scholarly journals Inter-enantiomer conversion dynamics and Johari–Goldstein relaxation of benzophenones

2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Michela Romanini ◽  
Roberto Macovez ◽  
Maria Barrio ◽  
Josep Lluís Tamarit
Keyword(s):  
Glass Transition ◽  
Dielectric Loss ◽  
Dielectric Spectroscopy ◽  
Parent Compound ◽  
Scanning Calorimetry ◽  
Molecular Conformations ◽  
Molecular Glass ◽  
Phenyl Ketone ◽  
Temperature And Pressure ◽  
Opposite Chirality

AbstractWe employ temperature- and pressure-dependent dielectric spectroscopy, as well as differential scanning calorimetry, to characterize benzophenone and the singly-substituted ortho-bromobenzophenone derivative in the liquid and glass states, and analyze the results in terms of the molecular conformations reported for these molecules. Despite the significantly higher mass of the brominated derivative, its dynamic and calorimetric glass transition temperatures are only ten degrees higher than those of benzophenone. The kinetic fragility index of the halogenated molecule is lower than that of the parent compound, and is found to decrease with increasing pressure. By a detailed analysis of the dielectric loss spectra, we provide evidence for the existence of a Johari–Goldstein (JG) relaxation in both compounds, thus settling the controversy concerning the possible lack of a JG process in benzophenone and confirming the universality of this dielectric loss feature in molecular glass-formers. Both compounds also display an intramolecular relaxation, whose characteristic timescale appears to be correlated with that of the cooperative structural relaxation associated with the glass transition. The limited molecular flexibility of ortho-bromobenzophenone allows identifying the intramolecular relaxation as the inter-enantiomeric conversion between two isoenergetic conformers of opposite chirality, which only differ in the sign of the angle between the brominated aryl ring and the coplanar phenyl-ketone subunit. The observation by dielectric spectroscopy of a similar relaxation also in liquid benzophenone indicates that the inter-enantiomer conversion between the two isoenergetic helicoidal ground-state conformers of opposite chirality occurs via a transition state characterized by a coplanar phenyl-ketone moiety.

Origin of Glass Transition of Poly(2-vinylpyridine). A Temperature- and Pressure-Dependent Dielectric Spectroscopy Study

2004 ◽  
Vol 37 (21) ◽  
pp. 8116-8122 ◽  
Author(s):  
P. Papadopoulos ◽  
D. Peristeraki ◽  
G. Floudas ◽  
G. Koutalas ◽  
N. Hadjichristidis
Keyword(s):  
Glass Transition ◽  
Dielectric Spectroscopy ◽  
Spectroscopy Study ◽  
Temperature And Pressure

scholarly journals PEG-POSS Star Molecules Blended in Polyurethane with Flexible Hard Segments: Morphology and Dynamics

Molecules ◽  
2020 ◽  
Vol 26 (1) ◽  
pp. 99
Author(s):  
Konstantinos N. Raftopoulos ◽  
Edyta Hebda ◽  
Anna Grzybowska ◽  
Panagiotis A. Klonos ◽  
Apostolos Kyritsis ◽  
...  
Keyword(s):  
Glass Transition ◽  
Star Polymer ◽  
Polymerization Process ◽  
Degree Of Crystallinity ◽  
Dielectric Relaxation Spectroscopy ◽  
Scanning Calorimetry ◽  
Similar System ◽  
Soft Phase ◽  
Hard Segments ◽  
Star Molecules

A star polymer with a polyhedral oligomeric silsesquioxanne (POSS) core and poly(ethylene glycol) (PEG) vertex groups is incorporated in a polyurethane with flexible hard segments in-situ during the polymerization process. The blends are studied in terms of morphology, molecular dynamics, and charge mobility. The methods utilized for this purpose are scanning electron and atomic force microscopies (SEM, AFM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), and to a larger extent dielectric relaxation spectroscopy (DRS). It is found that POSS reduces the degree of crystallinity of the hard segments. Contrary to what was observed in a similar system with POSS pendent along the main chain, soft phase calorimetric glass transition temperature drops as a result of plasticization, and homogenization of the soft phase by the star molecules. The dynamic glass transition though, remains practically unaffected, and a hypothesis is formed to resolve the discrepancy, based on the assumption of different thermal and dielectric responses of slow and fast modes of the system. A relaxation α′, slower than the bulky segmental α and common in polyurethanes, appears here too. A detailed analysis of dielectric spectra provides some evidence that this relaxation has cooperative character. An additional relaxation g, which is not commonly observed, accompanies the Maxwell Wagner Sillars interfacial polarization process, and has dynamics similar to it. POSS is found to introduce conductivity and possibly alter its mechanism. The study points out that different architectures of incorporation of POSS in polyurethane affect its physical properties by different mechanisms.

Evaluation of glass transition in model cell lines using differential scanning calorimetry

Cytotherapy ◽  
2021 ◽  
Vol 23 (5) ◽  
pp. S173
Author(s):  
C. Jones ◽  
J. Heimfeld ◽  
B.J. Hawkins ◽  
R. Marcu
Keyword(s):  
Differential Scanning Calorimetry ◽  
Glass Transition ◽  
Cell Lines ◽  
Scanning Calorimetry ◽  
Model Cell

scholarly journals Thermal analysis: basic concept of differential scanning calorimetry and thermogravimetry for beginners

2020 ◽  
Vol 0 (0) ◽  
Author(s):  
Nurul Fatahah Asyqin Zainal ◽  
Jean Marc Saiter ◽  
Suhaila Idayu Abdul Halim ◽  
Romain Lucas ◽  
Chin Han Chan
Keyword(s):  
Thermal Analysis ◽  
Differential Scanning Calorimetry ◽  
Glass Transition ◽  
Transition Temperature ◽  
Glass Transition Temperature ◽  
Commercial Application ◽  
Scanning Calorimetry ◽  
Teaching Activities ◽  
Sample Decomposition ◽  
Calibration Baseline

AbstractWe present an overview for the basic fundamental of thermal analysis, which is applicable for educational purposes, especially for lecturers at the universities, who may refer to the articles as the references to “teach” or to “lecture” to final year project students or young researchers who are working on their postgraduate projects. Description of basic instrumentation [i.e. differential scanning calorimetry (DSC) and thermogravimetry (TGA)] covers from what we should know about the instrument, calibration, baseline and samples’ signal. We also provide the step-by-step guides for the estimation of the glass transition temperature after DSC as well as examples and exercises are included, which are applicable for teaching activities. Glass transition temperature is an important property for commercial application of a polymeric material, e.g. packaging, automotive, etc. TGA is also highlighted where the analysis gives important thermal degradation information of a material to avoid sample decomposition during the DSC measurement. The step-by-step guides of the estimation of the activation energy after TGA based on Hoffman’s Arrhenius-like relationship are also provided.

scholarly journals Physical Aging Behavior of a Glassy Polyether

Polymers ◽  
2021 ◽  
Vol 13 (6) ◽  
pp. 954
Author(s):  
Xavier Monnier ◽  
Sara Marina ◽  
Xabier Lopez de Pariza ◽  
Haritz Sardón ◽  
Jaime Martin ◽  
...  
Keyword(s):  
Glass Transition ◽  
Transition Temperature ◽  
Glass Transition Temperature ◽  
Physical Aging ◽  
Glassy State ◽  
Aging Behavior ◽  
Scanning Calorimetry ◽  
Narrow Temperature Range ◽  
Glass Forming ◽  
Fast Scanning Calorimetry

The present work aims to provide insights on recent findings indicating the presence of multiple equilibration mechanisms in physical aging of glasses. To this aim, we have investigated a glass forming polyether, poly(1-4 cyclohexane di-methanol) (PCDM), by following the evolution of the enthalpic state during physical aging by fast scanning calorimetry (FSC). The main results of our study indicate that physical aging persists at temperatures way below the glass transition temperature and, in a narrow temperature range, is characterized by a two steps evolution of the enthalpic state. Altogether, our results indicate that the simple old-standing view of physical aging as triggered by the α relaxation does not hold true when aging is carried out deep in the glassy state.

scholarly journals Manipulation of the Glass Transition Properties of a High-Solid System Made of Acrylic Acid-N,N′-Methylenebisacrylamide Copolymer Grafted on Hydroxypropyl Methyl Cellulose

2021 ◽  
Vol 22 (5) ◽  
pp. 2682
Author(s):  
Nazim Nassar ◽  
Felicity Whitehead ◽  
Taghrid Istivan ◽  
Robert Shanks ◽  
Stefan Kasapis
Keyword(s):  
Glass Transition ◽  
Acrylic Acid ◽  
Methyl Cellulose ◽  
Small Deformation ◽  
Polymerization Reaction ◽  
Solid Matrix ◽  
Scanning Calorimetry ◽  
Modulated Differential Scanning Calorimetry ◽  
High Solid ◽  
Hydroxypropyl Methyl Cellulose

Crosslinking of hydroxypropyl methyl cellulose (HPMC) and acrylic acid (AAc) was carried out at various compositions to develop a high-solid matrix with variable glass transition properties. The matrix was synthesized by the copolymerisation of two monomers, AAc and N,N′-methylenebisacrylamide (MBA) and their grafting onto HMPC. Potassium persulfate (K2S2O8) was used to initiate the free radical polymerization reaction and tetramethylethylenediamine (TEMED) to accelerate radical polymerisation. Structural properties of the network were investigated with Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), modulated differential scanning calorimetry (MDSC), small-deformation dynamic oscillation in-shear, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The results show the formation of a cohesive macromolecular entity that is highly amorphous. There is a considerable manipulation of the rheological and calorimetric glass transition temperatures as a function of the amount of added acrylic acid, which is followed upon heating by an extensive rubbery plateau. Complementary TGA work demonstrates that the initial composition of all the HPMC-AAc networks is maintained up to 200 °C, an outcome that bodes well for applications of targeted bioactive compound delivery.

Sign in / Sign up

Export Citation Format

Share Document