two polymers. Furthermore, compatibility of CPE/EMA blends were also been investigated by FTIR spectroscopy and scanning electron microscopic analysis. A shifting of characteristic C? Cl stretching peak of CPE and C?O stretching peak of EMA toward lower wave number indicate the presence of specific interaction between the two polymers. Mechanical properties like tensile strength, modulus at 100% elongation, elongation at break, and hardness were observed above the line of additivity drawn between the two control polymers, which corroborate compatibility between CPE and EMA. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40316.