scholarly journals Synthesis and Polymerization Kinetics of Rigid Tricyanate Ester

Polymers ◽  
2021 ◽  
Vol 13 (11) ◽  
pp. 1686
Author(s):  
Andrey Galukhin ◽  
Roman Nosov ◽  
Ilya Nikolaev ◽  
Elena Melnikova ◽  
Daut Islamov ◽  
...  
Keyword(s):  
Kinetic Analysis ◽  
Single Step ◽  
Polymerization Kinetics ◽  
Scanning Calorimetry ◽  
Modulated Differential Scanning Calorimetry ◽  
Diffusion Controlled ◽  
Polymerization Product ◽  
The One ◽  
Kinetics Of

A new rigid tricyanate ester consisting of seven conjugated aromatic units is synthesized, and its structure is confirmed by X-ray analysis. This ester undergoes thermally stimulated polymerization in a liquid state. Conventional and temperature-modulated differential scanning calorimetry techniques are employed to study the polymerization kinetics. A transition of polymerization from a kinetic- to a diffusion-controlled regime is detected. Kinetic analysis is performed by combining isoconversional and model-based computations. It demonstrates that polymerization in the kinetically controlled regime of the present monomer can be described as a quasi-single-step, auto-catalytic, process. The diffusion contribution is parameterized by the Fournier model. Kinetic analysis is complemented by characterization of thermal properties of the corresponding polymerization product by means of thermogravimetric and thermomechanical analyses. Overall, the obtained experimental results are consistent with our hypothesis about the relation between the rigidity and functionality of the cyanate ester monomer, on the one hand, and its reactivity and glass transition temperature of the corresponding polymer, on the other hand.

scholarly journals Advanced Isoconversional Kinetic Analysis for the Elucidation of Complex Reaction Mechanisms: A New Method for the Identification of Rate-Limiting Steps

Molecules ◽  
2019 ◽  
Vol 24 (9) ◽  
pp. 1683 ◽  
Author(s):  
Nicolas Sbirrazzuoli
Keyword(s):  
Activation Energy ◽  
Kinetic Analysis ◽  
Single Step ◽  
Thermoanalytical Techniques ◽  
Diffusion Controlled ◽  
Physical Transformation ◽  
Exponential Factors ◽  
Isoconversional Kinetic Analysis ◽  
The Individual ◽  
Rate Limiting

Two complex cure mechanisms were simulated. Isoconversional kinetic analysis was applied to the resulting data. The study highlighted correlations between the reaction rate, activation energy dependency, rate constants for the chemically controlled part of the reaction and the diffusion-controlled part, activation energy and pre-exponential factors of the individual steps and change in rate-limiting steps. It was shown how some parameters computed using Friedman’s method can help to identify change in the rate-limiting steps of the overall polymerization mechanism as measured by thermoanalytical techniques. It was concluded that the assumption of the validity of a single-step equation when restricted to a given α value holds for complex reactions. The method is not limited to chemical reactions, but can be applied to any complex chemical or physical transformation.

On the Mechanism of Milling Induced Disordering in AlFe

1996 ◽  
Vol 460 ◽  
Author(s):  
M. T. Clavaguera-Mora ◽  
J. Zhu ◽  
M. Meyer ◽  
L. Mendoza-Zelis ◽  
F. H. Sanchez ◽  
...  
Keyword(s):  
Long Range ◽  
Milling Time ◽  
Continuous Heating ◽  
X Ray Diffraction ◽  
Mechanical Grinding ◽  
Scanning Calorimetry ◽  
X Ray ◽  
Diffusion Controlled ◽  
Transmission Mössbauer Spectroscopy ◽  
Kinetics Of

ABSTRACTThe evolution of the B2-AlFe phase during mechanical grinding in Ar has been examined as a function of milling time by X-Ray diffraction, transmission Mössbauer spectroscopy and differential scanning calorimetry. Short and long range disorder was observed to increase with the mechanical treatment up to the attainment of a steady state. The evolution of the long range order parameter and of the local atomic configurations at Fe sites were analyzed in terms of possible mechanisms for milling induced disordering. The kinetics of the thermal reordering was studied under continuous heating and isothermal calorimetrie regimes. Modeling of the reordering processes by diffusion controlled growth of pre-existing ordered grains is presented as well as the estimated values of both the enthalpy and the activation energy of the reordering process. The results are consistent with a non uniform distribution of disorder throughout the sample and will be compared with preceding information on related systems.

Preparation and Crystallization Kinetics of FeSiB Amorphous Ribbons under Non-Isothermal Regime

2014 ◽  
Vol 605 ◽  
pp. 35-38
Author(s):  
Eirini Varouti
Keyword(s):  
Thermal Stability ◽  
Differential Scanning Calorimetry ◽  
Chemical Composition ◽  
Crystallization Kinetics ◽  
Structural Changes ◽  
Scanning Calorimetry ◽  
Amorphous Ribbons ◽  
Isothermal Regime ◽  
Kinetics Of

The aim of the present work was the preparation and characterization of FeSiB amorphous magnetic ribbons with the following chemical composition: Fe80SixB20-x, x=5,6,8 and Fe75Si15B10. Differential Scanning Calorimetry was employed in order to study the thermal stability and structural changes during the transformations that took place. Much emphasis is placed on the analysis of the crystallization kinetics.

Characterization of Nanocrystalline γ–Fe2O3Prepared by Wet Chemical Method

1999 ◽  
Vol 14 (4) ◽  
pp. 1570-1575 ◽  
Author(s):  
G. Ennas ◽  
G. Marongiu ◽  
A. Musinu ◽  
A. Falqui ◽  
P. Ballirano ◽  
...  
Keyword(s):  
Isothermal Treatment ◽  
X Ray Diffraction ◽  
Ferrous Chloride ◽  
Scanning Calorimetry ◽  
Direct Transformation ◽  
X Ray ◽  
Transmission Electron ◽  
Xrd Techniques ◽  
Kinetics Of

Homogeneous maghemite (γ–Fe2O3) nanoparticles with an average crystal size around 5 nm were synthesized by successive hydrolysis, oxidation, and dehydration of tetrapyridino-ferrous chloride. Morphological, thermal, and structural properties were investigated by transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and x-ray diffraction (XRD) techniques. Rietveld refinement indicated a cubic cell. The superstructure reflections, related to the ordering of cation lattice vacancies, were not detected in the diffraction pattern. Kinetics of the solid-state phase transition of nanocrystalline maghemite to hematite (α–Fe2O3), investigated by energy dispersive x-ray diffraction (EDXRD), indicates that direct transformation from nanocrystalline maghemite to microcrystalline hematite takes place during isothermal treatment at 385 °C. This temperature is lower than that observed both for microcrystalline maghemite and for nanocrystalline maghemite supported on silica.

scholarly journals Study of Mechanical Properties of PHBHV/Miscanthus Green Composites Using Combined Experimental and Micromechanical Approaches

Polymers ◽  
2021 ◽  
Vol 13 (16) ◽  
pp. 2650
Author(s):  
Thibault Lemaire ◽  
Erica Gea Rodi ◽  
Valérie Langlois ◽  
Estelle Renard ◽  
Vittorio Sansalone
Keyword(s):  
Mechanical Properties ◽  
Tensile Modulus ◽  
Tensile Tests ◽  
Specific Class ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
Green Wood ◽  
Miscanthus Giganteus ◽  
The One

In recent years the interest in the realization of green wood plastic composites (GWPC) materials has increased due to the necessity of reducing the proliferation of synthetic plastics. In this work, we study a specific class of GWPCs from its synthesis to the characterization of its mechanical properties. These properties are related to the underlying microstructure using both experimental and modeling approaches. Different contents of Miscanthus giganteus fibers, at 5, 10, 20, 30 weight percent’s, were thus combined to a microbial matrix, namely poly (3-hydroxybutyrate)-co-poly(3-hydroxyvalerate) (PHBHV). The samples were manufactured by extrusion and injection molding processing. The obtained samples were then characterized by cyclic-tensile tests, pycnometer testing, differential scanning calorimetry, Fourier transform infrared spectroscopy, X-ray diffraction, and microscopy. The possible effect of the fabrication process on the fibers size is also checked. In parallel, the measured properties of the biocomposite were also estimated using a Mori–Tanaka approach to derive the effective behavior of the composite. As expected, the addition of reinforcement to the polymer matrix results in composites with higher Young moduli on the one hand, and lower failure strains and tensile strengths on the other hand (tensile modulus was increased by 100% and tensile strength decreased by 23% when reinforced with 30 wt % of Miscanthus fibers).

Glass Formation During Room Temperature, Isothermal Drying

2003 ◽  
Author(s):  
Alptekin Aksan ◽  
Mehmet Toner
Keyword(s):  
Glass Transition ◽  
Glassy State ◽  
Glass Transitions ◽  
Scanning Calorimetry ◽  
Modulated Differential Scanning Calorimetry ◽  
Glass Transition Kinetics ◽  
The Stability ◽  
Isothermal Drying ◽  
Kinetics Of

Isothermal drying and glass transition of solutions and films have drawn considerable attention from many industries. We here explore the feasibility of modifying the isothermal drying and vitrification kinetics of carbohydrate solutions in order to ensure the stability and quality of their ingredients. Modulated Differential Scanning Calorimetry experiments with isothermally dried trehalose and trehalose/dextran solutions were performed and the glass transition kinetics have been determined. Three distinct drying regimes were observed. With isothermal, isobaric drying at 0%RH, it was indeed possible to reach the glassy state for a trehalose and a trehalosedextran system. With the addition of high molecular weight sugars, the glass transitions of isothermally dried carbohydrate solutions can be accelerated as a function of dextran mass ratio in the sample.

scholarly journals Kissinger Method in Kinetics of Materials: Things to Beware and Be Aware of

Molecules ◽  
2020 ◽  
Vol 25 (12) ◽  
pp. 2813 ◽  
Author(s):  
Sergey Vyazovkin
Keyword(s):  
Activation Energy ◽  
Isoconversional Methods ◽  
Single Step ◽  
Order Reaction ◽  
Kissinger Method ◽  
Scanning Calorimetry ◽  
First Order ◽  
Kinetics Of ◽  
Final Equation ◽  
Derivative Thermogravimetry

The Kissinger method is an overwhelmingly popular way of estimating the activation energy of thermally stimulated processes studied by differential scanning calorimetry (DSC), differential thermal analysis (DTA), and derivative thermogravimetry (DTG). The simplicity of its use is offset considerably by the number of problems that result from underlying assumptions. The assumption of a first-order reaction introduces a certain evaluation error that may become very large when applying temperature programs other than linear heating. The assumption of heating is embedded in the final equation that makes the method inapplicable to any data obtained on cooling. The method yields a single activation energy in agreement with the assumption of single-step kinetics that creates a problem with the majority of applications. This is illustrated by applying the Kissinger method to some chemical reactions, crystallization, glass transition, and melting. In the cases when the isoconversional activation energy varies significantly, the Kissinger plots tend to be almost perfectly linear that means the method fails to detect the inherent complexity of the processes. It is stressed that the Kissinger method is never the best choice when one is looking for insights into the processes kinetics. Comparably simple isoconversional methods offer an insightful alternative.

scholarly journals Development, Fabrication, and Characterization of Composite Polycaprolactone Membranes Reinforced with TiO2 Nanoparticles

Polymers ◽  
2019 ◽  
Vol 11 (12) ◽  
pp. 1955 ◽  
Author(s):  
Karina del Ángel-Sánchez ◽  
César I. Borbolla-Torres ◽  
Luis M. Palacios-Pineda ◽  
Nicolás A. Ulloa-Castillo ◽  
Alex Elías-Zúñiga
Keyword(s):  
Acetic Acid ◽  
Titanium Dioxide Nanoparticles ◽  
Sol Gel ◽  
Tensile Tests ◽  
Experimental Characterization ◽  
X Ray Diffraction ◽  
Scanning Calorimetry ◽  
X Ray ◽  
The One

This paper focuses on developing, fabricating, and characterizing composite polycaprolactone (PCL) membranes reinforced with titanium dioxide nanoparticles (NPs) elaborated by using two solvents; acetic acid and a mixture of chloroform and N,N-dimethylformamide (DMF). The resulting physical, chemical, and mechanical properties of the composite materials are studied by using experimental characterization techniques such as scanning electron microscopy (SEM), differential scanning calorimetry (DSC), X-ray diffraction (XRD), Fourier-transform infrared (FTIR) analysis, contact angle (CA), uniaxial and biaxial tensile tests, and surface roughness measurements. Experimental results show that the composite material synthesized by sol-gel and chloroform-DMF has a better performance than the one obtained by using acetic acid as a solvent.

scholarly journals Commentary: Considerations in the Measurement of Glass Transition Temperatures of Pharmaceutical Amorphous Solids

2019 ◽  
Vol 21 (1) ◽  
Author(s):  
Ann Newman ◽  
George Zografi
Keyword(s):  
Glass Transition ◽  
Amorphous Solid ◽  
Amorphous Solids ◽  
Scanning Calorimetry ◽  
Modulated Differential Scanning Calorimetry ◽  
Preparation Methods ◽  
Glass Transition Temperatures ◽  
Pharmaceutical Applications ◽  
Sample Preparation Methods

AbstractAn increased interest in using amorphous solid forms in pharmaceutical applications to increase solubility, dissolution, and bioavailability has generated a need for better characterization of key properties, such as the glass transition (Tg) temperature. Although many laboratories measure and report this value, the details around these measurements are often vague or misunderstood. In this article, we attempt to highlight and compare various aspects of the two most common methods used to measure pharmaceutical Tg values, conventional and modulated differential scanning calorimetry (DSC). Issues that directly impact the Tg, such as instrumental parameters, sample preparation methods, data analysis, and “wet” vs. “dry” measurements, are discussed.

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