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Abstract  

Materials with high surface areas and small particle size (nanophases), metastable polymorphs, and hydrated oxides are increasingly important in both materials and environmental science. Using modifications of oxide melt solution calorimetry, we have developed techniques to study the energetics of such oxides and oxyhydroxides, and to separate the effects of polymorphism, chemical variation, high surface area, and hydration. Several generalizations begin to emerge from these studies. The energy differences among different polymorphs (e.g., various zeolite frameworks, the - and -alumina polymorphs, manganese and iron oxides and oxyhydroxides) tend to be small, often barely more than thermal energy under conditions of synthesis. Much larger contributions to the energetics come from oxidation-reduction reactions and charge-coupled substitutions involving the ions of basic oxides (e.g., K and Ba). The thermodynamics of hydration involve closely balanced negative enthalpies and negative entropies and are very dependent on the particular framework and cage or tunnel geometry.

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Abstract  

Polymer molecules have contour lengths which may exceed the dimension of microphases. Especially in semicrystalline samples a single molecule may traverse several phase areas, giving rise to structures in the nanometer region. While microphases have properties that are dominated by surface effects, nanometer-size domains are dominated by interaction between opposing surfaces. Calorimetry can identify such size effects by shifts in the phase-transition temperatures and shapes, as well as changes in heat capacity. Specially restrictive phase structures exist in drawn fibers and in mesophase structures of polymers with alternating rigid and flexible segments. On several samples shifts in glass and melting temperatures will be documented. The proof of rigid amorphous sections at crystal interfaces will be given by comparison with structure analyses by X-ray diffraction and detection of motion by solid state NMR. Finally, it will be pointed out that nanophases need special attention if they are to be studied by thermal analysis since traditional ‘phase’ properties may not exist.

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Abstract  

In this study, the thermal analysis of the ω nanophase transformation from a quenched metastable β Ti–12Mo alloy composition (mass%) was investigated by electrical resistivity and dilatometry measurements. The activation energy was observed to be 121 ± 20 kJ mol−1 (from resistivity measurements) and 114 ± 12 kJ mol−1 (from dilatometry measurements) during the early stage of the transformation process. The kinetic of the ω nanophase transformation was modelized by using the classical Johnson–Mehl–Avrami (JMA) theory and a modified Avrami (MA) analysis. An Avrami exponent close to 1.5 was found at the early stage of the transformation suggesting a pure growth mechanism from pre-existing nucleation sites. Nevertheless, it was observed a decrease of the Avrami exponent to 0.5 at higher transformed fraction demonstrating a dimension loss in the growth mechanism due to the existence of the high misfit strain at the interface β/ω.

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Abstract  

Contributions of modern, temperature-modulated calorimetry are qualitatively and quantitatively discussed. The limitations are summarized, and it is shown that their understanding leads to new advances in instrumentation and measurement. The new thermal analysis experiments allow to separate reversing from irreversible processes. This opens the irreversible states and transitions to a description in terms of equilibrium and irreversible thermodynamics. Amorphous systems can be treated frommacroscopic to nanometer sizes with weak to strong coupling between neighboring phases. Semicrystalline, macromolecular systems are understood on the basis of modulated calorimetry as globally metastable, micro-to-nanophase-separated systems with locally reversible transitions.

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Semi-crystalline polymers

Two phases or three? An overview and perspective

Journal of Thermal Analysis and Calorimetry
Author: R. Seyler
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microphase to nanophase dimensions. The modulation amplitudes of temperature-modulated DSC, TMDSC, in frequent use for the last 20 years, are also indicated in Fig. 1 . They show the usefulness of TMDSC to test the reversibility of phase changes

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Abstract  

Thermogravimetric (TG) and differential thermal analysis (DTA) curves of methyltributylammonium smectite (MTBAS), methyltrioctylammonium smectite (MTOAS), and di(hydrogenatedtallow)dimethylammonium smectite (DHTDMAS), and also corresponding sodium smectite (NaS) and tetraalkylammonium chlorides (TAAC) were determined. The TAACs was decomposed exactly by heating up to 500°C. The adsorbed water content of 8.0% in the pure NaS was decreased down to 0.2% depending on the size of the non-polar alkyl groups in the tetraalkylammonium cations (TAA+). The thermal degradation of the organic partition nanophase formed between 2:1 layers of smectite occurs between 250–500°C. Activation energies (E) of the thermal degradations in the MTBAS, MTOAS and DHTDMAS are 13.4, 21.9, and 43.5 kJ mol−1, respectively. The E value increases by increasing of the interlayer spacing along a curve depending on the size of the alkyl groups in the TAA+.

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Abstract  

Oxyfluoride glass-ceramics based on the aluminosilicate glass-matrix with the nano-phase of fluoride is an interesting material for optoelectronics. A new glass from the SiO2–B2O3–Na2O–LaF3 system in which nanocrystallization of LaF3 could be obtained as well is presented. Thermal stability of glass and the crystalline phases formed upon heat treatment were determined by DTA/DSC and XRD methods, respectively. The effect of the glass composition on thermal stability was investigated by the SEM method. It has been found that the addition of LaF3 increases the tendency to decomposition of the borosilicate glass. In glasses with the ratio B2O3/(Na2O+3La2F6)<1 it is possible to obtain the immersed crystallization of LaF3 in transparent glassy matrix. The process is preceded by LaOF formation. Glasses with the composition B2O3/(Na2O+3La2F6)≥1 revealed the tendency to La(BSiO5) crystallization.

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Abstract  

Calorimetry deals with the energetics of atoms, molecules, and phases and can be used to gather experimental details about one of the two roots of our knowledge about matter. The other root is structural science. Both are understood from the microscopic to the macroscopic scale, but the effort to learn about calorimetry has lagged behind structural science. Although equilibrium thermodynamics is well known, one has learned in the past little about metastable and unstable states. Similarly, Dalton made early progress to describe phases as aggregates of molecules. The existence of macromolecules that consist of as many atoms as are needed to establish a phase have led, however, to confusion between colloids (collections of microphases) and macromolecules which may participate in several micro- or nanophases. This fact that macromolecules can be as large or larger than phases was first established by Staudinger as late as 1920. Both fields, calorimetry and macromolecular science, found many solutions for the understanding of metastable and unstable states. The learning of modern solutions to the problems of materials characterization by calorimetry is the topic of this paper.

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