The effect of humidity on thermal process of zinc acetate

The thermal decomposition of zinc acetate dihydrate Zn(CH₃CO₂)₂·2H₂O in some humidity-controlled atmospheres has been successfully investigated by novel thermal analyses, which are sample-controlled thermogravimetry (SCTG), thermogravimety combined with evolved gas analysis using mass spectrometry (TG–MS) and simultaneous measurement of differential scanning calorimetry and X-ray diffractometry (XRD–DSC). The thermal processes of anhydrous zinc acetate in dry gas atmosphere by conventional linear heating experiment initiated with the sublimation around 180 °C, followed by the fusion and the decomposition over 250 °C. SCTG was useful to interpret clearly the successive reaction because the high-temperature parallel decompositions were effectively inhibited. The thermal behavior changed dramatically by introducing water vapor in the atmosphere and the thermal process was quite different from that in dry gas atmosphere. Zinc oxide (ZnO) was formed only in a humidity-controlled atmosphere, and could be easily synthesized at temperatures below 300 °C. XRD–DSC equipped with a humidity generator revealed directly the crystalline change from Zn(CH₃CO₂)₂ to ZnO. A detailed thermal process of Zn(CH₃CO₂)₂·2H₂O and the effect of water vapor are discussed.     

Synthesis of tridimensional polymers by the copolymerization of phenylglycidylether with aromatic diglycidylethers

Copolymers from phenylglycidylether and several aromatic diglycidylethers are prepared using different ratios of difunctional comonomers and the AIP/ZnCl₂ initiator system. It is found that the percentage of incorporated comonomer depends on the nature of the aromatic moiety introduced. The copolymers are characterized by ¹³C-NMR spectroscopy and turn out to be completely regular and with a high degree of isotacticity (about 80%) that confirms the high degree of regio- and stereoselectivity of the initiator system used. The thermal characteristics of copolymer networks are investigated using differential scanning calorimetry and thermogravimetry. Two fusion endotherms are observed which vary with the degree of crosslinking. By thermogravimetric analyses the thermal stability is found to increase when the crosslinking degree does. © 1994 John Wiley & Sons, Inc.     

Interaction of water with the regenerated cellulose membrane studied by DSC

One to three endothermal peaks atributted to melting of bulk and interfacial water were observed by DSC in the regenerated cellulose — water system. The profiles of thermal effects depend on water content, time of conditioning, film pretreatment and the conditions applied during the preceding freezing-thawing cycles. The occurrence might be deduced of melting-crystallisation processes. A large amount of non-freezable strongly bounded water was also detected. Although cellulose absorbs water quickly after immersion, the structural changes consisting on ordering of polymer fraction occur during further conditioning due to increase in strength of water binding. Using the membranes in the separation module at 90°C causes weakening of these bonds. Differences between interaction of particular cellulose films with water can be detected during the first, the second and the third heating. This revised version was published online in July 2006 with corrections to the Cover Date.     

DETECTION OF T_g BY MODULATED DIFFERENTIAL SCANNING CALORIMETRY

The glassy transition of the polyethylene terephthalate (PET) sampleswhich have been subjected to solvent induced crystallization (SINC) was investigated bymodulated differential scanning calorimetry (MDSC) and density measurement. The dif-ferential of heat capacity signal, d C_p/dT from MDSC, was used to monitor the SINCprocess. It reveals that the T_g temperature shifts to higher value with the advancement ofSINC. When the toluene-immersing time was longer (168h), the detection of T_g becomemore difficult, because some smaller peaks emerged at the lower temperatures and theseare explained as the movement of small segments in the amorphous region. These observedresults are due to the morphology and structure introduced by the SINC process.     

The influence of hydroxyapatite modification on the cross-linking of polydimethylsiloxane/HAp composites

Hydroxyapatite (HAp) was modified by the action of various hydrophobic agents based on silicon-containing compounds. The influence of the type of applied agent on the thermodynamic and kinetic parameters of the cross-linking of poly(dimethyl siloxane)/HAp composites was investigated. All the modified HAp particles became hydrophobic and these samples were used to synthesize the polysiloxane/hydroxyapatite composites (PDMS/HAp). The possible modes of interaction between the hydroxyapatite and hydrophobing agents were discussed. The most probable interaction between hydroxyapatite and the applied hydrophobing agents is hydrogen bonding. PDMS/HAp composites were formed directly in the cell of the DSC and cross-linking was investigated in situ. It was determined that the introduction of hydroxyapatite into polysiloxane matrices changed the enthalpy of cross-linking, as well as the activation energy of cross-linking and reaction order, while the introduction of modified HAp led to thermodynamic and kinetic parameters more similar to those of the cross-linking of unfilled elastomer.     

Thermal analysis and X-ray studies of chiral ferroelectric liquid crystalline materials and their binary mixtures

Summary Thermal properties of a homologous series of ferroelectric liquid crystals S-(-)-[4-(2-n-alkoxy-propionyloxy)]biphenyl-4'-[n-alkoxy-(3,5-dimethyl)]benzoate have been investigated by polarizing optical microscopy and differential scanning calorimetry. The mesophases were identified and confirmed by X-ray too. Three binary mixtures were prepared from the individual homologues. In one of the mixtures (Mix1), the ferroelectric SmC* phase has broadened and became enantiotropic. This mesophase remained monotropic in the other two mixtures (Mix2, Mix3). The chiral nematic N* phase did not appear in Mix1, but remained monotropic for the other two mixtures. Two molecular parameters, the layer spacing and the average intermolecular distance have been calculated from the X-ray results for the homologues and their mixtures. An intercalated tail-to-tail packing of molecules was found both in the single compounds and their mixtures resulting in the layer spacing about half of the molecular length of the single compounds.     

Thermal Stability of a Para-Cresol Novolac Resin

The thermal stability of p-cresol novolac resin was studied by means of DSC, X-ray diffraction, thermogravimetry and SEC investigations. After 30 thermal cycles in which the same sample was heated, cooled and heated again, without attainment of the temperature of degradation at any time in the experiment, important structural modifications are observed. At the end of the experiments, the resin, which is initially highly crystalline, exhibits all the characteristics of a semi-crystalline material. This revised version was published online in July 2006 with corrections to the Cover Date.     

The Glass Transition of Water and Aqueous Systems

After a brief introduction of the terms supercooling, amorphous solid state, glass transition and devitrification, the known ways of production of amorphous solid water are discussed. DSC experiments with quench cooled aqueous solutions show the phenomenon of glass transition and devitrification.This revised version was published online in November 2005 with corrections to the Cover Date.     

Thermoanalytische Charakterisierung Strahlengehärteter Polymerfilme

Thermo-oxidative and thermo-mechanical stabilities of radiation-cured acrylates and epoxides were examined by TG, DMA and DSC.The polymeric trifunctional acrylates PETIA, TMPTA and THEIC displayed the highest temperatures of onset of degradation. The high crosslinking density of the films resulted in an almost temperature-independent complex E-modulus, as measured by DMA. With increasing degree of ethoxylation or propoxylation of the monomers, decreases in thermal stability and strength were found. For difunctional polymeric acrylates and epoxides, the glass transition temperature was measured.The average degree of curing of UV-cured epoxy films can be determined from the temperature of the maximum in the loss modulus (E_max.This revised version was published online in November 2005 with corrections to the Cover Date.     

Influence of transcrystallinity on DSC analysis of polymers

Intense parasitic nucleation has been observed at the surface of differential scanning calorimetry samples for various polymers, whereas their crystallization traces exhibit complex shapes. Revisited overall kinetics theories and computer simulation, taking into account small thickness of samples and transcrystallinity effects, allow to explain and reproduce experimental ‘double peaks’, currently observed with polyamide 6-6. The beginning of the transformation and the main peak are attributed to surface and bulk nucleations, respectively. As a consequence, any DSC experiment should be followed by a microscopic observation and more accurate models including thermal gradients and resistances should be developed for their interpretation.