Enthalpic Recovery Research Articles

Thermal investigation on hydrated co-amorphous systems of nicotinamide and prilocaine

It is generally recognized that water, acting as a plasticizer, increases molecular mobility, leading to a decrease of the glass transition temperature (Tg) in amorphous systems. However, an anti-plasticizing effect of water was recently observed on prilocaine (PRL). This effect might be used in co-amorphous systems to moderate the plasticizing effect of water. Nicotinamide (NIC) can form co-amorphous systems with PRL. In order to investigate the effect of water on these co-amorphous systems, the Tgs and molecular mobility of hydrated co-amorphous NIC-PRL systems were compared with those of the respective anhydrous systems. Molecular mobility was estimated by considering the enthalpic recovery at the Tg using the Kohlrausch-Williams-Watts (KWW) equation. At molar ratios of NIC above 0.2, a plasticizing effect of water on co-amorphous NIC-PRL systems was observed with increasing the NIC concentration. In contrast, at molar ratios of NIC of 0.2 and below, water had an anti-plasticizing effect on the co-amorphous NIC-PRL systems, with increased Tgs and reduced mobility upon hydration.

Enhancing dielectric breakdown strength: structural relaxation of amorphous polymers and nanocomposites

Abstract

Densified network glasses and liquids with thermodynamically reversible and structurally adaptive behaviour.

If crystallization can be avoided during cooling, a liquid will display a substantial increase of its viscosity, and will form a glass that behaves as a solid with a relaxation time that grows exponentially with decreasing temperature. Given this 'off-equilibrium' nature, a hysteresis loop appears when a cooling/heating cycle is performed across the glass transition. Here we report on molecular dynamics simulations of densified glass-forming liquids that follow this kind of cycle. Over a finite pressure interval, minuscule thermal changes are found, revealing glasses of 'thermally reversible' character with optimal volumetric or enthalpic recovery. By analysing the topology of the atomic network structure, we find that corresponding liquids adapt under the pressure-induced increasing stress by experiencing larger bond-angle excursions. The analysis of the dynamic behaviour reveals that the structural relaxation time is substantially reduced in these adaptive liquids, and also drives the reversible character of the glass transition. Ultimately, the results substantiate the notion of stress-free (Maxwell isostatic) rigidity in disordered molecular systems, while also revealing new implications for the topological engineering of complex materials.

Physical aging in amorphous poly(ethylene furanoate): Enthalpic recovery, density, and oxygen transport considerations

The current work utilizes three separate techniques to study the physical aging process in amorphous poly(ethylene furanoate) (PEF), which is a recently introduced engineering thermoplastic with enhanced properties compared to petroleum-sourced poly(ethylene terephthalate). Differential scanning calorimetry aging experiments were conducted at multiple aging temperatures and times, and the resultant enthalpic recovery values compared to the theoretical maximum enthalpy loss evaluated from calculations involving extrapolation of the equilibrium liquid line. Density measurements reveal densification of the matrix for the aged versus unaged samples, and provide an estimate for the reduction in free volume for the aged samples. Complementary oxygen permeation and pressure-decay sorption experiments provide independent verification of the free volume reduction mechanism for physical aging in glassy polymers. The current work provides the first detailed aging study for PEF. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015, 53, 389–399

Molecular Mobility as a Predictor of the Water Sorption by Annealed Amorphous Trehalose

The work aims at investigating the correlation of water sorption potential with different measures of molecular mobility in an annealed amorphous model compound (trehalose). Amorphous trehalose, prepared by freeze-drying, was annealed at 100°C (17°C < T (g)) for up to 120h. Global molecular mobility was studied using a broadband dielectric spectrometer in the frequency range of 10(6)-10(-2) Hz. Enthalpic recovery was measured by differential scanning calorimetry and water sorption profiles were obtained using an automated vapor sorption balance. As a function of annealing time, there was an increase, both in average α-relaxation time and enthalpic recovery and a decrease in the amount of sorbed water. A strong linear correlation was observed between the water sorption potential and the dielectric relaxation time, indicating a common underlying mechanism of the effect of annealing time on these properties. Enthalpic recovery, which is widely used as a measure of structural relaxation, did not correlate well with the extent of water sorption. The α-relaxation time can be used as a predictor of the water sorption potential of amorphous trehalose. It will be of interest and value to develop such predictive models for other amorphous compounds of pharmaceutical interest.

Estimating the reversing and non‐reversing heat flow from standard DSC curves in the glass transition region

A mathematical model for the total heat flow obtained in differential scanning calorimetry (DSC) experiments from polymers with enthalpic relaxation is proposed. It is limited to the glass transition and enthalpic relaxation range of temperature and to the cases where the enthalpic relaxation is the only non‐reversing process taking place. The model consists of a mixture of functions representing the heat capacity heat flow of the glassy and non‐glassy fractions, the glass transition progress and the enthalpic relaxation heat flow.Optimal fittings of the model were performed on the experimental total heat flow data, obtained from two thermoplastics with different aging times. Considering which functions of the mixture represent reversing and non‐reversing processes, the reversing and non‐reversing heat flows were also estimated. The estimated reversing and non‐reversing signals were compared with the ones obtained by modulation. On the whole a good match was found, which was even better considering that the estimates are not affected by the frequency effect of the modulated temperature DSC (MTDSC) measurements. The model assumes linear trends for the heat capacity heat flow of the glassy and non‐glassy structures. The glass transition progress is represented by a generalized logistic function and the enthalpic relaxation heat flow by the first derivative of another generalized logistic. It brings about a new approach to these phenomena, where the parameters of these functions represent the temperature at which each event is centered, the change of heat capacity (Cp) at the glass transition and the energy involved in the enthalpic recovery. Copyright © 2011 John Wiley &amp; Sons, Ltd.

Assessment of the parameters influencing the fiber characteristics of electrospun poly(ethyl methacrylate) membranes

This work evaluates the influence of electrospinning process parameters on the mean diameter and standard deviation of fiber diameters in electrospun poly(ethyl methacrylate) (PEMA). Processing conditions were selected using Taguchi’s statistical method. Oriented and unoriented electrospun mats with good mechanical properties were produced and demonstrated with tensile stress–strain diagrams. Differential scanning calorimetry (DSC) experiments showed that the polymer chains were forced into non-equilibrium conformations due to electrospinning. Enthalpic recovery during a heating scan is shown by an endothermic peak in the initial DSC heating scan that disappears in subsequent heating scans. An increase in the glass transition temperature with respect to PEMA films shows that the polymer is not equilibrated by heating above glass transition. Cell attachment was tested with MC3T3-E1 pre-osteoblastic cells cultured for short time periods on the electrospun mats. It is shown that the cells present less extended morphology with more diffuse perimetral focal adhesions than cells cultured on flat substrates. A tendency of cells to align in the direction of the substrate fibers in oriented electrospun membranes was also found.

The Low-Temperature Endotherm in Poly(ethylene terephthalate): Partial Melting and Rigid Amorphous Fraction Mobilization

A detailed investigation of the low-temperature endotherm of poly(ethylene terephthalate) (PET) performed by temperature-modulated differential scanning calorimetry is presented. The origin of the small endotherm, generally observed a few degrees above the crystallization temperature in PET and in many other polymers, is a widely discussed matter. The most frequent interpretation considers it the result of partial fusion with superposition of a recrystallization process even if it has also been proposed that it can originate from enthalpic recovery connected to mobilization of the rigid amorphous fraction. In an attempt to resolve the question, a new method for the interpretation of the modulated heat-flow-rate curve resulting from a temperature modulation program is proposed. The procedure consists of the analysis of the initial points of the steady-state heat-flow-rate signals in the heating and cooling semiperiods with the temperature modulation being performed with a sawtooth profile. The study conducted in parallel on the reversing specific heat capacity and the heat-flow-rate curves, observed on heating after isothermal crystallization at various temperatures, showed that multiple processes, involving both the crystalline and the rigid amorphous fraction, overlap in the temperature range in which the low-temperature endotherm is observed. The origin of the endotherm under investigation is therefore connected with both partial fusion of the crystalline portions and enthalpy recovery subsequent to structural relaxation of the rigid amorphous fraction. An estimation of the relative percentages of the two different processes is presented and discussed.

Evolution of a Metallocenic sPP with Time: Changes in Crystalline Content and Enthalpic Relaxation

AbstractSummary: The structural evolution of a metallocenic syndiotactic poly(propylene), sPP, with time has been studied. Due to the low syndiotactic content, the analyzed sPP sample can be easily quenched to a completely amorphous state. This amorphous sample, when left at room temperature is able to crystallize at relatively long times. The degree of crystallinity, as a function of time, has been analyzed by X‐ray diffraction and DSC. The DSC melting curves show the presence of a very important low‐temperature endotherm, besides the main melting peak. Real‐time variable–temperature synchrotron experiments have been performed in order to analyze the origin of the two melting peaks. They seem to arise from the melting of two populations of sPP crystals with different size and/or perfection, rather than from the melting of different polymorphs. The changes in the crystalline regions are accompanied by important variations in the mechanical behavior, as revealed by DMTA and microhardness (MH) measurements. In addition, the sPP crystallization has been analyzed by MH measurements, showing the importance that a relative low crystallinity has on the stiffness of a polymeric material at temperatures above Tg. On the other hand, the kinetics of the enthalpic recovery of quenched amorphous sPP specimens has been analyzed by DSC with temperature modulation. It was found that this enthalpic relaxation can be described by the KWW model, and the relaxation times and shape parameters at three different aging temperatures have been determined, with the corresponding apparent activation energy of this process.Variation with temperature of the most probable long spacing of sPP.imageVariation with temperature of the most probable long spacing of sPP.

Measurement of enthalpic relaxation by differential scanning calorimetry—effect of experimental conditions

Differential scanning calorimetry (DSC) is the most commonly used technique for studying enthalpic relaxation in amorphous systems. Our objective was to study the effect of experimental conditions, specifically heating and cooling rates, on the enthalpic relaxation measurement by differential scanning calorimetry. Amorphous trehalose was prepared by freeze-drying an aqueous solution of trehalose dihydrate. It was subjected to differential scanning calorimetry. The enthalpic recovery (ER) at the glass transition temperature ( T g), for identically aged samples, depended on the heating rate (HR). The T g onset increased as a function of the heating rate and so did the completion of enthalpic recovery, i.e., the temperature at which the enthalpy curve meets the super-cooled liquid line after the glass transition. Therefore, the enthalpic recovery, and by extension the observed extent of relaxation, was influenced by the heating rate. As the aging time increased, there was an increase in the T g onset as well as the completion of enthalpic recovery. Since the calculated enthalpic recovery value is strongly dependent on this endpoint, there is a potential for overestimation of the relaxation below T g. This is particularly important for longer aging times and higher heating rates. It is generally believed that the enthalpic recovery can be minimized by keeping the cooling and heating rates identical. This observation can also be explained by the effect of heating rate on T g onset and the endpoint of enthalpic recovery. The enthalpic recovery at T g may not reflect the state of the sample, and may be strongly influenced by the experimental conditions. Thus, the effects of experimental conditions need to be carefully evaluated in order to obtain meaningful results.

Effect of preparation method on physical properties of amorphous trehalose.

To determine the effect of preparation method on the physical properties of amorphous trehalose. Amorphous anhydrous trehalose was prepared by four different methods. viz., freeze-drying, spray-drying, dehydration, and melt quenching. The glass transition temperature (Tg), enthalpic relaxation behavior, and crystallization were studied by differential scanning calorimetry, whereas X-ray diffractometry was used for phase identification. The rate and extent of water uptake at different relative humidity values were also obtained. Though the enthalpic relaxation and crystallization behaviors were influenced by the method of preparation of amorphous trehalose, the Tg and fragility were not. The phase prepared by dehydration showed the highest enthalpic recovery at Tg, indicating that aging may have occurred during preparation. Among the four methods used, trehalose prepared by dehydration had the highest tendency to crystallize, whereas there was no crystallization in melt-quenched amorphous trehalose. The method of preparation influenced not only the rate and extent of water sorption but also the phase crystallized. Water vapor sorption removed the effects of structural history in the amorphous phase formed by dehydration. The method of preparation strongly influenced the pharmaceutically relevant properties of amorphous trehalose. The resistance to crystallization can be rank ordered as trehalose prepared by dehydration < freeze-dried approximately spray-dried < melt-quenched. The rate of water sorption can be rank ordered as trehalose prepared by dehydration < freeze-dried < spray-dried.

Effect of aging on the physical properties of amorphous trehalose.

The purpose of this investigation was i) to study the effect of physical aging on crystallization and water vapor sorption behavior of amorphous anhydrous trehalose prepared by freeze-drying, and ii) to determine the effects of water sorption on the relaxation state of the aged material. Freeze-dried trehalose was aged at 100 dgrees C for varying time periods to obtain samples with different degrees of relaxation. The glass transition temperature (Tg) and enthalpic relaxation were determined by differential scanning calorimetry, and the rate and extent of water uptake at different relative humidity values were quantified using an automated vapor sorption balance. Annealing below the Tg caused nucleation in the amorphous trehalose samples, which decreased the crystallization onset temperature on subsequent heating. However, no crystallization was observed below the Tg even after prolonged annealing. Physical aging caused a decrease in the rate and extent of water vapor sorption at low relative humidity values. Moreover, the water sorption removed the effects of physical aging, thus effectively causing enthalpic recovery in the aged samples. This recovery occurred gradually in the glassy phase and was not associated with a glass to rubber transition. We believe this aging reversal to be due to volume expansion during water sorption in the amorphous structure. Thermal history of amorphous materials is a crucial determinant of their physical properties. Aging of amorphous trehalose led to nucleation below the Tg, and decrease in rate and extent of water sorption. Sorption of water resulted in irreversible changes in the relaxation state of the aged material.

Enthalpic relaxation in frozen aqueous trehalose solutions

Our object was to investigate the effect of annealing on the glass transition temperatures and enthalpic recovery of frozen aqueous solutions of trehalose. Trehalose solutions were subjected to differential scanning calorimetry wherein they were first cooled from room temperature to −60 °C, and heated to the annealing temperature, which ranged between −34 and −48 °C. Following isothermal annealing for the desired time period, the glass transition temperatures and the enthalpic recovery were determined in the final heating scan. Frozen unannealed trehalose solutions were characterized by two glass transition events. At a heating rate of 2 °C/min, the observed Tg 1′ and Tg 2′ were ∼−45 and −31 °C, respectively. Annealing resulted in an increase in the lower transition temperature, Tg 1′, while the higher transition temperature, Tg 2′, was unaffected. Enthalpic recovery due to annealing was associated only with Tg 2′. Annealing at −36 °C resulted in the highest value of Tg 1′ and the maximum enthalpic recovery. Irrespective of the heating rates, the magnitude of enthalpic recovery and Tg 1′ showed a similar trend (first an increase, followed by a decrease) as a function of annealing temperature. This suggests that annealing led to crystallization of ice and subsequently the system became maximally freeze-concentrated. Annealing, at temperatures higher than −36 °C, led to a reduction in enthalpic recovery associated with Tg 2′ and a lowering of Tg 1′. These observations are consistent with the hypothesis that the higher transition temperature coincides with the onset of ice melting. We have attempted to bridge two conflicting schools of thought regarding the origin of multiple glass transitions in frozen aqueous sugar solutions. The two glass transitions are attributed to the formation of two “populations” in the freeze-concentrated phase during “non-equilibrium” or rapid cooling—one, that is maximally freeze-concentrated and the other that contains a higher amount of water. The higher transition temperature also overlaps with the onset of ice melting.

Enthalpy relaxation in poly(ethylene terephthalate) and related polyesters

Enthalpic relaxation data are presented on poly(ethylene terephthalate), poly(ethylene naphthalate) and their copolymers. Analysis of these data allows the determination of the amount of energy absorbed at the glass transition, Qt, and the location of the enthalpic recovery peak, Tmax, as a function of the time of ageing of the samples. Ageing measurements were carried out for periods of up to 2016 h and at temperatures between 40 °C and 110 °C, depending upon the chemical composition of the system being investigated. The enthalpic relaxation rates are influenced by the chemical structure and reflect the effects of local order pinning the chains and influencing the rate of enthalpic recovery. © 2000 Society of Chemical Industry

Blends of amorphous and crystalline polylactides with poly(methyl methacrylate) and poly(methyl acrylate): a miscibility study

Blends of amorphous and crystalline polylactides (PDLA and PLLA) with poly(methyl methacrylate) (PMMA) and poly(methyl acrylate) (PMA) have been prepared. Thermal behaviour and miscibility of these blends along the entire composition interval were studied by differential scanning calorimetry (d.s.c.). The results were compared with those obtained by dynamic mechanical analysis (DMTA). Only one T g was found in PDLA/PMA and PDLA/PMMA blends, indicating a high degree of miscibility in both systems. Nevertheless, the PDLA/PMMA blend presented enlargements of the T g width at high PMMA contents. In this case, additional evidence of complete miscibility was obtained by studying the evolution of the enthalpic recovery peaks which appear after different thermal annealing treatments. When the polylactide used was semicrystalline (PLLA), once the thermal history of the blends had been destroyed, crystallization of PLLA was disturbed in both blends PLLA/PMMA and PLLA/PMA, but in a rather different fashion: in the first case crystallization was almost prevented while in the second one it was favoured. This behaviour was explained in terms of the effect of the higher stiffness as indicated by the value of T g for PMMA compared to that for PMA.

DSC studies of thermal events at the glass transition temperature region of partially oriented polyester fibers

The high rate of quenching and the excessive frozen-in stresses development that take place during the spinning process of partially oriented polyester yarns brings about a thermal behavior similar Co that of pressure vitrified and mechanically stressed polymeric glasses with a sub Tg exotherm preceded by an endotherm at 335°K. Annealing at 338° K relaxes the frozen-in stresses and eliminates the sub Tg events. Annealing above 355° K recovers the enthalpy of the aged fibers, minimizes the enthalpic recovery and drops the endothermic peak height in the DSC thermogram. The extent of enthalpic recovery during annealing of fibers containing different spin finishes indicates the p lasticization efficiency of the finishes.