Calorimetric and relaxation properties of xylitol-water mixtures

We present the first broadband dielectric spectroscopy (BDS) and differential scanning calorimetry study of supercooled xylitol-water mixtures in the whole concentration range and in wide frequency (10(-2)-10(6) Hz) and temperature (120-365 K) ranges. The calorimetric glass transition, T(g), decreases from 247 K for pure xylitol to about 181 K at a water concentration of approximately 37 wt. %. At water concentrations in the range 29-35 wt. % a plentiful calorimetric behaviour is observed. In addition to the glass transition, almost simultaneous crystallization and melting events occurring around 230-240 K. At higher water concentrations ice is formed during cooling and the glass transition temperature increases to a steady value of about 200 K for all higher water concentrations. This T(g) corresponds to an unfrozen xylitol-water solution containing 20 wt. % water. In addition to the true glass transition we also observed a glass transition-like feature at 220 K for all the ice containing samples. However, this feature is more likely due to ice dissolution [A. Inaba and O. Andersson, Thermochim. Acta, 461, 44 (2007)]. In the case of the BDS measurements the presence of water clearly has an effect on both the cooperative α-relaxation and the secondary β-relaxation. The α-relaxation shows a non-Arrhenius temperature dependence and becomes faster with increasing concentration of water. The fragility of the solutions, determined by the temperature dependence of the α-relaxation close to the dynamic glass transition, decreases with increasing water content up to about 26 wt. % water, where ice starts to form. This decrease in fragility with increasing water content is most likely caused by the increasing density of hydrogen bonds, forming a network-like structure in the deeply supercooled regime. The intensity of the secondary β-relaxation of xylitol decreases noticeably already at a water content of 2 wt. %, and at a water content above 5 wt. % it has been replaced by a considerably stronger water (w) relaxation at about the same frequency. However, the similarities in time scale and activation energy between the w-relaxation and the β-relaxation of xylitol at water contents below 13 wt. % suggest that the w-relaxation is governed, in some way, by the β-relaxation of xylitol, since clusters of water molecules are rare at these water concentrations. At higher water concentrations the intensity and relaxation rate of the w-relaxation increase rapidly with increasing water content (up to the concentration where ice starts to form), most likely due to a rapid increase of small water clusters where an increasing number of water molecules interacting with other water molecules.     

Crystallization, glass transition and morphology of (R)-3-hydroxybutyrate oligomers

The study focuses on the effect of the molecular length of isotactic hydroxybutyrate oligomers on the crystal morphology, crystallinity, and spherulitic superstructure. Furthermore, the process of solidification of the quiescent melt is evaluated by the analysis of the crystallization kinetics and of the glass transition. Melt-crystallization is strongly controlled by the chain length, and the regime of cooling. Crystallization can completely be avoided by rapid cooling. Slow cooling allows at best incomplete crystallization, with the crystallinity increasing with chain length. Typically, the maximum crystallinity is between 50% and 80% for OHB of molecular weights of 500 and 5000 g mol⁻¹, respectively. The temperatures of the glass transition and of crystallization/melting increase with molecular length, and are discussed in terms of the Fox-Flory and Gibbs-Thomson equations, respectively. For all samples, regardless of the chain length, spherulitic crystallization is observed, with the perfection of spherulites increasing with decreasing crystallization temperature. The transition of formation of extended-chain crystals to formation of folded-chain crystals occurs at a molecular weight of about 2000 g mol⁻¹, which corresponds to chain length of about 7 nm. Analysis of the heat-capacity increment at the glass transition temperature reveals the existence of a rigid amorphous fraction.     

Melt-crystallization, glass transition and morphology of a (R)-3-hydroxybutyrate pentamer

The melt-crystallization of an oligo[(R)-3-hydroxybutyrate] with five repeating units has been analyzed using standard and temperature-modulated calorimetry, optical microscopy, and atomic force microscopy. Specimens of different crystallinity and supermolecular structure were generated by variation of the rate of cooling of a quiescent melt, or by variation of the temperature of isothermal crystallization. Completely amorphous samples can be obtained by cooling of the melt at a rate of 40 K min⁻¹, or faster, to a temperature lower than the glass transition. The crystallinity depends on the crystallization temperature. The maximum enthalpy-based crystallinity of about 40-45% is obtained by crystallization at temperatures lower than the temperature of the maximum crystallization rate, which is between 310 and 320 K. Analysis of the apparent heat capacity in metastable structural equilibrium reveals reversible melting at temperatures between 320 and 370 K by observation of an excess heat capacity above the level of the vibrational heat capacity, i.e., in the temperature range of irreversible reorganization and melting. The reversible melting is discussed in the context of coupling of the crystalline and amorphous phases, and compared to earlier studies on oligoethylene and oligo(oxyethylene). The presence of crystals causes formation of a rigid amorphous fraction of about 30% at a crystallinity of 40%. Optical and atomic force microscopy reveal spherulitic crystallization. At relatively high crystallization temperature, and in the early stage of the crystallization process, dendrites are observed which finally yield spherulites of decreased perfection. Larger spherulites of higher perfection grow at relatively low crystallization temperature, as deduced from the appearance of the Maltese cross, and the regularity of banding. The band spacing is less than 5 μm, as is accurately determined by atomic force microscopy. The temperature dependence of the spherulitic growth rate is in accord with the calorimetric analysis of the crystallization rate.     

Non-isothermal crystallization behaviors of poly(4-methyl-pentene-1)

Non-isothermal crystallization of isotactic poly(4-methyl-pentene-1) (P4MP1) is studied by differential scanning calorimeter (DSC), and kinetic parameters such as the Avrami exponent and the kinetic crystallization rate (Z _c) are determined. From the cooling and melting curves of P4MP1 at different cooling rates, the crystalline enthalpy increases with the increasing cooling rate, but the degree of crystalline by DSC measurement shows not much variation. Degree of crystalline of P4MP1 calculated by wide angle X-ray diffraction pattern shows the same tendency with crystalline enthalpy, indicating that re-crystallization occurs when samples heated above the second glass transition temperature of P4MP1. By Jeziorny analysis, n ₁ value suggests that mainly spherulites’ growth at 2.5 K min⁻¹ transforms into a mixture mode of three-dimensional and two-dimensional space extensions with further increasing cooling rate. In the secondary crystallization process, n ₂ values indicate that the secondary crystallization is mainly the two-dimensional extension of the lamellar crystals formed during the primary crystallization process. The rates of the crystallization, Z _c and t _1/2 both increase obviously with the increase of cooling rate, especially at the primary crystallization stage. By Mo’s method, higher cooling rate should be required in order to obtain a higher degree of crystallinity at unit crystallization time.     

Crystallization and melting of a branched polyethylene with precisely controlled chemical structure

The heat capacity of a linear polyethylene with dimethyl branches, at every 21st backbone atom was analyzed by differential scanning calorimetry (DSC) and quasi-isothermal temperature-modulated DSC. This novel copolyethylene (PE2M) is relatively difficult to crystallize from the melt. On subsequent heating, a first, sharp melting peak is followed by a sharp cold-crystallization and crystal perfection and a smaller endotherm, before reaching the main melting at 315–320 K, close to the melting temperatures of eicosane and tetracontane. The low-temperature melting is sensitive to the cooling rate and disappears below 1.0 K min⁻¹. The cold crystallization can be avoided by heating with rates faster than 80 K min⁻¹. The PE2M exhibits some reversing and reversible melting, which is typical for chain-folded polymers. The glass transition of semicrystalline PE2M is broadened and reaches its upper limit at about 260 K (midpoint at about 0.355 K). Above this temperature, the crystals seem to have a heat capacity similar to that of the liquid. A hypothesis is that the melting transition can be explained by changes in crystal perfection without major alteration of the crystal structure and the lamellar morphology. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3461–3474, 2006     

Isothermal crystallization of P3HT:PCBM blends studied by RHC

Defining appropriate annealing temperatures and times is vitally important for increasing the efficiency of bulk heterojunction solar cells by favoring the crystallinity of the polymer-fullerene blend components. In order to better understand the annealing process, the isothermal crystallization of poly(3-hexyl thiophene) (P3HT) and [6,6]-phenyl C₆₁-butyric acid methyl ester (PCBM) blend investigated by means of rapid heating cooling calorimetry (RHC). Isothermal crystallization experiments at temperatures in between the glass transition and melting, within the temperature range of 70–150 °C, can successfully be performed since RHC permits cooling at a sufficiently high rate in order to prevent crystallization during cooling. Crystallization isotherms were determined from the subsequent melting behavior of the blend. They were measured for a wide set of annealing temperatures and times, and the evolution of the crystallization rate with temperature is compared for annealing from the glassy state and from the melt state.     

Non-isothermal crystallization kinetics of continuous glass fiber-reinforced poly(ether ether ketone) composites

Current studies on crystallization kinetics for glass fiber-reinforced poly(ether ether ketone) mainly focused on short glass fiber-reinforced composites and their isothermal crystallization. It is worth noting that continuous glass fiber-reinforced poly(ether ether ketone) composite (CGF/PEEK) possesses relatively higher mechanical performance than short fiber-reinforced PEEK under high temperature. Here, for the first time, we investigate the non-isothermal crystallization kinetics and melting behavior of CGF/PEEK by differential scanning calorimetry at four different cooling rates. By evaluating the crystallite size of CGF/PEEK using X-ray diffraction, it is found that with the decreasing cooling rate, the crystallite size distribution evolves more uniform, and the size of crystallites enlarges. Besides, by systematical analysis, we find the modified Avrami equation can well describe crystallization behavior of the CGF/PEEK. The higher Avrami value of CGF/PEEK than pure PEEK indicates that CGF could introduce a more complex geometry effect on the crystallization. The addition of CGF greatly reduces the absolute value of crystallization activation energy of PEEK, suggesting that CGF can reduce the nucleation energy barrier. The obtained results illustrate that CGF can accelerate the nucleation rate due to heterogeneous nucleation while reduce the growth rate due to retarded polymer chain mobility. And the cooling conditions can influence crystal growth and morphology.

     

Characterization, crystallization kinetics and melting behavior of poly(ethylene succinate-co-21 mol% trimethylene succinate) copolyester

A copolyester was synthesized and characterized to have 78.6 mol% ethylene succinate unit and 21.4 mol% trimethylene succinate unit by using NMR. The value of the random parameter is 0.97 that can be considered to be a random copolymer. The melting behavior after isothermal crystallization was studied using differential scanning calorimeter by varying the crystallization temperature, the heating rate and the crystallization time. Triple melting peaks were observed. The melting behavior indicates that the upper melting peaks are primarily due to the melting of lamellar crystals with different stability. The Hoffman-Weeks linear plot gives an equilibrium melting temperature of 94.0 °C. The spherulite growth of this copolyester from 72 °C to 30 or 15 °C at a cooling rate of 1 or 2 °C/min was monitored and recorded using an optical microscope equipped with a CCD camera and a DVD recorder. These experiments including the self-nucleation pretreatment took 72 min and 60 min, respectively. Continuous growth rates between melting and glass transition temperatures can be obtained after curve-fitting procedures. These data fit well with those data points measured in the isothermal experiments, which is time consuming. These isothermal and continuous data were separately analyzed with the Hoffman and Lauritzen theory. A regime II-III transition was detected at about 51.5 ± 0.1 °C.     

Thermochemical Properties of the 1-Ethyl-3-Methylimidazolium Bis(trifluoromethylsulfonyl)imide Ionic Liquid under Conditions of Equilibrium with Atmospheric Moisture

Thermochemical properties of the 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide ionic liquid [EMim]NTf₂ containing moisture absorbed from the atmosphere (0.242 wt %) are investigated. The phase behavior and thermal stability relative to salt dried in vacuum are studied by means of thermogravimetry and differential scanning calorimetry at different heating and cooling rates. The glass transition, crystallization, and melting temperatures, the enthalpies of phase transitions, and the changes in heat capacity during the formation of glass are determined. It is established that the absorbed water crystallizes at a temperature of around ?40.6°C and has virtually no effect on the thermal stability and phase behavior of the salt. Rapid cooling results in the ionic liquid transitioning into the glass state at ?91.7 °C and the formation of three mesophases with different melting temperatures; one crystalline modification that melts at a temperature of ?19.3°C forms upon slow cooling.     

非等温结晶对PLLA的热行为和形貌的影响

将聚L-乳酸(PLLA)熔化非等温熔融结晶, 采用DSC、POM、SEM等技术研究了降温速率对PLLA的热行为和形貌的影响. PLLA在低降温速率(2 ℃·min-1)下的结晶在118 ℃伴随有结晶机制的转变. 玻璃化温度和结晶度随着降温速率的降低而增大. 随着降温速率的降低, 球晶尺寸增大, 当降温速率为10 ℃·min-1 时, PLLA 为无定型材料. 采用模压成型的方法并控制降温速率制备了具有球晶结构的条状PLLA 生物材料, 与高降温速率下制备的PLLA相比,低降温速率下获得的具有球晶结构的PLLA材料的断面更光滑和致密, 但脆性增强.     

CRYSTALLIZATION AND MULTI-MELTING BEHAVIOR OF POLY (ETHYLENE TEREPHTHALATE) MODIFIED BY SODIUM SALT OF 5-SULPHO-ISOPHTHALIC ACID

The crystallization kinetics of the copolyester, poly(ethylene terephthalate) (PET) modified by sodium salt of 5-sulpho-isophthalic acid(SIPM), was investigated by means of differential scanning calorimeter. The experimental results and polari-microscopy observation all showed that the introduction of SIPM did not affect the nucleation of crystallization. Within the temperature range between their glass transition temperature T_θand melting point T_m, the crystallization rate of the copolyester sample decreased with increasing content of SIPM. The relative crystallization rate constant Z of SIPM/DMT (dimethyl terephthalate) 4mol % sample was about 1% pure PET's Z value. For isothermal crystallized copolyester samples, DSC heating curves displayed multi-melting behavior. This was interpreted by molecular weight fractionation during crystallization and premelting-recrystallization mechanism. This interpretation showed why the second melting point T_(m2) will change according to Hoffman-Weeks(H-W) equation and the first melting point T_(m1) will increase with increasing SIPM. The principal cause of these phenomena is the high temperature crystallization rate decreases rapidly with increasing SIPM.     

Crystallization kinetics of polymer–diluent mixtures. Influence of benzophenone on the spherulitic growth rate of isotactic polystyrene

As an extension of earlier work on the crystallization kinetics of isotactic polystyrene, the spherulite growth rate in mixtures of isotactic polystyrene and benzophenone has been measured over a concentration range extending from pure polymer to a mixture containing about 30% benzophenone. The glass transition temperature has been measured over the entire range from pure polymer to pure benzophenone. For the mixtures the dependence of the growth rate on temperature is similar to that of the undiluted polymer. The addition of benzophenone causes a shift of the crystallization range to lower temperatures. For mixtures containing up to about 20% benzophenone, the maximum in the growth rate increases with increasing content of benzophenone. On addition of more benzophenone, the maximum rate is depressed. Taking into account the glass transition temperature of the mixtures, the influence of benzophenone on the melting point of isotactic polystyrene, and the volume fraction of polymer, we can describe the influence of benzophenone on the growth rate in a semiquantitative way.     

Recent developments in thermal analysis of polymers: Calorimetry in the limit of slow and fast heating rates

This review focuses on new insights into the crystal melting transition and the amorphous glass transition of polymers that have been gained through recent advances in thermoanalytical methods. The specific heat capacity can now be studied under two extreme limits, that is, under quasi‐isothermal conditions (limit of zero heating rate) and, at the other end of the scale, under rapid heating conditions (heating rates on the order of thousands of degrees per second), made possible through nanocalorimetry. The reversible melting, and multiple reversible melting, of semicrystalline polymers is explored using quasi‐isothermal temperature modulated differential scanning calorimetry, TMDSC. The excess reversing heat capacity, above the baseline, measured under nearly isothermal conditions is attributed to locally reversible surface melting and crystallization processes that do not require molecular nucleation. Observations of double reversible melting endotherms in isotactic polystyrene suggest existence of two distinct populations of crystals, each showing locally reversible surface melting. The second subject of the review, nanocalorimetry, is utilized to study samples of small mass under conditions of very fast heating and cooling. The glass transition properties of thin amorphous polymer films are observed under adiabatic conditions. The glass transition temperature appears to be independent of film thickness, and is observed even in ultra‐thin films. Recrystallization and reorganization during rapid heating are studied by nanocalorimetry of semicrystalline polymers. The uppermost endotherm seen under normal DSC scanning of poly(ethylene terephthalate) is caused by reorganization, and vanishes under the rapid heating conditions (3000K/s) provided by nanocalorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 629–636, 2005     

快速扫描量热法研究聚对苯二甲酸-1,4-环己烷二甲醇酯的结晶和熔融行为

采用快速扫描量热法(FSC)结合传统的差示扫描量热仪(DSC)考察了聚对苯二甲酸-1,4-环己烷二甲醇酯(PCT)聚酯在接近玻璃化转变(T_g)和熔融温度(T_m)范围(100~270 ℃)的结晶和熔融行为。 较大过冷度时PCT聚酯结晶较快,FSC有效地抑制降温过程结晶的发生,而较低过冷度下传统DSC可以避免样品降解对实验结果的影响,二者的结合能很好地对PCT聚酯结晶动力学进行测量,实验结果表明在175 ℃时结晶速率最快。 并且利用Flash DSC对等温结晶温度下形成的片晶熔点进行加热速率的相关测量,在熔融动力学建模的基础上进行校准,以确定零加热速率下片晶的熔点。 Hoffman-Weeks方程中T_m与结晶温度(T_c)的线性关系与T_c=T_m的交点给出了PCT晶体的平衡熔融温度$T_m^o$为315 ℃。     

Characterization,crystallization kinetics,and melting behavior of poly(ethylene succinate) copolyester containing 10 mol % butylene succinate

Copolyester was synthesized and characterized as having 89.9 mol % ethylene succinate units and 10.1 mol % butylene succinate units in a random sequence, as revealed by NMR. Isothermal crystallization kinetics was studied in the temperature range (T_c) from 30 to 73 °C using differential scanning calorimetry (DSC). The melting behavior after isothermal crystallization was investigated using DSC by varying the T_c, the heating rate and the crystallization time. DSC curves showed triple melting peaks. The melting behavior indicates that the upper melting peaks are associated primarily with the melting of lamellar crystals with various stabilities. As the T_c increases, the contribution of recrystallization slowly decreases and finally disappears. A Hoffman‐Weeks linear plot gives an equilibrium melting temperature of 107.0 °C. The spherulite growth of this copolyester from 80 to 20 °C at a cooling rate of 2 or 4 °C/min was monitored and recorded using an optical microscope equipped with a CCD camera. Continuous growth rates between melting and glass transition temperatures can be obtained after curve‐fitting procedures. These data fit well with those data points measured in the isothermal experiments. These data were analyzed with the Hoffman and Lauritzen theory. A regime II → III transition was detected at around 52 °C. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2431–2442, 2008     

Thermodynamics of activated phase transitions of 8CB: DSC and MC calorimetry

The present paper reports the heating rate effect on the phase transitions of a pure liquid crystal octylcyanobiphenyl (8CB) with use of Differential Scanning Calorimetry (DSC) and Modulation Calorimetry (MC) techniques. The DSC runs were taken at various temperature ramp rates from 20 to 0.5 K/min for heating and cooling scans. Well-defined endothermic/exothermic peaks were found at the melting/crystallization, smectic-A to nematic (SmA-N), and nematic to isotropic (N-I) transitions on heating/cooling scans, respectively. All transitions shift in temperature significantly with different ramp rates. The temperature shift of C(p) peaks between heating and cooling scans indicates the order of the transitions. In addition, all transitions follow an Arrhenius behavior. The activation energy of a transition increases as the total energy involved in the transition decreases. The respective enthalpy and entropy change of each transition provides information on the Gibbs free energy. The significance of the results is discussed in terms of the order of transitions. A comparative analysis of MC and DSC techniques highlights the significance of the two techniques. MC is a practicable tool for observing the phase dynamics whereas DSC is a good tool for studying the rate kinematics of the transitions.     

Nonisothermal melt crystallization and subsequent melting behavior of biodegradable poly(hydroxybutyrate)/multiwalled carbon nanotubes nanocomposites

In this work, nonisothermal melt crystallization and subsequent melting behavior of poly(hydroxybutyrate) (PHB) and its nanocomposites at different multiwalled carbon nanotubes (MWCNTs) loadings were investigated. Increasing the MWCNTs loadings has enhanced the nonisothermal melt crystallization of PHB significantly in the nanocomposites when compared with that of the neat PHB; furthermore, increasing the cooling rates shift the crystallization exotherms to low temperature range for both neat PHB and its nanocomposites. Double melting behavior is found for both neat PHB and its nanocomposites crystallized nonisothermally from the melt, which is explained by the melting, recrystallization, and remelting model. Effects of the MWCNTs loadings, cooling rates, and heating rates on the subsequent melting behavior of PHB were studied in detail. It is found that increasing the MWCNTs loadings, decreasing the cooling rates, and increasing the heating rates would restrict the occurrence of the recrystallization of PHB in the nanocomposites. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2238–2246, 2009     

Morphology development during solid-state annealing of poly(ether-ester) multiblock copolymers

Morphology development during isothermal annealing of poly(ether-ester) multiblock copolymers with hard segments containing poly(tetramethylene isophthalate) is examined by differential scanning calorimetry (DSC) and small-angle x-ray scattering (SAXS). Reorganization in the solid-state occurs by melting and recrystallization. At temperatures close to the melting point, glass transition measurements after quenching from the annealing temperature suggest microphase mixing follows melting. The temperature of maximum recrystallization rate is elevated relative to that of isothermal crystallization. SAXS experiments suggest that a memory of the initial morphology is retained during annealing. Aspects of the DSC scans related to crystallization on cooling and rescanning also suggest that the morphology at the annealing temperature plays a governing role in the determination of the degree of order possible on cooling. The crystalline regions stable at the annealing temperature are envisioned to function in a dual role, acting as nucleation centers for recrystallization and as a form of “constraint” to ordering on cooling. © 1996 John Wiley & Sons, Inc.     

Phase transitions in mesophase macromolecules. III. The transitions in poly(ethylene terephthalate-co-p-oxybenzoate)

The glass and melting transitions of poly(ethylene terephthalate-co-p-oxybenzoate)s have been studied by differential scanning calorimetry. Despite the higher glass transition expected for polyoxybenzoate, there is almost no change in the glass transition temperature up to 63 mol % oxybenzoate (353 ± 4 K). At high oxybenzoate concentration there seems to be a discontinuous jump to a glass transition of 450 K. This high glass transition has been observed in two-phase materials down to 30 mol % oxybenzoate. The melting transition shows signs of isodimorphism with a minimum in melting temperature at about 60–70 mol % oxybenzoate, 60 K below the melting temperature of poly(ethylene terephthalate). The thermal properties are little affected by the change of the noncrystalline parts of the molecules to a mesophase structure. The transition to the isotropic phase could not be analyzed because of prior decomposition.