Differential scanning calorimetry of irradiated polymers

DSC was used to study the influence of fast electron irradiation on the molecular mobility and melting of semicrystalline polymers and copolymers of ethylene and of fluorocopolymer. The heat capacity-temperature dependences obtained in the range from 100 K to 500 K revealed the specific features of the irradiation effect on four relaxational transitions associated with the appearance of segmental motion in different molecular elements of the disordered regions in the polymer. The pronounced dependence of the radiation stability of crystallites on the thermal prehistory of the object under study was found. The results were interpreted on the basis of the decisive role of the molecular mobility and free volume for the predominance of the radiation cross-linking of the molecules. Correlations were established between the characteristics of the thermal transitions and the mechanical properties of the irradiated polymers.     

Differential scanning calorimetry (DSC) of semicrystalline polymers

Differential scanning calorimetry (DSC) is an effective analytical tool to characterize the physical properties of a polymer. DSC enables determination of melting, crystallization, and mesomorphic transition temperatures, and the corresponding enthalpy and entropy changes, and characterization of glass transition and other effects that show either changes in heat capacity or a latent heat. Calorimetry takes a special place among other methods. In addition to its simplicity and universality, the energy characteristics (heat capacity C _P and its integral over temperature T—enthalpy H), measured via calorimetry, have a clear physical meaning even though sometimes interpretation may be difficult. With introduction of differential scanning calorimeters (DSC) in the early 1960s calorimetry became a standard tool in polymer science. The advantage of DSC compared with other calorimetric techniques lies in the broad dynamic range regarding heating and cooling rates, including isothermal and temperature-modulated operation. Today 12 orders of magnitude in scanning rate can be covered by combining different types of DSCs. Rates as low as 1 μK s⁻¹ are possible and at the other extreme heating and cooling at 1 MK s⁻¹ and higher is possible. The broad dynamic range is especially of interest for semicrystalline polymers because they are commonly far from equilibrium and phase transitions are strongly time (rate) dependent. Nevertheless, there are still several unsolved problems regarding calorimetry of polymers. I try to address a few of these, for example determination of baseline heat capacity, which is related to the problem of crystallinity determination by DSC, or the occurrence of multiple melting peaks. Possible solutions by using advanced calorimetric techniques, for example fast scanning and high frequency AC (temperature-modulated) calorimetry are discussed.     

Differential scanning calorimetry study of Ge1−xSnxSe2.5 glasses

The glass-forming tendency and specific heat in ice cold water-quenched Ge_1?xSn_xSe_2.5 glassy alloys with 0H _f, the heat ΔH _c associated with the crystallization of an amorphous phase and the glass transition temperatureT _g were deduced from the DSC curves. The composition dependence of glass forming ability,T _g and crystallization behavior has been discussed.     

Differential scanning calorimetry and Fourier transform infrared spectroscopic studies of phospholipid organization and lipid-peptide interactions in nanoporous substrate-supported lipid model membranes

High-sensitivity differential scanning calorimetry was utilized to examine whether lipids capable of forming an inverted nonlamellar hexagonal II (HII) phase can be deposited into nanoporous substrate-supported arrays. Particularly, we compare the thermotropic phase properties of nanoconfined unsaturated 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine lipid bilayers with unsupported dispersions to assess nanoconfinement effects, focusing on the lamellar fluid (Lalpha) to HII phase transition. Experimental results provide direct and clear evidence for the formation of an HII phase upon both heating and cooling. However, a small shift in the Lalpha/HII phase transition temperature, as well as an increase in the magnitude of the associated temperature hysteresis, was observed in the nanoporous substrate-supported system. Additionally, nanoconfinement effects on the interaction and location of the antimicrobial peptide gramicidin S (GS) with nanoporous substrate-supported cardiolipin bilayers were examined by Fourier transform infrared spectroscopy as a function of temperature and phospholipid phase state. Upon heating, GS molecules began to insert into nanoconfined, substrate-supported cardiolipin bilayers at lower temperatures relative to the gel/liquid-crystalline phase transition temperature than into unsupported bilayers. The reduction in the polarity and hydrogen-bonding potential environment of GS in the Lalpha state suggests that GS is located at the polar/apolar interfacial region in both supported and unsupported cardiolipin bilayers and that the capacity of GS to interact with nanoporous substrate-supported cardiolipin bilayers was not significantly hindered by nanoconfinement. These studies further demonstrate the usefulness of supported lipid bilayers inside nanoporous substrates.     

Differential scanning calorimetry study of reactions of epoxides with polyamines

The reactions of 1,2,3,4-diepoxybutane (DEPB), 1,2,7,8-diepoxyoctane (DEPO), the diglycidyl ether of 1,4-butanediol (DGEBU) and the diglycidyl ether of bisphenol A (DGEBA) with ethylenediamine (EDA), diethylenetriamine (DETA) and tetraethylene-pentamine (TEPA) have been studied with DSC only. The epoxide reactivity decreases according to the sequence: DEPO > DEPB > DGEBU > DGEBAAt low amine concentration the conversion of epoxy groups increases as the active hydrogen concentration increases, no matter which polyamine is used.From DSC dynamic measurements, according to Freeman and Carroll's treatment, the reaction activation energy is about 98 kJ/E.M.M. for a large range of polyamine/ epoxy ratios, while as calculated from isothermal experiments using Barton's equation, it is 38–42 kJ/E.M.M.

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Zusammenfassung Die Reaktion von 1.2.3.4-Diepoxybutan (DEPB), 1.2.7.8-Diepoxyoctan (DEPO) und der Diglycidyläther von 1.4-Butandiol (DGEBU) und Bisphenol A (DGEBA) mit Äthylendiamin (EDA), Diäthylentriamin (DETA) und Tetraäthylenpentamin (TEPA) wurde ausschließlich mit DSC untersucht. Die Reaktivität der Epoxide nimmt in der Reihenfolge DEPO > DEPB > DGEBU > DGEBAab. Die Konversion der Epoxygruppen steigt mit zunehmender Konzentration an aktivem Wasserstoff an, gleich welches Polyamin benutzt wird. Dynamische DSC-Messungen, ausgewertet nach Freeman und Caroll, ergeben für einen weiten Bereich des Polyamin/Epoxy-Verhältnisses eine Aktivierungsenergie von 98 kJ/E.M.M., während aus isothermen Experimenten nach Barton's Gleichung Werte von 38–42 kJ/E.M.M. berechnet werden.

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1,2,3,4- (), 1,2,7,8- (), 1,4- (), () , . : > > > . , . - - 98 /. M. M. , , 38–42 /. M. M.

     

Thermogravimetry and differential scanning calorimetry of natural and synthetic melanins

The thermal stability of natural melanins from bovine eyes, black human hair and the hard core of banana peel, synthetic melanins obtained enzymatically or by autoxidation of various precursors, and chemically modified synthetic melanins was studied by DSC and TG analysis. It was shown that the resistance of melanins to thermal degradation depends on their origin. Synthetic melanins were found to be more stable to thermal decomposition than natural melanins. Methylation of melanins caused a significant increase in thermal stability. The DSC curves of melanins reveal typical relaxation phenomena in the temperature range 293–413 K.

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Zusammenfassung Mittels DSC und TG wurde die thermische Stabilität von natürlichen Melaninen aus Rindsaugen, aus schwarzem menschlichen Haar und aus Hartteilen von Bananenschalen, weiterhin von enzymatisch oder durch Autoxidation aus verschiedenen Präkursoren synthetisierten Melaninen sowie von chemisch modifizierten synthetischen Melaninen untersucht. Es zeigte sich, daß die Beständigkeit von Melaninen gegenüber thermischem Abbau von ihrem Ursprung abhängt. Synthetische Melanine erwiesen sich in der thermischen Zersetzung als stabiler als Melanine natürlichen Ursprunges. Durch Methylierung wird eine eindeutige Steigerung der thermischen Stabilität verursacht. Im Temperaturbereich 293–413 K zeigen weisen die DSC-Kurven der Melanine typische Relaxationserscheinungen auf.

     

Differential scanning calorimetry of univalent dihydrogen phosphates and arsenates

The high temperature phase relations (20°C) of LiH₂PO₄, NaH₂PO₄, KH₂PO₄, RbH₂PO₄, CsH₂PO₄, NH₄H₂PO₄, KH₂AsO₄, RbH₂AsO₄, CsH₂AsO₄ and NH₄H₂AsO₄ have been studied. All materials decompose at higher temperatures. Solid—solid transitions are studied when present and transition temperatures, transition enthalpies, decomposition temperatures, decomposition enthalpies and decomposition products are discussed.     

Differential scanning calorimetry of spun and drawn polyester yarn

Polyester yarn spun over a range of wind-up speeds and subsequently drawn at 373 K has been characterized by differential scanning calorimetry. Samples that are constrained from shrinking during the thermal scan respond differently than samples that are free-to-shrink. In the region of intermediate orientation, the constrained samples typically show a lower cold crystallization temperature: In the region of high orientation, the constrained samples typically show a higher melting temperature. The results are quantitatively similar to those based on fibers in which the orientation is imparted directly by high speed spinning.     

Differential scanning calorimetry of sodium and potassium nitrates and nitrites

Differential scanning calorimetry (DSC) experiments were performed with NaNO₃, KNO₃, (Na,K)NO₃, NaNO₂ and KNO₂ over the temperature range 350–990 K. Endothermic peaks, indicative of decomposition reactions, were observed to occur in the single salts above their melting points. The equimolar mixture of sodium and potassium nitrate did not decompose in the temperature range specified. The nitrites began to decompose at 800±10 K. Sodium nitrate began to decompose at 840±10 K and potassium nitrate began to decompose at 820±20 K. These results were compared with previously reported differential thermal analysis investigations of NaNO₃ and KNO₃.     

Differential scanning calorimetry study of complex fluorides of titanium,niobium and tantalum

The enthalpy and temperature of the sublimation of nitrosyl fluoride or nitryl fluoride—titanium, niobium and tantalum fluoride adducts were determined from DSC measurements. A closed-cell DSC technique was employed to determine the enthalpies and temperatures and to study the dissociation reactions of some of these adducts.     

Differential scanning calorimetry of chloroquine sulphate exposed to sun,heat and ultraviolet radiation

Chloroquine sulphate, like the phosphate, is an antimalarial formulation widely used in the tropics. The stability of such formulations is therefore of interest in the combat against malaria. A DSC study has been made of the effects of exposure to the sun, heat and UV radiation on the stability of chloroquine sulphate, similarly as performed earlier for chloroquine phosphate. When freshly recrystallized from a water-acetone mixture, chloroquine sulphate exhibits two endothermic peaks, at 169.4° and 204.7°, for the expulsion of crystal water (one molecule) and for the melting process, respectively. The exposure of chloroquine sulphate to the sun, heat and UV radiation leads to splitting of the peak for melting.

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Zusammenfassung Chloroquine-Sulfat ist ebenso wie das entsprechende Phosphatderivat ein in den Tropen weitverbreitet angewandtes Antimalaria-Präparat. Die Stabilität dieses Präparates hat damit Bedeutung für die Malariabekämpfung. Die vorliegende Arbeit ist eine Erweiterung einer Untersuchung über den Effekt der Einwirkung.von Sonne, Hitze und UV-Strahlen auf die Stabilität von Chloroquine-Phosphat auf Chloroquine-Sulfat. Aus Wasser-Aceton-Mischungen frisch kristallisiertes Chloroquine-Sulfat zeigt zwei endotherme Peaks bei 169,4 und 204,7 °C, die durch Abgabe von Kristallwasser (ein Molekül) bzw. durch den Schmelzvorgang bedingt sind. Wird Chloroquine-Sulfat der Sonne, Wärme oder UV-Licht ausgesetzt, so wird der dem Schmelzvorgang zuzuscheibende Peak aufgespalten.

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, -, , . . , . , , 169,4 204,7°, , , . , .

     

Differential scanning calorimetry study of reactions of phenyl glycidyl ether with phosphoric acid

The reactions of phenyl glycidyl ether (PGE) with phosphoric acid in three molar ratios have been studied by means of DSC alone. The results obtained from isothermal measurements are as follows:H=–91.0 kJ/mole PGE(1:1 molar ratio);H=–100.5 kj/mole PGE (1:2/3 molar ratio).The DSC curves obtained from dynamic experiments are multipeaked and giveHvalues higher than those obtained from isothermal measurements. These results can be explained by taking into account the acid concentration, the different reactivities of the hydrogens of the phosphoric acid and the possibility that secondary reactions occur.

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Zusammenfassung Die Reaktion von Phenylglycidyläther (PGE) mit Phosphorsäure wurde bei drei verschiedenen molaren Verhältnissen allein mittels DSC untersucht. Isotherme Messungen ergaben folgende Werte:H=–91.0kJ/mol PGE (molares Verhältnis 1:1);H=–100.5 kJ/mol PGE (molares Verhältnis 3:2). Die bei dynamischen Experimenten erhaltenen DSC-Kurven weisen viele Peaks auf und ergebenH-Werte, die größer als die durch isotherme Messungen erhaltenen sind. Diese Ergebnisse können erklärt werden, wenn die Säurekonzentration, die unterschiedliche Reaktivität der Wasserstoffatome der Phosphorsäure und die Möglichkeit des Verlaufs sekundärer Reaktionen in Rechnung gestellt werden.

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() () . 11 12/3, H, –91.0 –100.5 ·^–1. , , H . , , .

     

Differential scanning calorimetry of hydrogen peroxide and hydrogen peroxide-treated lignocellulose. I. Ambient pressure conditions

The decomposition reaction of aqueous solutions of hydrogen peroxide was examined by DSC at ambient pressure, and the heat of evaporation of H₂O₂ was determined. The reaction parameters for the oxidation reaction of lignocellulose (wood powder) with hydrogen peroxide were also examined. The pans made from gold and alodined (pyrophosphate /fluoride treated) aluminum were unsuitable for the work due to surface catalysis, in contrast to pure aluminum which proved to be acceptable within the temperature range examined. In pans made from pure aluminum, the reaction between lignocellulose and hydrogen peroxide takes place after the latter evaporates, i.e. it represents a gas—solid reaction.     

Differential scanning calorimetry and the advanced solidification processing of metals and alloys

This paper describes some examples of the use of differential scanning calorimetry (DSC) in providing information for advanced solidification processing of metals and alloys. Spray forming, squeeze casting, grain refinement and crystallization of amorphous alloys are all discussed. DSC measurements are shown to be valuable for testing kinetic theories of nucleation and growth, and validating solidification process models.     

Differential scanning calorimetry study of fluoride complexes of germanium,tungsten, uranium,lithium and gallium

The enthalpy and temperature of the sublimation, transition and dissociation of nitrosyl fluoride-germanium, tungsten, uranium, lithium and gallium fluoride adducts were determined from DSC measurements. A closed-cell DSC technique was employed for this purpose and to postulate possible reaction mechanisms of the dissociation.     

Differential scanning calorimetry studies of irradiated polyethylene: I. Melting temperatures and fusion endotherms

The effect of ionizing radiation on the melting behavior of high-density and low-density polyethylene was examined with data obtained by differential scanning calorimetry. Melting temperatures and fusion endotherms were obtained after absorbed doses of gamma radiation up to 3 MGy. The changes in melting temperatures and heat of fusion for the first and second meltings are related to the radiation chemistry of polyethylene. The changes in the first melting temperature are caused by radiation-induced links that decrease the melt entropy and increase the flod surface free-energy-per-unit area of chain-folded polyethylene crystals. These effects are dependent on the lamellar thickness distribution and on the types of links formed (intramolecular or intermolecular). The changes in melting temperature and heat of fusion obtained in the second melting are related to the inhibition of crystallization caused by the presence of radiation-induced links.     

Differential scanning calorimetry studies of irradiated polyethylene: II. The effect of oxygen

The effect of absorbed doses of ionizing radiation up to 2MGy in the presence of air on the melting behavior of high- and low-density polyethylene was analyzed from data obtained by differential scanning calorimetry. Thermal measurements were made during the first melting after irradiation. The first melting temperature of polyethylene irradiated in air decreased with increasing absorbed dose. Above approximately 0.6 MGy bimodal endotherms were observed for high-density polyethylene. The heat of fusion remained unchanged after irradiation in air for absorbed doses of less than 2 MGy. Bimodal endotherms were not obtained for low density polyethylene samples irradiated in air. The changes in melting temperature and the appearance of bimodal endotherms are related to the radiation chemistry of polyethylene in the presence of oxygen.