Heat capacity and glass transition of ethylene oxide clathrate hydrate

1990 ◽  
Vol 8 (1-2) ◽  
pp. 45-58 ◽  
Author(s):  
O. Yamamuro ◽  
Y. P. Handa ◽  
M. Oguni ◽  
H. Suga
1991 ◽  
Vol 23 (5) ◽  
pp. 485-494 ◽  
Author(s):  
N. Kuratomi ◽  
O. Yamamuro ◽  
T. Matsuo ◽  
H. Suga

2021 ◽  
Vol 43 (2) ◽  
pp. 123-132
Author(s):  
N.A. Busko ◽  
◽  
V.K. Grishchenko ◽  
A.V. Barantsova ◽  
N.V. Gudzenko ◽  
...  

The aim of the work was to develop methods for the synthesis and study of the properties of silicon-containing oligomeric azo- and polyazoinitiators based on bis-γ-hydroxypropylpolysiloxane (HPS) and bis-γ-aminopropylpolysiloxane (APS). Silicon-containing oligomeric azoinitiators using HPS were synthesized on the basis of cyclohexanone azo-bis-isobutyrohydrazone (AGN-CH) and bis-γ-hydroxypropylpolysiloxane bifunctional macrodiisocyanate (MDIHPS). MDIHPS was obtained by the interaction of GPS with 2,4 toluene diisocyanate (2,4-TDI). Oligomeric azoinitiators have been obtained, which have the structure RXR and (RX)nR, where R is a propylpolysiloxane block, X is a azo initiator block. For the synthesis of an oligomeric azo initiator based on bis-γ-aminopropyl polysiloxane (APS), a method was first developed for the synthesis of a monomeric azo initiator with terminal oxadiazolinylcarbamanate isocyanate groups (AGN-NCO) by the interaction of AGN-CH and 2,4-TDI at a molar ratio of 1: 2. On the basis of the obtained AGN-NCO and APS at a molar ratio of AGN-NCO: APS = 1: 1, an oligomeric azo initiator (OAI APS-P) was synthesized, which has the structure (RX)nR, where R is a propylpolysiloxane block, X is an azo initiator block. The structures of monomeric and oligomeric azo initiators have been studied by UV and IR spectroscopy, and the kinetic regularities of their synthesis have been calculated. On the basis of oligomeric azo initiators and styrene, block copolymers of the (AB)nA type were obtained by the method of thermal and photoinitiated radical polymerization, where A is a propylpolysiloxane block, B is an oligosyrene block with a constant value of the organosilicon block and a different size of the oligostyrene block. The structure of block copolymers was investigated by IR spectroscopy. It was shown that during photopolymerization, oligostyrene blocks of shorter length are formed than during thermopolymerization, and possible oxidation processes. The study of relaxation transitions by DSC in oligostyrene and propylpolysiloxane blocks of the BCP showed that the common heat capacity curves are the presence of two jumps in the heat capacity at the glass transition temperatures of the polysiloxane and oligostyrene microphase. A slight shift in the glass transition temperature of polysiloxane microphases in BCP towards higher temperatures compared to the homopolymer may be associated with the effect of oligostyrene microphase. With a decrease in the length of the oligosyrene block, a low-temperature shift in the glass transition temperature of oligostyrene blocks relative to the homopolymer and a depression of ∆Cp,2 are observed, which is associated with the suppression of mobility in oligodienic microphases by less mobile propylpolysiloxane blocks.


1982 ◽  
Vol 60 (7) ◽  
pp. 881-892 ◽  
Author(s):  
Russell G. Ross ◽  
Per Andersson

Solid phases in the tetrahydrofuran–water (THF–H2O) system were investigated in the temperature range 100–260 K and at pressures up to 1.5 GPa. Thermal conductivity, λ, and heat capacity per unit volume, ρcp, were measured, using the transient hot-wire method. We made measurements on solid phases having nominal compositions THF•17H2O, THF•7•1H2O, and THF•4•6H2O, which we refer to as phases α, β, and γ, respectively. Phase α is known to be a structure II clathrate hydrate, and λ for this phase was found to be similar to other crystalline solids which are glass-like in relation to their thermal properties. Low-energy excitations are known to be relevant to the properties of glass-like solids, and, in the case of phase α, were probably rotational vibrations of the THF guest molecules. Phase β was similar, and we inferred that it was probably a structure I clathrate hydrate. Phase γ behaved nearly like a normal crystal phase at low temperatures, but λ became almost independent of temperature near melting. At 1.1 GPa and 130 K, we found evidence that phase α transformed, on pressurization, to a metastable modification which may be a new high-density form of clathrate hydrate. The astrophysical implications of our results were mentioned briefly.


2011 ◽  
Vol 108 ◽  
pp. 91-94 ◽  
Author(s):  
Shao Jian He ◽  
Jun Lin

Nanocomposites based on hyperbranched polymers and sodium montmorillonite were prepared over the full range of compositions. The XRD analysis showed the full exfoliation of silicate layers at lower silicate content (up to 9.1 wt%). With the further increase of silicate loading, an intercalated structure was developed with a constant d-spacing due to the unique structure of hyperbranched polymers. The heat capacity jump at the glass transition of the nanocomposites was found to deviate from the two-phase model prediction, indicating the formation of a rigid amorphous fraction. The glass transition temperature and heat capacity jump behaviors suggested that the molecular mobility of hyperbranched polymers were restricted by the introduction of silicate layers. The mechanical properties of the nanocomposites were also investigated.


2015 ◽  
Vol 59 (1) ◽  
pp. 109-118 ◽  
Author(s):  
Jolanta Tomaszewska-Gras ◽  
Sławomir Bakier ◽  
Kamila Goderska ◽  
Krzysztof Mansfeld

Abstract Thermodynamic properties of selected honeys: glass transition temperature (Tg), the change in specifi c heat capacity (ΔCp), and enthalpy (ΔH) were analysed using differential scanning calorimetry (DSC) in relation to the composition i.e. water and sugar content. Glass transition temperatures (Tg) of various types of honey differed significantly (p<0.05) and ranged from -49.7°C (polyfloral) to -34.8°C (sunflower). There was a strong correlation between the Tg values and the moisture content in honey (r = -0.94). The degree of crystallisation of the honey also influenced the Tg values. It has been shown that the presence or absence of sugar crystals influenced the glass transition temperature. For the decrystallised honeys, the Tg values were 6 to 11°C lower than for the crystallised honeys. The more crystallised a honey was, the greater the temperature difference was between the decrystallised and crystallized honey. In conclusion, to obtain reliable DSC results, it is crucial to measure the glass transition after the complete liquefaction of honey.


1987 ◽  
Vol 3 (5) ◽  
pp. 611-617 ◽  
Author(s):  
L Ferrari ◽  
W. A Phillips ◽  
G Russo

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