Effects of composition on the water uptake and hydroplasticisation of the glass transition temperature of methacrylate copolymers

The effects of composition on the glass transition of dry and hydroplasticised copolymers of methyl methacrylate (MMA), butyl methacrylate (BMA) and 2-hydroxypropyl methacrylate (HPMA) were studied by differential scanning calorimetry. Results from the hydroplasticisation studies showed that a high PHPMA content (>75 wt.%) was required for high water absorption and that the amount of water uptake was not linear with HPMA content but increased in an accelerating manner with increasing HPMA content. This behaviour was attributed to the increase in the hydrophilic character of the copolymer due to the strong hydroxyl-hydroxyl interactions at high PHPMA content. The T_gs of the dry copolymers were successfully predicted by all three equations used (rule of mixtures, Fox and Gordon-Taylor) but were poorly predicted for the hydroplasticised copolymers. This failure was attributed to the inadequacy of the equations in accounting for the specific interactions between the different segments of the copolymer chains. HPMA depressed the T_g of the water-saturated copolymers but enhanced the T_g of the dry system and this behaviour has particular relevance to its use in water-based latex paints.     

Glass transition investigated by a combined protocol using thermostimulated depolarization currents and differential scanning calorimetry

Relaxation times of bisphenol A polycarbonate around the glass transition temperature are estimated using the combination of differential scanning calorimetry (DSC) and thermostimulated depolarization currents (TSDC). These measurements are performed using samples with different thermal histories below and above the vitrification transformation. This protocol enables the extension of the range of equilibrium relaxation times measured by dielectric spectroscopy. By this mean we may recalculate the values of the Kauzmann temperature and fragility index.     

Note on the glass transition temperature of Poly(vinylphenol)

Critical overview of literature data on the glass transition temperature T_g of poly(4-vinylphenol) PVPh revealed a large scatter of values ranging between 53 and 194 °C, which can only partially be attributed to molecular-mass effect. The reason could be seen in residual moisture and/or solvent in samples subjected to insufficient or even no drying. Based on selected two thirds of literature data, a regression equation is proposed for the dependence of T_g on 1/M_n. Two samples of commercial PVPh (M_n 11,500; M_w 22,100) and (M_n 19,700; M_w 40,900) were studied by DSC, ATR-FTIR, and SEC methods. A procedure of preparing well defined samples is proposed: PVPh vacuum-dried at 140 °C for 24 h is dissolved in tetrahydrofuran and precipitated in hexane. The precipitate is vacuum-dried at 40 °C for 24 h, weighed into a pierced DSC pan. After final vacuum drying at 140 °C for 24 h, the sample is analyzed. The PVPh samples treated in this way showed T_g of 175.0 °C and 179.6 °C, respectively.     

Study of poly(bisphenol A carbonate) relaxation kinetics at the glass transition temperature

In this work, the variations of the relaxation times are investigated above and below the glass transition temperature of a model amorphous polymer, the polycarbonate. Three different techniques (calorimetric, dielectric and thermostimulated currents) are used to achieve this goal. The relaxation time at the glass transition temperature was determined at the temperature dependence convergence of the relaxation times calculated with dynamic dielectric spectroscopy (DDS) for the liquid state and thermostimulated depolarisation currents (TSDC) for the vitreous state. We find a value of τ(T_g) = 110 s for PC samples. The knowledge of the temperature dependence, τ(T), and the value τ(T_g) enables to determine the glass-forming liquid fragility index, m. We find m = 178 ± 5.     

Glass transition and enthalpy relaxation of ethylene glycol and its aqueous solution

Differential scanning calorimetry (DSC) and cryomicroscopy were employed to investigate the glass transition and enthalpy relaxation behaviors of ethylene glycol (EG) and its aqueous solution (50% EG) with different crystallization percent. Isothermal crystallization method was used in devitrification region to get different crystallinity after samples quenched below glass transition temperature. The DSC thermograms upon warming showed that the pure EG has a single glass transition, while the 50% EG solution has two if the solution crystallized partially. It is believed that the lower temperature transition represents the glass transition of bulk amorphous phase of EG aqueous solution glass state, while the higher one is related to ice inclusions, whose mobility is restricted by ice crystal. Cryomicroscopic observation indicated that the EG crystal has regular shape while the ice crystal in 50% EG aqueous solution glass matrix has no regular surface. Isothermal annealing experiments at temperatures lower than T_g were also conducted on these amorphous samples in DSC, and the results showed that both the two amorphous phases presented in 50% EG experience enthalpy relaxation. The relaxation process of restricted amorphous phase is more sensitive to annealing temperature.     

Effects of moisture on the glass transition temperature of polyurethane shape memory polymer filled with nano-carbon powder

One simple approach to produce electrically conductive polymers is to fill them with conductive powders. This paper investigates the effects of moisture on the glass transition temperature of a polyurethane shape memory polymer (SMP) filled with nano-carbon powders. It is found that the SMP composites before immersion in water have a slightly lower glass transition temperature, and in the mean time, the moisture fraction at the saturation point upon immersion is also lower. On the other hand, the moisture can remarkably reduce the glass transition temperature of the composites. Heating to over 180 °C is an effective way to remove the moisture, which also results in the glass transition temperature back to the original. As the glass transition temperature can be greatly reduced by moisture, a novel feature, namely, the water actutable recovery of SMP composites is also proposed based on this study.     

New evidences of glass transitions and microstructures of soy protein plasticized with glycerol

Soy protein isolate (SPI) and glycerol were mixed under mild (L series) and severe (H series) mixing conditions, respectively, and then were compression-molded at 140 degrees C and 20 MPa to prepare the sheets (SL and SH series). The glass transition behaviors and microstructures of the soy protein plasticized with glycerol were investigated carefully by using differential scanning calorimetry and small-angle X-ray scattering. The results revealed that there were two glass transitions in the SPI/glycerol systems. When the glycerol contents ranged from 25 to 40 wt.-%, all of the SL- and SH-series sheets showed two glass transition temperatures (T(g1) and T(g2)) corresponding to glycerol-rich and protein-rich domains, respectively. The T(g1) values of the sheets decreased from -28.5 to -65.2 degrees C with an increase of glycerol content from 25 to 50 wt.-%, whereas the T(g2) values were almost invariable at about 44 degrees C. The results from wide-angle X-ray diffraction and small-angle X-ray scattering indicated that both protein-rich and glycerol-rich domains existed as amorphous morphologies, and the radii of gyration (R(g)) of the protein-rich domains were around 60 nm, a result suggesting the existence of stable protein domains. The results above suggest that protein-rich domains were composed of the compact chains of protein with relatively low compatibility to glycerol and glycerol-rich domains consisted of relative loose chains that possessed good compatibility with glycerol. The significant microphase separation occurred in the SPI sheets containing more than 25 wt.-% glycerol, with a rapid decrease of the tensile strength and Young's modulus. [illustration in text].     

Effect of hydrophilicity of polymer particles on their glass transition temperatures in the emulsion state

The glass transition temperatures (Tg) of three kinds of poly(methyl methacrylate)-based copolymer emulsions having wide polymer compositions, which were prepared by emulsifier-free emulsion copolymerizations of methyl methacryalate with ethyl acrylate, n-buthyl methacrylate and methacrylic acid, were measured with a power compensation-type highly sensitive differential scanning calorimeter. The Tg values of the copolymers in their emulsion state (Tg _E) were always lower than those in their dry states (Tg _D), and the difference between Tg _E and Tg _D increased with an increase in copolymer hydrophilicities.Part CCLIII of the series Studies on Suspension and Emulsion     

Calorimetric study of the conformational relaxation times in polystyrene

The temperature dependence of the relaxation times of the structural relaxation process of polystyrene is determined by temperature-modulated differential scanning calorimetry (TMDSC) and by conventional differential scanning calorimetry (DSC) in the latter by modelling the experimental heat capacity curves measured in heating scans after different thermal histories. The good agreement between both measuring techniques in the temperature interval just above the glass-transition temperature is a guide for the interpretation of the results of the TMDSC technique in the glass-transition region. In addition, the same model applied to DSC scans is used to simulate the TMDSC experiment and the calculated response is compared with the measured scans. Received: 22 February 1999 Accepted in revised form: 11 June 1999     

Glass transition study of blends of poly(N-methyldodecano-12-lactam) with poly(styrene-co-acrylic acid)

The blends of poly(N-methyldodecano-12-lactam) (MPA) with poly(styrene-co-acrylic acid) (PSAA) prepared from dioxane solutions were studied by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The experimental DSC data of glass transition temperature T_g as a function of composition of amorphous phase were fitted for the as-prepared and re-scanned samples using theoretical approaches. The as-prepared blends show monotonic single-T_g dependence. The values of the Gordon-Taylor coefficient not far from unity suggest miscibility of the blend system in amorphous phase in the whole concentration range. As documented by FTIR, this miscibility is associated with hydrogen bonds between COOH groups of the acrylic acid units in PSAA molecules acting as the H-bond donor and CO groups of MPA acting as the H-bond acceptor. The T_g-dependencies obtained form the second runs have a profound sigmoid character. The Schneider treatment induced an idea of partial limited miscibility in the MPA/PSAA blends caused by prevalence of homogeneous contacts. The difference in T_g between the first and second run can partly be attributed to higher crystallinities in the former.     

Kinetic characterization of barium titanate–bismuth oxide–vanadium pentoxide glasses

The glasses with the composition (80 − x)V₂O₅·20Bi₂O₃·xBaTiO₃ with x = 2.5, 5, 7.5 and 10 mol % were prepared by a melting technique. The crystallization behavior and the microstructure of the glasses were investigated by using differential scanning calorimetry (DSC), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The mean value of the activation energy of structural relaxation (〈E_g〉) decreased from 395 ± 3 to 369 ± 1.83 kJ/mol when BaTiO₃ increased from 2.5 to 10 mol %. The activation energies obtained by the methods Kissinger and Ozawa were in the range from 213 ± 0.65 to 256 ± 1.23 kJ/mol. Different analysis methods were used to estimate the Avrami exponents. Their values range from 4.26 ± 0.6 to 2.62 ± 0.11 for the exothermic peak of the prepared glasses. Moreover, synthesized glasses-ceramic containing BaTi₄O₉ and Ba₃TiV₄O₁₅ were estimated by using XRD.     

Glass transition temperature and thermal decomposition of cellulose powder

Cellulose powder and cellulose pellets obtained by pressing the microcrystalline powder were studied using differential scanning calorimetry (DSC), differential thermal analysis (DTA), and thermal gravimetry (TG). The TG method enabled the assessment of water content in the investigated samples. The glass phase transition in cellulose was studied using the DSC method, both in heating and cooling runs, in a wide temperature range from −100 to 180 °C. It is shown that the DSC cooling runs are more suitable for the glass phase transition visualisation than the heating runs. The discrepancy between glass phase transition temperature T _g found using DSC and predictions by Kaelbe’s approach are observed for “dry” (7 and 5.3% water content) cellulose. This could be explained by strong interactions between cellulose chains appearing when the water concentration decreases. The T _g measurements vs. moisture content may be used for cellulose crystallinity index determination.     

Phase and state transition effects on dielectric, mechanical, and thermal properties of polyols

The present study investigated the glass transition, crystallisation and melting behaviour of erythritol, xylitol, and glucitol (sorbitol) using dielectric analysis (DEA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). Sorbitol and xylitol were plasticised by water and their glass transition temperatures decreased when water content was increased. Erythritol crystallised rapidly, and its water plasticisation behaviour could not be determined. Melting of the crystalline polyols occurred at their specific melting temperatures. Melts of erythritol and xylitol crystallised on recooling and no glass transition was apparent on reheating. Quench cooled sorbitol melt remained amorphous and showed a glass transition on reheating. Glass transition and crystallisation were apparent in the DSC thermogram and the dielectric and the dynamic mechanical spectra of mixtures of amorphous and crystalline xylitol.     

木糖醇玻璃焓松弛的量热分析

为了考察木糖醇的玻璃化转变和焓松弛行为,寻求碳链长度对线性多元醇玻璃化转变和焓松弛行为的影响,利用差示扫描量热(DSC)技术测定了不同降温速率下木糖醇在玻璃化转变温度(Tg)前后的比热容(Cp),通过曲线拟合获得了TNM(Tool-Narayanaswamy-Moynihan)模型参数,并和其他多元醇类已有研究结果进行对照.结果表明,尽管TNM模型可以很好地重现不同降温速率体系的实验比热容数据,但模型参数并不是材料常数,而是和热历史有关,不同的降温速率对应不同的模型参数.指前因子(A)、非线性参数(x)和非指数参数(β)均随着降温速率的增加而降低,松弛活化焓(△h*)的变化趋势刚好相反.几种线性多元醇玻璃化转变和TNM模型参数的对照表明,玻璃化转变温度,松弛活化焓和动力学脆度(m)都随着烷基碳链长度的增加而增加.虽然非线性参数、非指数参数随碳链长度的增加有降低的趋势,但木糖醇展现出反常变化的情形.     

Melting and glass transitions in paraffinic and naphthenic oils

Naphthenic and paraffinic oils were analyzed by modulated differential scanning calorimetry (MDSC). The results showed several improvements in the analysis of thermal properties when compared with standard DSC. The glass transition temperature (T_g), the enthalpy relaxation at T_g, and the melting endotherms could be deconvoluted, and reversible melting could be identified. This allowed for an easier interpretation of the thermal properties of the oils. With MDSC, the T_gs in mineral oils were found to coincide with endothermic enthalpy relaxation, which is generally regarded as a melting endotherm with standard DSC. A decrease in heat capacity after T_g was attributed to the existence of rigid amorphous material. From Δc_p at T_g and the oil molecular weight, the number of repeat units in the oil chains was estimated at less than 20. The T_g of a hypothetical pure aromatic oil was found to be similar to that for petroleum asphaltenes, and that for a naphthenic oil of infinite molecular weight to be similar to that of petroleum resins.     

Two novel phase transition materials based on 1-isopropyl-1,4-diazabicyclo[2.2.2]octan-1-ium

Two novel phase transition materials,[C₉H₂₀N₂] [Na(BF₄)₃] (1) and[C₉H₂₀N₂] [(PF₆)₂] (2), were synthesized based on 1-isopropyl-1,4-diazabicyclo[2.2.2]octan-1-ium with sodium tetrafluoroborate and hexafluorophosphoric acid, respectively. Differential scanning calorimetry measurements detected that 1 and 2 underwent reversible phase transitions, which were confirmed by dielectric measurements. Single crystal X-ray diffraction data suggested that compound 1 changed from a high temperature phase with a space group of P6₃ to a low temperature one with a space group of P2₁/c, and that compound 2 transformed from the space group of Pbca at room temperature to P2₁/c at low temperature. Formation of hydrogen bonds and distortion of 1,4-diazabicyclo[2.2.2]octane rings may drive the transitions.     

不同结晶度的乙二醇及其水溶液玻璃化转变与焓松弛

为了考察晶体成分对无定形成分玻璃化转变和结构松弛行为的影响,利用差示扫描量热法(DSC),结合低温显微技术,研究了乙二醇(EG)及其50％水溶液在不同结晶度时的玻璃化转变和焓松弛行为.采用等温结晶方法控制骤冷的部分结晶玻璃体中的晶体份额.DSC结果表明,对于部分结晶的EG,只有单一的玻璃化转变过程,而对于50％EG,当结晶度不同时,不同程度地表现出两次玻璃化转变（无定形相Ⅰ和无定形相Ⅱ）.相Ⅰ的玻璃化转变温度和完全无定形态的含水EG的玻璃化转变温度相一致;相Ⅱ的玻璃化转变温度要比此温度约高6 ℃.低温显微观察结果印证了DSC实验结果.DSC等温退火的实验和KWW(Kohlrausch-Williams-Watts)衰变函数分析结果表明,EG无定形和50％EG中的两种无定形有不同的焓松弛行为.     

Measurement and modeling of the glass transition temperatures of multi-component solutions

Protein crystals are usually grown in multi-component aqueous solutions containing salts, buffers and other additives. To measure the X-ray diffraction data of the crystal, crystals are rapidly lowered to cryogenic temperatures. On flash cooling, ice frequently forms affecting the integrity of the sample. In order to eliminate this effect, substances called cryoprotectants are added to produce a glassy (vitrified) state rather than ice. Heretofore, the quantity of cryoprotectant needed to vitrify the sample has largely been established by trial and error. In this study, differential scanning calorimetry (DSC) was used to measure the melting (T_m), devitrification (T_d) and glass transition (T_g) temperatures of solutions with a range of compositions typical of those used for growing protein crystals, with the addition of glycerol as cryoprotectant. The addition of cryoprotectant raises the T_g and lowers the T_m of bulk solution thereby decreasing the cooling rates required for vitrification of protein crystals. The theoretical T_g value was calculated using the apparent volume fraction using the Miller/Fox equation extended for multi-component systems. The experimental values of T_g were within approximately ±4% of that predicted by the model. Thus, the use of the model holds the promise of a rational method for the theoretical determination of the composition of cryoprotectant requirement of protein crystallization solutions.     

Calorimetric glass transition temperature and absolute heat capacity of polystyrene ultrathin films

The absolute heat capacity and glass transition temperature (T_g) of unsupported ultrathin films were measured with differential scanning calorimetry with the step-scan method in an effort to further examine the thermodynamic behavior of glass-forming materials on the nanoscale. Films were stacked in layers with multiple preparation methods. The absolute heat capacity in both the glass and liquid states decreased with decreasing film thickness, and T_g also decreased with decreasing film thickness. The magnitude of the T_g depression was closer to that observed for films supported on rigid substrates than that observed for freely standing films. The stacked thin films regained bulk behavior after the application of pressure at a high temperature. The effects of various preparation methods were examined, including the use of polyisobutylene as an interleaving layer between the polystyrene films. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3518–3527, 2006     

Water sorption and glass transition of freeze-dried camu-camu (myrciaria dubia (H.B.K.) Mc Vaugh) pulp

Differential scanning calorimetry (DSC) was used to determine phase transitions of freeze-dried camu-camu pulp in a wide range of moisture content. Samples were equilibrated at 25°C over saturated salt solutions in order to obtain water activities (a_w) between 0.11–0.90. Samples with a_w>0.90 were obtained by direct water addition. At the low and intermediate moisture content range, Gordon–Taylor model was able to predict the plasticizing effect of water. In samples, with a_w>0.90, the glass transition curve exhibited a discontinuity and T^’_g was practically constant (–58.8°C), representing the glass transition temperature of the maximally concentrated phase(T_g ).