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  • oxidation  (64)
  • DSC  (58)
  • Springer  (122)
  • 2000-2004  (122)
  • 1965-1969
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  • Springer  (122)
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  • 1
    ISSN: 1572-879X
    Keywords: oxidation ; reduction of palladium catalysts ; chlorine effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Pd–chloride precursor salt was used to prepare Pd/Al2O3 catalysts. TPSR measurements showed three distinct reactions for the oxidation of propane on palladium surface under excess of hydrocarbon: complete oxidation, steam reforming and propane hydrogenolysis. Propane oxidation on palladium catalysts was related to the Pd2+ sites observed on Pd/Al2O3 through infrared of adsorbed carbon monoxide. In fresh catalysts reduced by H2, the IR spectra showed the linear and bridge adsorbed CO species on the Pd0 surface. After propane reaction, a new band at 2130 cm-1 related to CO adsorption on Pd2+ species was noted. Carbon monoxide species adsorbed on Pd0 were also observed in all samples after reaction. Our results suggest surface ratios of Pd0/PdO during the propane oxidation. On the other hand, time on stream conversions of the complete oxidation of propane were affected by either the water generated during the reaction or added as a reactant at 10 vol%. The water generated by the reaction helped to eliminate chlorine residues in the form of oxychloride species leading to an increasing of the activity. However, the presence of water into the reaction mixture caused a strong decreasing of the activity. The inhibition mechanism of propane oxidation in the presence of water consisted in the dissociative adsorption of water on palladium sites with the possible formation of palladium hydroxide (Pd–OH) at the surface, diminishing the number of active surface sites. Dynamic fluctuations into the reaction conditions supported the idea that a pseudo‐equilibrium adsorption–desorption of water was reached. After water removal or increasing in the reaction temperature the equilibrium was shifted to the direction of OH–Pd decomposition. This behavior suggests that the inhibitory effect of water is a reversible phenomenon, being a function of the amount of water and the reaction temperature.
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  • 2
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    Journal of thermal analysis and calorimetry 61 (2000), S. 719-730 
    ISSN: 1572-8943
    Keywords: DSC ; TSDC ; unsaturated polyester resin ; X-ray fluorescence spectroscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This work reports on the curing kinetics of unsaturated polymer resins (UPRs) cured with styrene, studied by differential scanning calorimetry and Fourier transform infrared spectroscopy. The data lead to determination of the experimental conditions with which to obtain a fully cured material and open the way for study of the relaxation phenomena by means of thermally stimulated depolarization current analysis (TSDC). In relaxation studies on fully cured resins, the TSDC spectra revealed important overlapping of the main relaxation peak with an extra upper peak. The importance of this extra peak a priori prevents further analysis of the main relaxation. To identify the origins of this peak (space charge or other), the purity of the resin was checked by X-ray fluorescence spectroscopy. The use of UPR specimens with different compositions (in terms of the resin/activator/initiator ratio) demonstrated that the bulk of the impurities Cl, K, Ca, Sr, Zr and Ba are due to the promoter. Decoupling of the mixed peaks (α-relaxation and extra) revealed that the a peak is independent of the proportion of the promoter in the resin and that the extra peak is principally due to the presence of these impurities.
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  • 3
    ISSN: 1572-8943
    Keywords: chiral complex ; DSC ; hydrate ; optical resolution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal behaviour of O,O'-dibenzoyl-(2R,3R)-tartaric acid (DBTA), its monohydrate, and its potential supramolecular compounds with achiral alcohols and phenols were investigated with TG, DSC, EGD. The structural differences among the anhydrous DBTA, its monohydrate, and the supramolecular derivatives were investigated with X-ray powder diffraction. The thermal behaviour of DBTA-supramoleculars with isopropyl, tert-butyl, and 5-cyclohexyl alcohols is found to be similar to each other but essentially different from that of both DBTA and its monohydrate. On heating they melt and decompose between 60–180°C while they loose in one or two steps the bound alcohol. The thermal stability of the supramolecular compounds increases with the boiling point of the alcohol component. According to the X-ray powder diffraction patterns each supramolecular substance has different structure, that may also result in the different thermal stability of the compounds. The molar ratio of DBTA:achiral alcohol samples is 1:1.01–1:1.57 estimated from the corresponding mass losses. The XRD patterns of the prepared two DBTA-phenol materials are different from those of DBTA-achiral alcohol samples. The phenol compounds melt with slow mass losses and give an endothermic peak between 73–83°C but the melting point of the anhydrous DBTA cannot be observed. DBTA:phenol molar ratio is estimated to be 1:0.41 and 1:0.65 for phenol and 2-methylphenol, respectively.
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  • 4
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    Journal of thermal analysis and calorimetry 61 (2000), S. 731-743 
    ISSN: 1572-8943
    Keywords: DSC ; phase transition ; phospholipid ; phthalates ; plasticizers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Phthalic acid esters, and in particular bis-2-(ethylhexyl) phthalate, are common environmental contaminants with long-term toxic and carcinogenic effects that readily dissolve in lipid substances. DSC measurements of hydrated multilamellar dipalmitoyl phosphatidylcholine liposomes in the presence of different amounts of bis-2-(ethylhexyl) phthalate, dioctyl phthalate, dibutyl phthalate (DBP) and diethyl phthalate (DEP) were considered. The effects on the main transition temperature, ΔH, and the shape and width of the transition were studied. A decrease in Tm, without an accompanying decrease in ΔH,and increases in both the asymmetry and the width of the main transition peak were observed. In some cases, the calorimetric curve showed complex peak structures arising from the coexistence of various aggregates of different sizes. This was particularly evident in the liposomes with DEP and DBP contents ranging from 5.0 to 7.5% m/m. For all the considered model systems, the effects were noticeable even in the presence of small amounts of phthalates; in the presence of greater amounts, the overall structure of the bilayer was in some cases strongly modified, with the appearance of new different phases. Since the function of a membrane-associated protein is dependent on the lipid structure, phthalates could modify the function by modifying the membrane structure.
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  • 5
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    Journal of thermal analysis and calorimetry 61 (2000), S. 805-818 
    ISSN: 1572-8943
    Keywords: aluminium ; ARC ; DSC ; kinetics ; nanometric size ; SDT ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal properties of Alex, a nanosized Al powder, were determined using various techniques, including DSC, TG, simultaneous TG-DTA (SDT) and accelerating rate calorimetry (ARC). The results demonstrate that the specific heat capacities of nano and micron size Al powders are similar between 30 and 400°C. Dynamic and isothermal methods were used to determine the kinetic parameters for the oxidation reaction of Alex, which was detected at an onset temperature of 481°C. The results obtained were in good agreement with each other. From the ARC experiments, exotherms were detected near 340 and 260°C for experiments started at ambient pressure and at 0.72 MPa, respectively.
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  • 6
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    Journal of thermal analysis and calorimetry 62 (2000), S. 51-62 
    ISSN: 1572-8943
    Keywords: DSC ; kinetic models ; protein denaturation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract New approaches to the analysis of differential scanning calorimetry (DSC) data relating to proteins undergoing irreversible thermal denaturation have been demonstrated. The experimental approaches include obtaining a set of DSC curves at various scanning rates and protein concentrations, and also reheating experiments. The mathematical methods of analysis include construction of a linear anamorphosis and simultaneous fitting of a theoretical expression for the dependence of the excess heat capacity on temperature to a set of experimental DSC curves. Different kinetic models are discussed: the one-step irreversible model, the model including two consecutive irreversible steps, the Lumry and Eyring model with a fast equilibrating first step, and the whole kinetic Lumry and Eyring model.
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  • 7
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    Journal of thermal analysis and calorimetry 62 (2000), S. 715-719 
    ISSN: 1572-8943
    Keywords: computer simulation ; DSC ; non-isothermal crystallization kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The applicability of the kinetic analysis of data obtained by non-isothermal differential scanning calorimetry (DSC) is discussed. The Johnson-Mehl-Avrami (JMA) model was used for the computer simulation of DSC traces subsequently analysed by common methods of kinetic analysis of non-isothermal data. For the temperature-independent kinetic exponent n of the JMA equation, the kinetic analysis was shown to provide correct results, e.g. a correct kinetic model and apparent activation energy. On the other hand, for the temperature-dependent kinetic exponent, there is a great possibility of erroneous determination of the correct kinetic model and apparent activation energy, especially at higher heating rates. Since the temperature dependence of n cannot be determined on the basis of non-isothermal DSC experiments, conclusions must be drawn with appropriate caution.
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  • 8
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    Journal of polymer research 7 (2000), S. 257-266 
    ISSN: 1572-8935
    Keywords: Poly(ether sulfone) ; Epoxy resin ; Physical aging ; DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Abstract The physical aging process of 4-4′-diaminodiphenylsulfone (DDS) cured diglycidyl ether bisphenol-A (DGEBA) blended with various molecular weights of poly(ether sulfone) (PES; Mn = 28,600, 10,600, and 6,137) was studied by DSC. For DGEBA/DDS system blended with a low MW PES-3 (Mn = 6,137), no phase separation of the polymer blend and only one enthalpic relaxation process due to physical aging was observed. Since the high MW PES-1 (Mn = 28,600) had a Tg close to that of fully cured DGEBA/DDS, the fully cured DGEBA/DDS/PES-1 blend had a broader glass transition than a neat DGEBA/DDS system. However, the DSC results showed two enthalpic relaxation processes due to the physical aging of PES-rich and cured epoxy-rich phases as the material was aged at 155 °C (30 °C below Tg). Since the Tgs of PES-1-rich and epoxy-rich phases overlapped with each other, the enthalpic relaxation processes corresponding to each phase coupled to each other in the earlier stage of physical aging. The medium MW PES-2 (Mn = 10,600) has a much lower Tg than that of fully cured DGEBA/DDS, two well separated Tgs were observed for the cured DGEBA/DDS/PES-2 blend, indicating the cured epoxy was immiscible with PES. Aging the polymer blend at 155 °C (24 °C below Tg1 of the PES-2-rich phase and 53 °C below Tg2 of the epoxy-rich phase) produced two well separated relaxation processes due to PES-2-rich and epoxy-rich phases. The experimental results suggested that aging the polymer blend at a suitable temperature would improve the phase separation between PES-1-rich and epoxy-rich phases.
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  • 9
    ISSN: 1572-879X
    Keywords: alkylbenzene ; toluene ; ethylbenzene ; xylene ; mesitylene ; p‐ethyltoluene ; cumene ; p‐cymene ; oxidation ; palladium ; 1,10‐phenanthroline
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Only the side‐chain oxidation of alkylbenzenes (R–C6H3–R′–R″ R=H, Me, Et, Pri R′=H, Me; and R″=H, Me) by oxygen (35–50 atm, 200)C° is promoted in the presence of [Pd(phen)(OAc)2].
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  • 10
    ISSN: 1572-879X
    Keywords: methane ; oxidation ; aliphatic hydrocarbons ; zeolite ; recycle reactor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Conversion of methane in high yields to C4+ nonaromatic hydrocarbons was demonstrated in a recycle system. The principal components of the recycle system included an oxidative coupling reactor with a Mn/Na2WO4/SiO2 catalyst at 800°C for conversion of methane to ethylene, and a reactor with an H-ZSM-5 zeolite at 275°C for subsequent conversion of ethylene to higher hydrocarbons. Total yields of C4+ products were in the range of 60–80%, and yields of C4+ nonaromatic hydrocarbons were in the range of 50–60%.
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  • 11
    ISSN: 1572-9028
    Keywords: oxidation ; oxyacetoxylation ; alloy ; palladium ; bismuth ; benzylacetate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Benzylacetate synthesis from toluene, acetic acid and oxygen on Pd–Bi binary catalyst was studied in the liquid phase. By incorporation of Bi with Pd, both the activity and selectivity were improved. Especially better stability was obtained with the catalyst having Pd/Bi = 3. Deactivation of the catalyst was investigated in detail by XRD, XPS, TEM, elemental analysis, EPMA and so on. Comparing the used catalyst with the fresh one, it was indicated that the main cause of deactivation was the dissolution of Pd into the reaction mixture from the most outer surface of the catalyst. By adopting proper reaction conditions to prevent the Pd dissolution, the catalyst having Pd/Bi = 3 was suggested to be used as an industrial catalyst.
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  • 12
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    International journal of infrared and millimeter waves 21 (2000), S. 31-37 
    ISSN: 1572-9559
    Keywords: HgCdTe ; oxidation ; surface treatment ; passivation ; XPS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Abstract This report presents a surface pre-treatment method of LPE HgCdTe epilayer to reduce and remove the oxides and contaminants. The surface oxidative characterization of LPE HgCdTe epilayer has been studied by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). HgCdTe surface exposed by various processing steps has been measured and analyzed, the results show the native oxide film can be removed by the solution of lactic acid in ethylene glycol after etching by bromine in absolute ethyl alcohol. It indicates that the mainly optical and electrical parameters of LPE HgCdTe epilayer have not been changed. It is evident that the pre-treatment before HgCdTe surface passivation affects the passivant/HgCdTe interface properties.
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  • 13
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    Catalysis letters 64 (2000), S. 113-118 
    ISSN: 1572-879X
    Keywords: X‐ray photoelectron spectroscopy (XPS) ; scanning electron microscopy (SEM) ; silver ; oxidation ; surface chemical reaction ; NO ; NO x
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The behavior of a AgNO3/Ag2O/Ag “sandwich” upon heating in vacuum was studied by in situ X‐ray photoelectron spectroscopy (XPS) and ex situ scanning electron microscopy (SEM). The AgNO3/Ag2O/Ag “sandwich” was prepared by exposure of a silver foil to a NO : O2 mixture. The upper layer of the “sandwich” consists of AgNO3 crystals of a mean size between 0.1 and 0.4 μm. Heating at 550 K in vacuum results in melting of the AgNO3 crystals. A liquid film of AgNO3, readily wetting the silver, covers the surface. Cooling below the melting point of AgNO3 leads to the agglomeration of silver nitrate to long islands with a size reaching a few tens of micrometers (μm). The possible effects of AgNO3 liquid‐phase formation on surface processes are discussed.
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  • 14
    ISSN: 1572-879X
    Keywords: chlorinated hydrocarbons ; chromia ; titania ; alumina ; CVOCs ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of perchloroethylene (PCE) was investigated over chromium oxide catalysts supported on TiO2, Al2O3, SiO2, SiO2–Al2O3 and activated carbon. The phase of chromium oxide on the catalyst surface is critical for the oxidation of PCE. The catalytic activity of PCE removal enhances as the formation of Cr(VI) species on the catalyst surface increases. The surface area and the type of the catalyst supports were also essential for high performance in the PCE oxidation. In addition, the structure of Cr(VI) on the catalyst surface also plays an important role for the decomposition of PCE. The polymerized Cr(VI) mainly formed by the interaction of metals with the support is the active reaction site for the present reaction system. CrOx/TiO2 reveals the strongest PCE removal activity among the catalysts examined in the present study.
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  • 15
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    Topics in catalysis 11-12 (2000), S. 359-367 
    ISSN: 1572-9028
    Keywords: zeozyme ; encapsulated complexes ; copper acetate ; copper dimers ; enzyme mimic ; EPR of copper ; tyrosinase ; oxidation ; oxygenase ; tyrosine oxidation ; phenol oxidation ; hydroxylation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxygenase mimicking activity of copper acetate dimers in the regioselective ortho-hydroxylation of L-tyrosine to L-dopa is enhanced on encapsulation in zeolite Y. The structure and magnetic properties of the catalytic active site were characterized by EPR spectroscopy. The spectra of this “zeozyme” reveal the presence of (1) copper acetate dimers in the supercages and (2) isolated Cu(II) ions in the sodalite cages of the zeolite. There are significant differences in the EPR spectra of the “neat” and encapsulated complexes: on encapsulation in zeolite, the Cu–Cu exchange coupling constant, −, increases to 310 from 259 cm−1 for the “neat” complex (i.e., by about 19.7%). Simultaneously the Cu–Cu separation in the dimer, estimated indirectly from the exchange coupling constant, shortens to 2.40 Å in the encapsulated state from 2.64 Å in the “neat” complex. There is, hence, a relatively greater overlap of the metal orbitals of the dimer copper atoms inside the restricted confines of the zeolite cages. The consequent, enhanced, trans axial lability of the phenolate and dioxygen ligands promotes the catalytic oxygenase activity of copper acetate dimers on encapsulation in zeolites. A causal relationship between changes in the structural features of an active site on encapsulation in the zeolite and the corresponding catalytic activity has, thus, been established.
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  • 16
    ISSN: 1572-9028
    Keywords: nitric oxide ; ammonia ; oxidation ; X-ray photoelectron spectroscopy ; scanning tunnelling microscopy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The dissociative chemisorption of nitric oxide at Cu(110) has been shown to result in rapid ordering of oxygen adatoms as (2×1)O chains oriented along the 〈100〉 direction while the associated nitrogen adatoms are mainly disordered at 295 K. Surface diffusion of the N adatoms, following bond cleavage, is activated and ordering of the (2×3)N strings occurs on heating to 430 K. A number of distinct reaction pathways have been isolated during the oxidation of ammonia resulting in the formation of either chemisorbed imide or nitrogen adatoms. The latter depending on temperature, may exhibit a (2×3)N, a (3×3)N or both structures may exist simultaneously. The concentration of nitrogen in the complete (2×3)N structure has been determined to be 6.6×1014 cm-2, with only a 25% decrease in nitrogen concentration leading to the transformation to the (3×3)N structure. The oxygen atoms at a Cu(110)–O overlayer, and present at the ends of the (2×1) strings terminating in steps, show specific reactivity when exposed to ammonia at 375 K resulting in the “decoration” of the steps with imide species while the oxygens within the (2×1) strings remain unreactive.
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  • 17
    ISSN: 1573-904X
    Keywords: methionine-enkephalin ; oxidation ; solid state ; secondary ion mass spectrometry ; peptide stability ; methionine
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Purpose. A surface sensitive mass spectrometric technique: Time ofFlight Secondary Ion Mass Spectrometry (ToF-SIMS) was introducedto study the solid state instability of a methionine containing peptidecaused by the oxidation of the methionine residue. Methods. The oxidation of a neuropeptide Methinonine-Enkephalin(ME) in air and under UV acceleration was studied by ToF-SIMS. Results. The apparent oxidation rate is defined by the peak ratio ofoxidized molecular ion over unoxidized molecular ion. ME is oxidizedat a faster rate to its sulfoxide derivative in the UV accelerated oxidationenvironment than in lab air. The calibration curve for evaluating theionization probability ratio of the oxidized deprotonated molecular iondivided by the unoxidized deprotonated molecular ion was obtained.This could be used to extract the real oxidation rate of ME in thesolid state. Conclusions. The preliminary results showed that ToF-SIMS with simplesample handling, fast data acquisition, together with excellentsurface sensitivity and detection limit could be an applicable and convenienttool to study peptide reactions in the solid state such as oxidationand deamidation process.
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  • 18
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    Chemistry of natural compounds 36 (2000), S. 416-417 
    ISSN: 1573-8388
    Keywords: cotton lignin ; oxidation ; redox catalysts
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effects of anthraquinone and demethylated lignin on the oxidation of cotton lignin are compared. Results of the estrogen activity of certain aromatic acids are presented.
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  • 19
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    Chemistry of heterocyclic compounds 36 (2000), S. 870-871 
    ISSN: 1573-8353
    Keywords: sesquiterpene lactones ; britanin ; bigelovin ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
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  • 20
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    Chemistry of heterocyclic compounds 36 (2000), S. 885-898 
    ISSN: 1573-8353
    Keywords: 2,3-dihydroimidazo[1,2-a]pyridines ; reduction ; nucleophilic reactions ; oxidation ; electrophilic reactions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Published data on the physical and chemical characteristics of 2,3-dihydroimidazo[1,2-a]pyridines to 1998 are reviewed.
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  • 21
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    Journal of materials synthesis and processing 8 (2000), S. 359-363 
    ISSN: 1573-4870
    Keywords: Mechanical activation ; brown coal ; electrophoretic mobility ; oxidation ; humic acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract This paper presents a study of the influence of mechanochemical activation of coal on the process of formation and degradation of humic acids. The increasing period of mechanical activation of coal causes an increase in hydrophility, electrophoretic mobility, and of electrokinetic potential of surface layers as a result of acidic carboxyl and phenolic OH groups. The effective activation requires a short period of grinding. The increased time of activation causes the secondary processes of grain agglomeration and degradation of humic acids.
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  • 22
    ISSN: 1573-4889
    Keywords: ion plating ; steel ; TiAlN coating ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract To improve the high-temperature oxidation resistance of STD61 steels used ashot dies or cutting tools, Ti0.3Al0.2N0.5films were deposited on STD61 steel substrates by arc-ion plating. Thedeposited film consisted of Ti3Al2N2 andTi2N phases. The oxidation characteristics were studied attemperatures ranging from 700 to 900°C in air. The deposited STD61steels displayed excellent oxidation resistance up to 800°C, butexhibited large weight gains and breakaway oxidation at 900°C. Theoxidation products were primarily Fe2O3, TiO, TiO2,and α-Al2O3, the relative amount of each oxidebeing dependent on the oxidation condition. Among various oxides, TiO2and α-Al2O3 were the major oxides at 800°Cfor at least up to 16 hr. However, at a higher temperature or a longeroxidation period, the significant outward diffusion of iron from thesubstrate resulted in the formation of iron oxides, together with otheroxides of Ti and Al.
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  • 23
    ISSN: 1573-4889
    Keywords: oxidation ; marginal chromia formers ; water vapor effect ; chromia evaporation ; breakaway corrosion ; flow-rate dependence ; 304L
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The effect of roman PH 2 O and flow rate on the oxidation of 304Lat 873 K in oxygen is reported. High concentrations of water vapor and highflow rates result in breakaway corrosion. The mass gain after 168 hrincreased by four to five times, compared to oxidation in dry O2. Inthe presence of H2O, the corrosion products consisted of arelatively thin (Cr,Fe)2O3 oxide plus large oxide islandsconsisting mainly of Fe2O3. A mechanism explaining theeffect of water vapor on marginal chromia formers is proposed.
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  • 24
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    Oxidation of metals 54 (2000), S. 47-62 
    ISSN: 1573-4889
    Keywords: oxygen sensor ; oxygen pump ; solid-state electrolyte ; ZrO2 ; oxygen partial pressure ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract An ultralow oxygen partial pressure-controlling system, based on solid-stateelectrochemical principles, has been developed. This system consists of anoxygen sensor and an oxygen pump and is controlled by a PC computer. Theoxygen sensor is used to measure the oxygen partial pressure in an enclosedsystem, while the oxygen pump is used to transport oxygen from the ambientair into the enclosed system or from the enclosed system to the ambientair. The operating conditions of this system have been studied. The resultsshowed that it can be used to establish a stable oxygen partial pressure inthe range of 10−18∼5×105 Pa (1×10−23∼5 atm)in the enclosed system. This system has been used to investigate theselective oxidation of the Cr and the oxide formation on the surface of aNi–Cr alloy under three different low oxygen partial pressures. Theoxide morphology was studied using atomic force microscopy (AFM). The resultsagreed well with those in the literature and also confirm the reliability of this system.
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  • 25
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    Oxidation of metals 54 (2000), S. 121-138 
    ISSN: 1573-4889
    Keywords: titanium aluminides ; oxidation ; oxygen-affected zone ; alpha case ; TEM
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The isothermal oxidation behavior of binary Ti–25 at.% Al was studiedat 1073, 1173, and 1273 K in air and oxygen with emphasis on themicrostructure of the subsurface zone underneath the external oxidescale. Thermogravimetric analysis, acoustic-emission (AE) analysis, lightmicroscopy, scanning electron microscopy (SEM), atomic force microscopy(AFM), and cross-sectional transmission electron microscopy (TEM) werecarried out. Three layers could be identified in the subsurface regionconsisting of an internal oxidation zone of α-Al2O3,and α-Ti, a ternary phase with the empirical formulaTi–21Al–15O (at.%), and an oxygen penetration zone consisting ofα2-Ti3Al(O).
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  • 26
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    Oxidation of metals 54 (2000), S. 559-574 
    ISSN: 1573-4889
    Keywords: silver–nickel ; mechanical alloying ; oxidation ; two-phase alloys
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Two nanophase Ni-base alloys containing 50 and 25 at.% Ag prepared by mechanical alloying, denoted Ni–50Ag and Ni–25Ag were oxidized in air at 600 and 700°C for 24 hr. Ni–50Ag underwent internal oxidation of nickel, associated with the formation of a continuous outermost layer of silver metal with scaling rates larger than those for pure nickel. On the contrary, Ni–25Ag formed a continuous NiO layer surmounted by a discontinuous silver layer and internal oxidation was suppressed. The oxidation rate of Ni–25Ag decreased with time much more rapidly than predicted by the parabolic rate law during the initial stage and eventually became parabolic, with rate constants much lower than those for the oxidation of pure nickel. These results are attributed to the two-phase nature and, particularly, to the very small grain size of the two alloys.
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  • 27
    ISSN: 1573-4889
    Keywords: ion implantation ; oxidation ; thermal ; stainless steel ; ion-beam analysis ; aluminum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract AISI-321 steel samples were implanted with Al ions (implantation-energy:40 keV; dose: 2×1017 ions/cm2). Thermal oxidationof the samples was performed at 450, 550, 600, and 650°C for periodsvarying from 1 to 6 days in air and in a corrosive CO2-containingenvironment. Nuclear Reaction Analysis (NRA) and Rutherford BackscatteringSpectrometry (RBS) were used to investigate the oxidized samples. Asignificant improvement of the oxidation resistance of the implantedmaterial in comparison to the nonimplanted material was observed. Thisespecially applies for samples oxidized at high temperatures. The aluminumdepth distribution determined by NRA [using the resonance at 992 keV of the27Al(p, γ )28Si nuclear reaction] and RBS,indicated no variation of the Al profile in the temperature region450–600°C, whereas at 650°C a slight Al diffusion wasobserved. Scanning electron microscopy (SEM–EDS) was applied to studythe surface morphology and the constitution of the oxide scale formed, aswell as to explain the influence of Al implantation on the oxidation behaviorof AISI-321 austenitic stainless steel.
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  • 28
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    Oxidation of metals 53 (2000), S. 467-479 
    ISSN: 1573-4889
    Keywords: Ni–5Cr–5Al ; oxidation ; magnetron sputtering ; nanocrystalline coating
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract A NiO-forming Ni–5Cr–5Al (at.%) alloy has been developed anddeposited as a sputtered nanocrystalline coating. The oxide formation andoxidation behavior of this coating have been studied at 1000°C inair. The oxidation rate markedly decreased with time and the oxidationkinetics obeyed the fourth power law. Complex oxide scales, consisting ofNiO, NiAl2O4 and α-Al2O3,were formed during 200 hr oxidation. The outer oxide layer consisted of NiOand NiAl2O4 and an inner oxide layer ofα-Al2O3. The sputtered Ni–5Cr–5Alnanocrystalline coating showed good oxidation resistance due to theformation of an α-Al2O3 inner layer andexcellent adhesion of the complex oxide scales.
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  • 29
    ISSN: 1573-4889
    Keywords: oxidation ; chromia ; alumina ; thin oxide films ; reactive element
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract In order to study the effects on oxidation behavior of changing thecomposition of oxide scales without changing the composition of theunderlying alloys, thin films, which contained various amounts of Y2O3,Cr2O3, or Al2O3 have been deposited on Fe–25%Cr andFe–25%Cr–5%Al prior to oxidation. There were major differencesbetween the (Fe–25%Cr)–(Cr2O3–Y2O3) and(Fe–25%Cr–5%Al)–(Al2O3–Y2O3) systems. A film ofCr2O3 on Fe–25%Cr reduced the oxidation rate and Cr2O3–Y2O3films reduced it still further. A film of Al2O3 onFe–25%Cr–5%Al reduced the rate considerably, butAl2O3–Y2O3 films exhibited rates that were greater than those forAl2O3 alone. A film, which consisted entirely of Y2O3, greatly decreasedthe oxidation rate of Fe–25%Cr, but increased that ofFe–25%Cr–5%Al. The changes in oxidation rate produced byY2O3 in the (Fe–25%Cr)–(Cr2O3–Y2O3) system weremuch greater than those produced in the(Fe–25%Cr–5%Al)–(Al2O3–Y2O3) system. As far asoxidation rate is concerned, the optimum amount of Y2O3 in the(Fe–25%Cr)–(Cr2O3–Y2O3) system was found to begreater than or equal to 40% and less than 100%; in theFe–25%Cr–5%Al)–(Al2O3–Y2O3) systemit was approximately 10%. In thermal-cycling tests, the resultsfor the (Fe–25%Cr)–(Cr2O3–Y2O3) system followedthe same pattern as that for the isothermal tests; a film of Y2O3reduced the oxidation rate and a film of Cr2O3–33%Y2O3reduced it still further.
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  • 30
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    Oxidation of metals 54 (2000), S. 575-589 
    ISSN: 1573-4889
    Keywords: TiAl ; oxidation ; Si3N4 ; dispersed particles
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    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The oxidation kinetics of TiAl alloys with and without 3 and 5 wt.%additions of Si3N4 particles were studied at 1173 and1273 K in 1 atm of air. The Si3N4 dispersions wereunstable in the matrix phase, so that some of them reacted with titaniumduring sintering to form Ti5Si3 and dissolvednitrogen. The oxide scale formed on TiAl–Si3N4alloys consisted of an outer TiO2, an intermediate(Al2O3+TiO2), and an inner(TiO2+Al2O3) mixed layers. The enhancedalumina-forming tendency, the presence of discrete SiO2 particlesbelow the outer TiO2 layer, and the improved scale adhesion bySi3N4 dispersions were attributable mainly to theincreased oxidation resistance compared to the Si3N4-freeTiAl alloys. Marker experiments showed that, for TiAl–Si3N4 alloys, the primary mode of scale growth was the outward diffusion oftitanium ions for the outer scale and the inward transport of oxygen ionsfor the inner scale.
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  • 31
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    Chemistry of heterocyclic compounds 36 (2000), S. 1359-1360 
    ISSN: 1573-8353
    Keywords: 1,2,5-thiadiazoles ; 1,2,5-selenadiazoles ; oxidation
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    Topics: Chemistry and Pharmacology
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  • 32
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    Reaction kinetics and catalysis letters 69 (2000), S. 31-38 
    ISSN: 1588-2837
    Keywords: MMH ; oxidation ; gas-phase ; oxygen
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The objective of this study is to characterize the lifetime of monomethylhydrazine mixed with O2, both in the gas phase, at 298 K. A detailed kinetic model has been built to allow a numerical study of the homogeneous MMH/O2 reactivity.
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  • 33
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    Reaction kinetics and catalysis letters 69 (2000), S. 247-252 
    ISSN: 1588-2837
    Keywords: Phosphorous acid ; oxidation ; kinetics ; mechanism
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of lower phosphorus oxyacids by benzyltrimethylammonium chlorobromate (BTMACB) proceeds by a mechanism involving a hydride-ion transfer from oxyacids to the oxidant in the rate-determining step.
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  • 34
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    Reaction kinetics and catalysis letters 69 (2000), S. 369-374 
    ISSN: 1588-2837
    Keywords: Thioacids ; oxidation ; mechanism ; hexamethylenetetramine-bromine
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Oxidation of thioacids by hexamethylenetetramine-bromine proceeds through an intermediate complex in the pre-equilibrium and its subsequent decomposition in the slow step.
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  • 35
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    Reaction kinetics and catalysis letters 71 (2000), S. 319-323 
    ISSN: 1588-2837
    Keywords: Benzene ; oxidation ; aqueous phase
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Aqueous phase heterogeneous catalytic oxidation of benzene by dissolved oxygen is reported. Using a bimetallic platinum-ruthenium catalyst supported on a high surface area activated carbon, good conversions were obtained at temperatures above 100°C and space-times greater than 40 seconds. Complete conversion of benzene to carbon dioxide and water was achieved at 100°C with a reactor space-time of 300 s.
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  • 36
    ISSN: 1588-2837
    Keywords: Hydrogen sulfide ; oxidation ; iron compounds
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The correlation of the state of iron in supported Fe/Al2O3 catalysts with catalytic properties in H2S oxidation, studied by Mössbauer spectroscopy, indicates that the Fe oxide particles promote the formation of sulfur, whereas FeS2 catalyzes the H2S oxidation to SO2.
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  • 37
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    Reaction kinetics and catalysis letters 71 (2000), S. 115-120 
    ISSN: 1588-2837
    Keywords: Mechanism ; oxidation ; alkylperoxo complexes ; vanadium ; NMR spectroscopy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Using 51V, 17O, 13C and 1H NMR spectroscopy, vanadium(V) alkylperoxo complexes VO(OOtBu)k(OnBu)3-k, where k = 1, 2 and 3, were characterized in the reaction of VO(OnBu)3 with tBuOOH in CH2Cl2.
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  • 38
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    Topics in catalysis 11-12 (2000), S. 195-204 
    ISSN: 1572-9028
    Keywords: 3-fluorotoluene ; 3-fluorobenzaldehyde ; iron molybdate ; Fe–Mo/boralite ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The gas-phase selective synthesis of 3-fluorobenzaldehyde from 3-fluorotoluene over bulk iron molybdate and Fe–Mo oxide in a host boralite sample is described. The latter samples, prepared by adding Fe and Mo by chemical vapor deposition to the boralite, show high selectivity in oxidation, making yields of 3-fluorobenzaldehyde of over 40% possible. The pretreatment of the zeolite to eliminate extra-framework boron improves behavior, and secondary post-addition of molybdenum by CVD to increase the Mo/Fe ratio in the catalyst has a similar enhancing effect. The behavior of Fe–Mo/boralite samples proves significantly better, in terms of both specific activity (per mass of active phase) and selectivity, than bulk Fe2(MoO4)3, but at high conversion lower selectivities are found probably due to the presence of limitations in the backdiffusion of 3-fluorobenzaldehyde.
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  • 39
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    Topics in catalysis 11-12 (2000), S. 213-222 
    ISSN: 1572-9028
    Keywords: CaO ; MgO ; carbon monoxide complexes ; oxidation ; adsorption calorimetry
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The heat evolved during the adsorption and oligomerization of CO on outgassed CaO and MgO has been determined with a heat-flow calorimeter. The chemisorbed complexes formed include highly-conjugated (CO) n 2 anions which impart colour to the oxides. The reaction of these complexes with oxygen has been quantified calorimetrically and correlated with changes observed spectroscopically.
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  • 40
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    Journal of thermal analysis and calorimetry 59 (2000), S. 83-92 
    ISSN: 1572-8943
    Keywords: cationic and photoinitiated polymerization ; DSC ; interfacial mixing ; interpenetrating polymer network (IPN) ; glass transition temperature ; NMR ; quantitative thermal analysis of phases ; reactive epoxy and acrylate systems ; Tg broadening
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this study NMR and DSC are used to probe the structure, thermal characteristics and morphology of a network formed from a diepoxide/acrylate system. Separate chemistries are employed to polymerize the diepoxide and acrylate components. The cationic polymerization of the diepoxide exhibits excellent selectivity in producing a crosslinked polyether network without affecting the acrylate monomer. Subsequent photoinitiated free-radical polymerization of the acrylate produces a phase separated, semi-interpenetrating polymer network (SIPN).
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  • 41
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    Journal of thermal analysis and calorimetry 59 (2000), S. 93-100 
    ISSN: 1572-8943
    Keywords: catalyst ; cure kinetics ; DSC ; HTPB ; kinetic compensation effect ; urethane
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The kinetics of theurethane-forming cure reaction of hydroxyl terminated polybutadiene (HTPB) with isophorone diisocyanate (IPDI) in presence of ferric tris (acetyl acetonate) (FeAA) catalyst was investigated using differential scanning calorimetry (DSC). The Arrhenius activation parameters, viz., activation energy E and pre-exponential factor A were evaluated using the non-isothermal integral Coats-Redfern equation. The cure reaction was catalysed by ferric acetyl acetonate (FeAA), as revealed from the decrease in reaction temperatures and the increase in rate constants; however, the computed activation energy did not show any correlation to the catalyst concentration. The values of E and A for the uncatalysed reaction at different heating rates showed interdependence through kinetic compensation (KC) effect. Using KC correction, E values were normalised for the value of A for the uncatalysed reaction under identical conditions. The normalised E values decreased exponentially with increase in concentration of FeAA, showing high propensity of the HTPB-IPDI system for catalysis.
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  • 42
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    Journal of thermal analysis and calorimetry 59 (2000), S. 157-168 
    ISSN: 1572-8943
    Keywords: cellulose acetate ; DSC ; glass transition ; melting ; polycaprolactone
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Cellulose acetate-based polycaprolactones (CAPCL's) were synthesized by the polymerization of ε-caprolactone which was initiated by non-substituted OH group in cellulose acetate. The CL/OH (mol mol−1) ratios of the CAPCL's were changed from 2 to 20. Thermal and viscoelastic properties of the CAPCL sheets were studied by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Glass transition, cold crystallization and melting were determined by DSC. Dynamic modules (E'), dynamic loss modules (E'') and tanδ were measured in a temperature range from −150 to 50°C by DMA. Apparent activation energy of a dispersion was calculated from the frequency dependency of E'' peak temperature. It was found that the main chain motion of both CA and PCL is observed in a CL/OH ratio from 0 to 10 mol mol−1. However, when CL/OH ratio exceeds 10 mol mol−1, the crystalline region which is rearranged by the PCL chain association is observed and only the main chain motion of PCL can be detected.
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  • 43
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    Journal of thermal analysis and calorimetry 59 (2000), S. 245-255 
    ISSN: 1572-8943
    Keywords: DSC ; metallocene ; polyethylenes ; SAXS ; synchrotron radiation ; thermal fractionation ; WAXD ; Ziegler-Natta
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this study, the stepwise isothermal crystallization or thermal fractionation of Ziegler—Natta and metallocene based polyethylenes (ZN-PE and m-PE) with two kinds of branch lengths (ethyl and hexyl) and branch compositions were studied using simultaneous synchrotron small-angle X-ray scattering (SAXS)/wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC). The crystal long period and the invariant were determined by SAXS, and the variations of crystal unit cell parameters and the degree of crystallinity were determined by WAXD. The arithmetic mean length (Ln), the weightedmean length (Lw) and the broadness index (Lw/Ln) of the studied polyethylenes were previously determined by DSC. Results from these studies were interpreted using the model of branch exclusion, which affects the ability of the chain-reentry into the crystal phase. Multiple SAXS peaks and step-change in crystallinity change (WAXD) were seen during heating, which corresponded well with the crystal thickness distribution induced by stepwise crystallization. The effects of the heterogeneity of the 1-olefin branch length and the distribution on the crystal long period and the invariant as well as the degree of crystallinity were discussed.
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  • 44
    ISSN: 1572-8943
    Keywords: annealing ; DSC ; self-nucleation ; SSA ; thermal fractionation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A new technique to thermally fractionate polymers using DSC has been recently developed in our laboratory. The applications of the novel successive self-nucleation and annealing (SSA) technique to characterize polyolefins with very dissimilar molecular structures are presented as well as the optimum conditions to thermally fractionate any suitable polymer sample with SSA. For ethylene/α-olefin copolymers, the SSA technique can give information on the distribution of short chain branching and lamellar thickness. In the case of functionalized polyolefins, detailed examinations of SSA results can help to establish possible insertion sites of grafted molecules. The application of the technique to characterize crosslinked polyethylene and crystallizable blocks within ABC triblock copolymers is also presented.
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  • 45
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    Journal of thermal analysis and calorimetry 59 (2000), S. 497-508 
    ISSN: 1572-8943
    Keywords: Avrami equation ; crystallization ; dibenzylidene sorbitol ; DSC ; isothermal kinetics ; nucleating agents ; nucleation ; pine crystal ; polypropylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The effects of nucleating agents such as dibenzylidene sorbitol (DBS) (a derivative of sorbitol), pine crystal 1500, sodium and potassium benzoates in commercial grade isotactic polypropylene iPP are studied using differential scanning calorimetry (DSC). Isothermal crystallization kinetics of polypropylene to the alpha phase have been analyzed using Avrami's model. Results indicate that dibenzylidene sorbitol and pine crystal are very effective in increasing the crystallization temperature of the polymer and number of nuclei formed during crystallization.
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  • 46
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    Journal of thermal analysis and calorimetry 59 (2000), S. 559-570 
    ISSN: 1572-8943
    Keywords: adhesive ; composition analysis ; curing kinetics ; DMA ; DSC ; TGA ; thermal cure ; thermoplastic/thermoset blend
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract DSC, TGA and DMA thermal analysis techniques are used to characterize a complex adhesive blend. The chemical and thermomechanical property development shown to follow a two-stage process. Beneficial synergy between these analysis tools is demonstrated in this study.
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  • 47
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    Journal of thermal analysis and calorimetry 59 (2000), S. 23-31 
    ISSN: 1572-8943
    Keywords: DSC ; fullerene ; glass transition ; star-like polystyrene ; segmental dynamics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Segmental dynamics around Tg in the 4- and 6-arm fullerene (C60) core star-like polystyrenes with different preset arm lengths was studied by DSC as compared to that in the linear PS and PS/C60 blend. The ‘anomalies’ in glass transition behavior were found for the stars including both suppression and facilitation of segmental motion, and pronounced dynamic heterogeneity within a transition range. The results are interpreted in terms of breakdown of intermolecular cooperativity of segmental motions and PS-C60 interactions.
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  • 48
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    Journal of thermal analysis and calorimetry 59 (2000), S. 675-680 
    ISSN: 1572-8943
    Keywords: conducting polymer ; DSC ; kinetic analysis ; PPV ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The title polymer was obtained electrochemically by the reduction of 4,4'-bis(dibromomethyl)-2,2'-dimethoxybiphenyl under very smooth conditions. The DSC and TG/DTG curves registered at four different heating rates showed that the polymer is stable in air up to 150°C, where smooth degradation starts. Above 300°C, decomposition is fast and exothermic (ΔH= –323 J g–1) . The activation energy (116±4 kJ mol–1 ) was determined by Ozawa's method.
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  • 49
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    Journal of thermal analysis and calorimetry 59 (2000), S. 721-727 
    ISSN: 1572-8943
    Keywords: ageing ; annealing ; DSC ; polyaniline ; relaxation transition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermally treated films of polyaniline-emeraldine base (PANI-EB) cast from NMP solution were studied by using differential scanning calorimetry. Dependence of the thermodynamic parameters of the relaxation transitions on temperature and annealing period as well as the effect of the thermal history of the samples upon the crosslinking processes were investigated. For the first time DSC analysis of PANI-EB films after prolonged ageing was performed. It was found that relaxation transitions can be registered only for crosslinked PANI-EB. The crosslinking processes proceed both upon short-time heating of the polymer studied over80°C and during long-time storage at room temperature.
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  • 50
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    Journal of thermal analysis and calorimetry 59 (2000), S. 711-719 
    ISSN: 1572-8943
    Keywords: cure ; dicyandiamide ; DSC ; epoxy ; hermetic ; solvent
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The curing characteristics of adicyandiamide-cured epoxy system under the influence of solvents in a closed environment were studied by means of isothermal differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The DSC analyses revealed that the presence of solvent results in decreases in the curing exotherm, the initial curing rate, the glass transition temperature, the reaction rate and the reaction order of the epoxy resin. The greatest decreases were caused by the solvent with the highest boiling temperature. A change in temperature-dependent curing route due to the heat absorbed during solvent evaporation is responsible for the difference. The FTIR analyses confirmed that the composition of the cured resin is affected by the solvent, the curing temperature and the specimen configuration. As compared with those obtained from open systems, specimens produced in a closed environment have an enhanced curing exotherm, initial curing rate, glass transition temperature, reaction rate and reaction order because of the retention of volatile catalytic by-products.
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  • 51
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    Journal of thermal analysis and calorimetry 61 (2000), S. 579-587 
    ISSN: 1572-8943
    Keywords: cure kinetics ; DSC ; modified epoxy-amine ; epoxy rubber system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In this work the curing kinetics behaviour of a rubber modified epoxy amine system is investigated through calorimetric analysis. This study is part of a wider investigation on new epoxy formulations to be used as matrices of composite materials. The aim is to enhance both the processing behaviour and the mechanical properties of the matrix in order to obtain higher performance composites for more demanding applications. The epoxy system is blended with a high molecular mass rubber containing functional groups reactive towards the epoxies. The formation of a rubber/epoxy network can be achieved by means of a 'pre-reaction' between the epoxy monomers and the rubber functional groups, carried out in the presence of a suitable catalyst and before the resin is cured with the amino hardener. In this work the influence of both the rubber and the catalyst on the resin cure kinetics is analysed.
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  • 52
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    Journal of thermal analysis and calorimetry 61 (2000), S. 565-578 
    ISSN: 1572-8943
    Keywords: crystallization ; DSC ; PK99 ; rigid amorphous fraction ; WAXD
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract An analysis of the crystallization behaviour of a new poly(aryl-ether-ether-ketone-ketone), PK99, by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) is presented. Isothermal crystallization TG were obtained in the whole range between the glass transition temperature (T g) and the melting temperature (T m) as a consequence of the slow crystallization kinetics stemming from the closeness of these transitions. The calorimetric results, compared with WAXD data, were applied to determine the theoretical melting temperature and crystallization enthalpy. The DSC and WAXD data were combined in order to calculate the total amount of the crystallizable fraction of the polymer, and a model was proposed to explain the difference between the fractions of crystallinity observed with these techniques. The thermal and X-ray data were also correlated with different lamellar morphologies arising from the crystallization conditions. Finally, DSC experiments on the crystallized sample were used to detect the presence of a rigid amorphous phase which does not relax at T g.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 607-614 
    ISSN: 1572-8943
    Keywords: composted materials ; DSC ; thermal characterization
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry (DSC) was applied to the study of material composted from sawdust, used coffee, farmyard manure and the organic fraction of domestic solid waste. Composting trials were carried out in Morocco and samples were collected after different periods of composting. The results obtained provided evidence that sawdust substrate is not a suitable source for composting due to the high content of lignin; samples from used coffee are characterized by a degree of aromaticity that is lower and a functional group heterogeneity that is higher than those of organic wastes from manure and the organic fraction of domestic wastes. The latter organic waste substrates appear to be easily degraded and humified and to give DSC curves that at the end of composting are vary close to those of native soil humic acids.
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  • 54
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    Journal of thermal analysis and calorimetry 61 (2000), S. 711-718 
    ISSN: 1572-8943
    Keywords: DSC ; PEG ; T-CR-T
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A modified isoconversional method is applied to perform the kinetic analysis of non-isothermal processes. The solidification process of a polyethylene glycol with a mean molecular of 4000 (PEG 4000) was here analyzed. It was stated that the Avrami model provides a good description of the solidification process. Temperature-cooling rate-transformation diagrams were constructed and there was a good agreement between experimental data and the calculated T-CR-T curves. Moreover, morphological qualitative analysis has been performed by means of scanning electron microscopy.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 771-778 
    ISSN: 1572-8943
    Keywords: burning rate ; DATH ; DSC ; TG ; thermal decomposition
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal decomposition characteristics of1,7-diazido-2,4,6-trinitrazaheptane (DATH) and multi-component systems containing DATH were studied by using DSC, TG and DTG techniques. Three –NO2 groups in the DATH molecule break away first from the main chain when DATH is heated up to 200°C. Following this process, the azido groups and the residual molecule decompose rapidly to release a great deal of heat within a short time. In the multi-component systems, DATH undergoes a strong interaction with the binder of the double-base propellant and a weak interaction with RDX. The burning rates of the two propellants were determined by using a Crawford bomb. The results showed that the burning rate rises by about 19–66% when 23.5%DATH is substituted for RDX in a minimum smoke propellant. Meanwhile, the N2 level in the combustion gases is enhanced, which is valuable for a reduction of the signal level of the solid propellant.
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  • 56
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    Journal of thermal analysis and calorimetry 62 (2000), S. 177-186 
    ISSN: 1572-8943
    Keywords: binary phase diagram ; DSC ; enthalpic method ; eutectic composition
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    Topics: Chemistry and Pharmacology
    Notes: Abstract We construct with a differential scanning calorimeter (DSC) a phase diagram for the ethylene carbonate (EC)-dimethyl carbonate (DMC) binary system for its liquid-solid phase equilibria. We determine the eutectic composition of the binary system using an enthalpic method that we devised based on the composition dependence of the enthalpy of solidus melting, with highly consistent results. We also discuss the merits and limitations of this enthalpic method.
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  • 57
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    Journal of thermal analysis and calorimetry 63 (2000), S. 397-413 
    ISSN: 1572-8943
    Keywords: Cu–5 at%Zn ; DSC ; F.C.C. (Face Centered Cubic) ; kinetics ; short-range-order ; solute-vacancy complexes
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A modified first order kinetic law, which describes the roles of bound and unbound vacancies, is proposed in order to predict defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. The model has been applied to differential scanning calorimetry (DSC) curves of Cu–5 at%Zn quenched from different temperatures. Activation energy for migration of solute-vacancy complexes was also assessed from the kinetics of short-range-order using DSC traces. A value of 89.5±0.32 kJ mol–1 was obtained. The relative contribution of bound and unbound vacancies to the ordering process as influenced by quenching temperature was determined. In conjunction, a parametric study of the initial total defect concentration and effective energy for defect migration was performed in order to envisage their influence on the calculated DSC profiles.
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  • 58
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    Journal of thermal analysis and calorimetry 63 (2000), S. 507-515 
    ISSN: 1572-8943
    Keywords: boron carbide ; kinetic modelling ; oxidation ; water vapour
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation behaviour of a B4C based material was investigated in a dry atmosphere O2(20 vol.%)-CO2(5 vol.%)-He and also in the presence of moisture H2O (2.3 vol%) as boron oxide is very sensitive to water vapour. The mass changes of samples consisting of a chemical vapour deposit of B4C on silicon nitride substrates were continuously monitored in the range 500–1000°C during isothermal experiments of 20 h. The stability of boron oxide formed by oxidation of B4C was also studied in dry and wet atmospheres to explain the kinetic curves. In both atmospheres, oxidation is diffusion controlled at 700 and 800°C and enhanced by water vapour. At 900°C and higher temperatures, boron oxide volatilisation and consumption by reaction with water vapour modifies the properties of the oxide film and the material is no more protected. At 600°C, B4C oxidation is weak but the process remains diffusion controlled in dry conditions as boron oxide volatilisation is negligible. However, in the presence of water vapour, B2O3 consumption rate is significant and mass losses corresponding to this consumption and to the combustion of the excess carbon are observed.
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  • 59
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    Journal of thermal analysis and calorimetry 61 (2000), S. 551-564 
    ISSN: 1572-8943
    Keywords: amphiphile oligomers ; DSC ; thermo-reversible gelation ; water states
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Symmetrical block oligomers having in common terminal groups (A) consisting of polyoxyethylene (20) stearyl ether are materials of pharmaceutical and cosmetic interest. Phase properties of their aqueous systems and amounts of water typologies were determined by differential scanning calorimetry (DSC). The overall amount of water absorbed by each investigated oligomer was not significantly influenced by the type of central bridging block, whereas the amount of free water decreased with increasing oligomer concentration in the gel. A number of 60–70 moles of water was found to solvate the oligomer chain. The oligomers studied presented a thermo-reversible gelation with and precipitation under determined temperature conditions.
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  • 60
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    Journal of thermal analysis and calorimetry 61 (2000), S. 889-896 
    ISSN: 1572-8943
    Keywords: crystallization ; DSC ; Fe40Ni40P14B6 glassy alloy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract In this paper a DSC study is reported of the behavior of Fe40Ni40P14B6 alloy produced by rapid quenching. The experimental results show that relaxation phenomena can be studied directly from the DSC curves. From these experiments, the spread of the E c values in the literature is attributed to differences in the quenching rates and the presence of variable number of quenched-in nuclei. It is also shown that the microstructure (number and size of crystals) of the non-isothermally devitrified metallic alloy changes with the heating rate; this is a consequence of the shift of crystallization temperatures and, therefore, of the change of the ratio of nucleation and crystal growth rates.
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  • 61
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    Journal of thermal analysis and calorimetry 62 (2000), S. 163-171 
    ISSN: 1572-8943
    Keywords: alkylcyclohexanes ; binary phase diagrams ; DSC ; metastable solutions
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry (DSC) was used to construct phase diagrams of binary mixtures of alkylcyclohexanes and to characterize metastable phases formed in the binary mixtures. The experimentally measured liquidus curves were compared to the liquidus curves calculated using ideal solution theory. The measured phase diagrams of pentadecylcyclohexane/nonadecylcyclohexane and octadecylcyclohexane/nonadecylcyclohexane binary mixtures are consistent with theoretical phase diagrams constructed based on the assumption that these mixtures form eutectic systems. It was also observed that a metastable phase formed in some binary mixtures of pentadecylcyclohexane/nonadecylcyclohexane under fast cooling conditions. It is hypothesized that this metastable phase recrystallizes into the eutectic phase upon heating.
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  • 62
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    Journal of thermal analysis and calorimetry 59 (2000), S. 999-1015 
    ISSN: 1572-8943
    Keywords: DSC ; PID controllers ; tuning PID parameters
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Some DSC calorimeters such as the model Setaram DSC 111 allow the user to set the parameters of temperature programming. Default values furnished by the constructor are often used, but it is very interesting to study the thermal behaviour of the regulation of the calorimeter under different conditions and kinds of set point temperatures. For this research we have developed in C a set of softwares in order to show the behaviour of the proportional integral derivative (PID) controller of the DSC. It can help the user to choose correct values for P, I and D parameters according to the kind of experiment conducted. The software allows studies for extra parameters such as the sampling rate of the computerized PID controller or the determination of filtering of the correction.
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  • 63
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    Journal of thermal analysis and calorimetry 59 (2000), S. 1023-1027 
    ISSN: 1572-8943
    Keywords: DMA ; DSC ; fibers ; polybenzimidazole ; secondary transitions
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Fibers drawn form poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole] (PBI) were studied by DSC and DMA. PBI is a high temperature polymer T g is between 387 and450°C depending on the measurement technique used. The as-spun fiber is free of orientation. The oriented fiber exhibits considerable dependence on whether the DSC measurements were carried out in free-to-shrink or fixed-length modes. The β-relaxation is at 290°C, and was associated with loss of water. The γ-transition at 20°C was not identified, while theδ-transition at –90°C seems to correspond to rotation of the m-phenylene ring.
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  • 64
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    Journal of thermal analysis and calorimetry 63 (2000), S. 339-344 
    ISSN: 1572-8943
    Keywords: amphiphile ; DSC ; D-xylose ; derivatives ; lyotropy ; thermotropy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract We studied the phase transition temperatures of a series of amphiphilic D-xylopyranose and D-xylofuranose derivatives in which the lipophilic part is an alkyl chain R (n-CnH2n+1), regiospecifically linked to D-xylose, at different positions, by Z which is an atom or a functional group (O, S, O–(CH2)3–S). The alkyl chain was moved from the C-1 to the C-5 position in the xylose moiety, thereby allowing us to compare directly the phase transition temperatures of the individual materials. These compounds give thermotropic and/or lyotropic liquid crystals. In some cases, we also observed solid–solid phase transitions.
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  • 65
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    Journal of thermal analysis and calorimetry 60 (2000), S. 25-33 
    ISSN: 1572-8943
    Keywords: DSC ; kinetics ; thermal decomposition ; 2,4,6-trinitrotoluene
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    Topics: Chemistry and Pharmacology
    Notes: Abstract An autocatalytic model involving the limited solubility of volatile catalytic products was applied to the thermal decomposition of 2,4,6-trinitrotoluene. The critical supersaturation of the thermal decomposition products with the catalytic properties was higher at a low heating rate. Decrease of the sample mass led to an increased critical supersaturation of the decomposition products. This is probably a result of the greater contribution of products adsorption on the aluminium pan surface. It is presumed that the differences observed in the rate constant are connected with the uncontrolled critical supersaturation of the volatile thermal decomposition products.
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  • 66
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    Journal of thermal analysis and calorimetry 60 (2000), S. 45-52 
    ISSN: 1572-8943
    Keywords: compatibilization ; DMTA ; DSC ; polyamide 6/thermoplastic polyurethane blends
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Blends obtained from polyamide 6 and a thermoplastic polyurethane compatibilized by diblock copolyurethaneamides were investigated by means of DMTA and DSC. The blends were prepared by compounding in a Brabender mixer. The compatibilizer affected the glass transition temperature of the amorphous phase of the blends. The non-isothermal crystallization temperature of the polyamide phase was lowered in the presence of the polyurethane and the copolyurethaneamide.
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  • 67
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    Journal of thermal analysis and calorimetry 60 (2000), S. 117-121 
    ISSN: 1572-8943
    Keywords: biopol/polyamide 6 blends ; DSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Blends obtained from Biopol D600G and polyamide 6 reveal in DSC investigations multiphase structure with a distinct crystalline polyamide 6 phase. Due to rapid crystallization of the polyamide 6 the crystallization of the Biopol D600G is retarded. The grade of crystallization of Biopol D600G is lower in the blends than in the pure state, as calculated from the melting enthalpies. Crystallization of polyamide 6 in the blends is faster and results in increasing of the grade of crystallization of polyamide 6 phase comparing to the unblended component.
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  • 68
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    Keywords: cyanazine ; DSC ; kinetics ; thermal stability
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Cyanazine was taken as an example for investigations under the influence of different conditions on thermal decomposition of triazine herbicides. DSC measurements were carried out under atmospheric pressure and hermetically closed, under pressure 1.3 kPa. The influence of the pressure on the constant reaction rate of decomposition of cyanazine was discussed. It was also proved that the predicted reaction constant rates from isothermal and non-isothermal measurements are consistent.
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  • 69
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    Journal of thermal analysis and calorimetry 60 (2000), S. 111-116 
    ISSN: 1572-8943
    Keywords: DMTA ; DSC ; HMDI ; mesogenic chain extender ; polyurethane
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    Topics: Chemistry and Pharmacology
    Notes: Abstract New polyurethanes with mesogenic units in the main chain due to the use of a liquid crystalline chain extender were synthesized from 4,4'-methylenebis(cyclohexyl isocyanate) (HMDI)using diisocyanates of different trans, trans isomer content, a low molecular diol4,4'-bis(6-hydroxyhexoxy)biphenyl (BHHBP) and a high molecular poly(hexyleneadipate)diol (PHA). The growth of trans, trans isomer content in HMDI used to syntheses of PU induces monotonic growth of melting point, rectilinear growth of crystallization temperatures and the growth of crystallization enthalpy, both for hard segment polyurethanes and block polyurethanes. The increase of trans, trans isomer content in HMDI increases also glass transition temperatures and dynamic storage modulus of the polyurethanes.
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  • 70
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    Journal of thermal analysis and calorimetry 60 (2000), S. 163-166 
    ISSN: 1572-8943
    Keywords: comparison ; decomposition ; DSC ; enthalpy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The comparison of thermal and calorimetric properties of metal derivatives of 6-aminopicolinic acid (APH) is presented. The salts and complexes of APH with Cr(III), Cd(II), Cu(II), Ni(II), Pb(II), Co(II)and Ag(I) have been studied by TG-DTA and DSC methods up to 1200°C in a nitrogen atmosphere. Decomposition processes are proposed. The decarboxylation, deamination and carbonation of the organic fragments of molecules take place. The compounds decompose to metal or to metal oxides. The values of the transition enthalpy were determinated.
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  • 71
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    Keywords: DMA ; DSC ; physical aging ; TGDDM epoxy
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The physical aging of a system containing tetraglycidyl-4-4′-diaminodiphenylmethane (TGDDM), with a multifunctional novolac glycidyl ether resin hardened by 4,4′-diaminodiphenylsulphone (DDS) has been investigated by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Samples fully cured were aged at temperatures between 200 and 250°C, during periods of time from 1 to a maximum of 336 h. Furthermore, the dynamic mechanical relaxation behaviour annealed at temperature of 220°C, was studied, aging during 24 and 168 h. The effect of the enthalpy relaxation during DSC heating scan is shown by the presence of an endothermic peak whose position and intensity depends on the aging conditions, both temperature and time. DSC studies suggest that enthalpy relaxation increases gradually with aging time to a limiting value for each temperature where structural equilibrium is reached. DMA results show that the effect of aging is to cause chain stiffening and a decrease in the height of the peak value of the loss factor.
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  • 72
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    Keywords: 2-benzylamino-butanol ; DSC ; mandelic acid ; melting phase diagram ; optical resolution
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The optical resolution of racemic mandelic acid (I) by S-2-benzylamino-butanol (II) was performed in water, ethyl acetate, and water saturated ethyl acetate. It was found that the efficiency of the resolution is three times higher in water saturated ethyl acetate than in either water or ethyl acetate. The salt mixtures produced during the resolutions and the pure diastereoisomeric salts were analyzed by TG, DSC and X-ray powder diffraction measurements. The R-(-)-I×S-(+)-II salt has the higher melting point and heat of fusion value which indicates that this is the more stable salt. Though the general assumption is that diastereoisomeric salt pairs of successful optical resolutions form eutectic systems, the R-mandelic acid-S-2-benzylamino-butanol and the S-mandelic acid-S-2-benzylamino-butanol system was found to behave in a different way. Melting did not start at or near the estimated eutectic temperature. The difference can be explained either by miscibility in the solid phase (solid solution) or by a blocked interaction between the crystals of the two solid salts. This unusual behaviour of the salt pair should be responsible for the unusual difference in the efficiency of the resolutions performed in different solvents
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  • 73
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    Journal of thermal analysis and calorimetry 60 (2000), S. 535-539 
    ISSN: 1572-8943
    Keywords: DSC ; ferrite ; Mössbauer spectra ; TG ; thermal decomposition ; zinc ferriformate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal analysis of zinc hexa(formato)ferrate(III) decahydrate, Zn3 [Fe(HCOO)6]2 10H2O has been investigated up to 800°C in static air atmosphere employing TG, DSC, XRD, IR, ESR and Mössbauer spectroscopic techniques. After dehydration at 160°C, the anhydrous complex decomposes into α-Fe2 O3 and zinc carbonate in successive stages. Subsequently the cations remix to yield fine particles of zinc ferrite, ZnFe2 O4 , as a result of solid state reaction between α-Fe2 O3 and zinc carbonate at a temperature (600°C) much lower than for ceramic method.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 595-604 
    ISSN: 1572-8943
    Keywords: crystal structure ; DSC ; oxides ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The formation of TiO2 prepared by hydrolysis method was presented. Thermodynamics and kinetics of anatase crystallization reaction were investigated. Differential method of kinetic data evaluation in non-isothermal conditions according toKissinger, Ozawa and Kazeev-Yerofeev was applied. Starting, crystallized and thermally treated powders were determined using X-ray powder diffraction analysis. The characteristic parameters (the activation energy, constant rate and formal kinetic order of reaction) of TiO2 formation were calculated using DSC data.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 683-689 
    ISSN: 1572-8943
    Keywords: DSC ; heat capacity ; mixed oxide TiO2-RuO2 ; RuO2 ; TiO2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract DSC was used for heat capacity measurements of pure RuO2 in the temperature range from 300 to 1170 K of solid solutions corresponding to the compositions of (Ti1−x Rux )O2 (x ≤0.15 and x ≥0.85) and in the temperature range from 300 to 1550 K of pure TiO2. The analysis of experimental data obtained within ±2% of accuracy has shown that the characteristic temperatures representing the harmonic lattice vibrations do not strongly depend on the chemical composition x . It was demonstrated that non-harmonic heat capacity is strongly correlated to x. The existence of additional excess heat capacity was observed with the mixed oxide solid solution samples of low Ru content and explained by the defect formation model.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 333-343 
    ISSN: 1572-8943
    Keywords: base line ; DSC ; kinetics ; modeling ; thermodynamics ; TMDSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The application of non-linear heating program to a heat-flux DSC apparatus has attracted much attention. From thermodynamics viewpoint, it is shown that the variation of enthalpy of a sample changing with temperature change is due, to both the true heat capacity of the sample and the enthalpy of some transformations occurring in the sample, characterized by its degree of advance. Using the simple assumption that the rate of the transformation is proportional to the distance from the thermodynamic equilibrium, an electrical model of the thermal event is given. Using the coupled cell model of the DSC apparatus, we show how to obtain the rate of transformation of the sample and heat capacity, which is directly related to the base line of the experiment.
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  • 77
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    Journal of thermal analysis and calorimetry 60 (2000), S. 357-369 
    ISSN: 1572-8943
    Keywords: blends of polyamides ; copolyamides ; crystallization ; DSC ; melting point ; structure
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The DSC method was used to obtain more information on changes of thermal properties connected with different comonomers bound in the (co)polymer chains. The copolyamides propered were block ones which were less crystalline and compatible with poly-ε-caprolactam. The results have confirmed the crystalline nature of polyamides and copolyamides.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 345-355 
    ISSN: 1572-8943
    Keywords: DSC ; PID controllers ; tuning PID parameters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Some DSC calorimeters, such as the model DSC 111, built by the society Setaram, allow the user to set the temperature programming parameters. Usually default values furnished by the constructor are often used, but it is very interesting to study the thermal behaviour of the regulation of the calorimeter under different conditions and with different kinds of set point temperatures. For this research, we have developed in C language a set of software in order to demonstrate the behaviour of the (proportional integral derivative) PID controller of the DSC. It can help the user to choose correct values for P, I and D parameters according to the kind of experiment conducted. The software allows studies of extra parameters, such as the sampling rate of the computerized PID controller or the determination of filtering of the correction.
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    Journal of thermal analysis and calorimetry 60 (2000), S. 917-926 
    ISSN: 1572-8943
    Keywords: ARC ; DSC ; HFC ; KDNBF ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract KDNBF (potassium 4,6-dinitrobenzofuroxan) has been used as a primer explosive in igniters and detonators for many years. Considerable information about the sensitivity of KDNBF to various stimuli, such as impact, friction, shock and electrostatic charge, is known. However, the thermal sensitivity of KDNBF has been relatively unexplored. Hence, there is very little information available concerning the fundamental thermal properties of KDNBF. Therefore, as part of an extensive thermal hazard assessment, DSC, TG, accelerating rate calorimetry (ARC) and heat flux calorimetry (HFC) measurements have been undertaken on KDNBF. The results demonstrate that KDNBF decomposes via a multi-step exothermic process directly from the solid state. The decomposition process does not appear to depend on the nature of the atmosphere, except in the final stage of the TG decomposition in air, where remaining carbonaceous material is converted to CO2. The first stage of the decomposition is sufficiently rapid that ignition occurs if too large a sample is used. Dynamic and isothermal methods were used to obtain the kinetic parameters and a range of activation energies were obtained, depending on the experimental conditions. The kinetic results have been analyzed in terms of various solid state decomposition models.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 75-89 
    ISSN: 1572-8943
    Keywords: DSC ; Fourier transformation ; heat capacity ; sawtooth-modulation ; TMDSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The determination of heat capacity data with sawtooth-type, temperature-modulated differential scanning calorimetry is analyzed using the Mettler-Toledo 820 ADSC™temperature-modulated differential scanning calorimeter (TMDSC). Heat capacities were calculated via the amplitudes of the first and higher harmonics of the Fourier series of the heat flow and heating rates. At modulation periods lower than about 150 s, the heat capacity deviates increasingly to smaller values and requires a calibration as function of frequency. An earlier derived correction function which was applied to the sample temperature-controlled power compensation calorimeter enables an empirical correction down to modulation periods of about 20 s. The correction function is determined by analysis of the higher harmonics of the Fourier transform from a single measurement of sufficient long modulation period. The correction function reveals that the time constant of the instrument is about 5 s rad−1 when a standard aluminum pan is used. The influence of pan type and sample mass on the time constant is determined, the correction for the asymmetry of the system is described, and the effect of smoothing of the modulated heat flow rate data is discussed.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 91-98 
    ISSN: 1572-8943
    Keywords: DSC ; heat flow calibration ; temperature calibration
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermoanalytical instruments are extensively used in R&D as well as in industrial quality control. A quantitative analysis of the data of a thermoanalytical measurement requires a careful calibration of the instrument. In differential scanning calorimetry (DSC) the quantities that have to be calibrated are the temperature and the heat flow. These two quantities are usually calibrated by evaluating melting or solid-solid transitions of some reference materials with well known transition enthalpies and temperatures. In this contribution we investigate temperature and heat flow calibration in the temperature range between −100 and 160°C. We included 9 different samples for the analysis and established some general rules for the calibration process. As a result we found that with a well calibrated instrument the heat flow can be measured with 90% confidence to about ± 3% accuracy in this temperature range. With respect to temperature calibration we find that accuracies of ±0.8°C (90% confidence) may be expected. These values represent general accuracy limitations of DSC’s due to varying heat transfer conditions within the samples.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 181-189 
    ISSN: 1572-8943
    Keywords: characteristic temperatures ; concentrates ; DTA ; DTG ; oxidation ; sulphides ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of metal sulphides and sulphide concentrates was studied by means of DTA, TG and DTG curves. The behaviour of ZnS, CdS, GaS, Tl2S, Sb2S3 and Sb2S5 during thermal treatment in an oxidizing medium was investigated. The properties of these sulphides were compared and conclusions were drawn about their probable oxidation reactions and the kind of end-products obtained. The characteristic temperatures of the studied sulphides were determined on the basis of curves (DTA). The values obtained were used to compare the behaviour of the sulphides during the oxidation process in a fluid bed. The results can be used to improve the technological and economic indices in the industrial production of zinc.
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    Journal of thermal analysis and calorimetry 61 (2000), S. 363-368 
    ISSN: 1572-8943
    Keywords: DSC ; glycosylated ribonuclease ; thermodynamic stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermodynamic stability of pancreatic ribonuclease B (RNase B), which possesses identical protein structure of pancreatic ribonuclease A (RNase A), but differs by the presence of a carbohydrate chain attached to Asn 34, was studied by means of differential scanning calorimetry (DSC) at different pH conditions. The comparison between the two proteins has shown a little but significant stabilization of RNase B with respect to the unglycosylated one at pH values higher than 7.0. The thermodynamic analysis reveals the carbohydrate moiety to have a small stabilization effect of 3 kJ mol–1 at pH 8.0 and 63°C on the protein.
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  • 84
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    Journal of thermal analysis and calorimetry 61 (2000), S. 341-350 
    ISSN: 1572-8943
    Keywords: DSC ; polymorphism ; X-ray
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of the hydrocarbon chain length in the formation of interdigitated and non-interdigitated bilayers in n -alkylammonium chlorides has been investigated for chain lengths varying between 8 and 14 carbon atoms. The formation of non-interdigitated bilayers during crystallization from solution is favoured for shorter chains whilst the interdigitated structure is predominant for larger chains. The thermodynamic parameters of the solid to solid phase transitions in the non-interdigitated samples depend on chain length showing the odd-even alternation that characterized homologous series in n -paraffins. The solid to liquid crystal phase transition temperatures and enthalpies show a linear dependence with the chain length.
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  • 85
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    Journal of thermal analysis and calorimetry 61 (2000), S. 369-376 
    ISSN: 1572-8943
    Keywords: diclofenac ; DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry was applied to the determination of diclofenac in three 'Voltaren' formulas. The pharmaceutical products (soluble tablets, suppositories and vials) were selected in order to show that calorimetric analysis is an easy technique to perform and can be competitive with other conventional methods. In the tablets diclofenac (DH) was determined, without any pre-treatment, from the area of the endothermic peak which occurs at about 180°C in the DSC curve obtained in N2 atmosphere. In the analysis of the suppositories and vials, nitrilotriacetic acid (NTA) was added to transform the diclofenac sodium salt (DS) into the thermally active form (DH). In both cases, it was necessary to eliminate the interference of excipient by cyclohexane extraction (suppositories) or by a multistep program for the DSC run (vials). The accuracy of the results and the simplicity of the procedure justify the important role of DSC in the analysis of these drugs and certainly of several other commercial products.
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  • 86
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    Journal of thermal analysis and calorimetry 61 (2000), S. 389-396 
    ISSN: 1572-8943
    Keywords: compost ; DSC ; organic matter ; TG ; thermal stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The possibility to use thermal analysis for a quick characterisation of chemical changes in the organic matter of composted materials was tested. Nine samples were taken at progressive stages of maturation from the same trench of a fully automated composting plant. DSC and TG were simultaneously performed in static air conditions on whole ground composts. Progressive stages in the composting process yielded samples whose DSC traces revealed appreciable modifications in thermal patterns that agreed well with quantitative data obtained from TG measurements. The ratio between the mass losses associated with the two main exothermic reactions (R1) showed a good sensitivity in detecting the changes in the level of stabilisation during the composting process. Thermal methods seem to be a valid comparative method in evaluating the level of bio-transformation of materials during a composting process.
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  • 87
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    Journal of thermal analysis and calorimetry 61 (2000), S. 411-423 
    ISSN: 1572-8943
    Keywords: bread baking ; DSC ; starch gelatinization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Starch gelatinization in wheat flour dough of various moisture contents was quantitatively evaluated by means of DSC. The experimental records were worked out in the form of excess heat capacity vs. T traces which were deconvoluted to single out the contribution of starch gelatinization from that of the decomposition of amylose-lipid complexes. The quantitative procedure used put into evidence that a third endothermic process would take place in the dough with a poor moisture content. DSC runs carried out with sealed pans (i.e., at constant moisture level) and open pans (from which some water was free to evaporate) allow simulation of two extreme conditions of a real baking process, namely that relevant to the central core and to superficial layer of a dough loaf, respectively. The extent of starch gelatinization occurred in these conditions was quantitatively assessed. These data were collected at various heating rates and used to define temperature-time-transformation(TTT) diagrams which are useful tools to predict the progress of baking for any given thermal history of the system.
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  • 88
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    Journal of thermal analysis and calorimetry 61 (2000), S. 451-459 
    ISSN: 1572-8943
    Keywords: DSC ; gelatin films ; high angle X-ray
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry and high angle X-ray diffraction analyses were performed on gelatin films, air dried at different values of constant elongation, crosslinked with glutaraldehyde and examined at constant relative humidity of 75%. Drawing induces a preferential orientation of the chain segments of gelatin parallel to the stretching direction,and a linear increase of the renaturation level, calculated as the ratio between the denaturationenthalpy of gelatin films and that of tendon collagen. The comparison with the results previously obtained on the mechanical properties of the films, puts into evidence the different contributions of orientation and renaturation on the improvement of the mechanical parameters on drawing. The results offer important information on the role of glutaraldehyde (GTA) crosslinking on the stability of collagenous materials.
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  • 89
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    Journal of thermal analysis and calorimetry 62 (2000), S. 797-807 
    ISSN: 1572-8943
    Keywords: dimenhydrinate ; DSC ; film coating ; HPMC ; thermal conductivity
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Dimenhydrinate is a heat-sensitive antihistamine with a low melting point. The heat-sensitive feature is of importance if direct compression is used. Direct measurement of the heat originating in the texture of tablets during compression is very difficult. Thermoanalytical methods were used as indirect methods to describe the changes in material properties at high temperature: differential scanning calorimetry, thermomicroscopy and thermogravimetric analysis. Film coating method is widely used in pharmaceutical technology. A fluidized bed apparatus was applied to coat the crystals. The coating film forming agent was hydroxy-propyl-methylcellulose (HPMC), which is a gastric-soluble polymer. Thermoanalytical measurements reveal that dimenhydrinate crystals are sensitive to heat. Film coating method does not alter the shape of the DSC curve of dimenhydrinate, but increases the melting point. The presence of a macromolecular film reduces the thermal conductivity, because it separates the particles.
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  • 90
    ISSN: 1572-9001
    Keywords: Dynamic NMR ; 15N NMR ; 13C NMR ; DSC ; tautomerism ; melting point
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The behavior of neat 3(5)-methylpyrazole has been studied at low temperatures by DSC and by NMR (13C and 15N). The main conclusion is that the supercooled liquid is a mixture of four trimers formed by 3-methyl and 5-methyl tautomers.
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  • 91
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    Journal of applied electrochemistry 30 (2000), S. 727-731 
    ISSN: 1572-8838
    Keywords: electrosynthesis ; oxidation ; lignin ; vanillin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Electrical Engineering, Measurement and Control Technology
    Notes: Abstract Electrochemical oxidative degradation of Kraft lignin was investigated in batch and flow cells on Pt, Au, Ni, Cu, DSA–O2 and PbO2 anodes. Production of vanillin was evaluated by means of formal kinetic analyses. Conversion and chemical yields were found to be dependent mainly on the applied current density, that is on the partial pressure of oxygen at the interface, while the nature of the electrode influenced the reaction rates.
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  • 92
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    Journal of thermal analysis and calorimetry 59 (2000), S. 837-846 
    ISSN: 1572-8943
    Keywords: DSC ; γ-irradiation ; laser Raman ; microelectrophoresis ; XRD ; zeta-potential ; zirconium hydroxide ; ZrO2
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Zirconium hydroxide particles produced by rapid precipitation at pH 10.4, 7 or 2 were subjected toγ-irradiation up to a final dose of 20 MGy. The effects of the γ-irradiation were examined by X-ray powder diffraction, laser Raman spectroscopy, differential scanning calorimetry and microelectrophoretic measurements. It was found that γ-irradiation had no influence on the behaviour of zirconium hydroxide during calcination and subsequent cooling. The results of microelectrophoretic measurements showed that γ-irradiation influences the surface properties of zirconium hydroxide as a function of the precipitation pH. Zirconium hydroxide precipitated at pH 2 proved to be the most susceptible to γ-irradiation, while the sameγ-irradiation had very little (if any) effect on the surface properties of zirconium hydroxide precipitated at pH 10.5. After γ-irradiation, the electrophoretic mobility of zirconium hydroxide precipitated at pH 2 was increased at both low and high pH, thereby indicating an increase in its adsorption capacity. The analogy observed between the pH-dependence of the effects of γ-irradiation on the electrokinetic behaviour of zirconium hydroxide and the influence of ball-milling on the thermal behaviour of zirconium hydroxide [8] suggested that the susceptibility of amorphous zirconium hydroxide increases with decrease of the precipitation pH.
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  • 93
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    Journal of thermal analysis and calorimetry 62 (2000), S. 575-578 
    ISSN: 1572-8943
    Keywords: active metal ; high-dispersed iron powder ; oxidation ; thermogravimetry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Two oxidation stages of electrolytic ultradispersed iron powder at the temperature range of 90–450°C have been stated. The contribution of increasing mass and evolving heat at the first oxidation stage due to changing Fe0 into Fe2O3 in the total oxidation effect is predominant. The thermal method of active metal determination in electrolytic iron powders has been developed. The coarse-grained reduced iron powder was not oxidized completely just to 900°C because of local sintering of big iron particles as a result of evolving heat at oxidation of high-dispersed iron particles.
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  • 94
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    Journal of nanoparticle research 2 (2000), S. 315-319 
    ISSN: 1572-896X
    Keywords: nanostructure ; silicon ; oxidation ; CNT tip ; ion trap ; research management
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics , Technology
    Notes: Abstract Joint Research Center for Atom Technology (JRCAT) and its Atom Technology Project are described. The project covers a wide range of research subjects; manipulation of atoms and molecules, formation of nanostructures of semiconductors, spin electronics and first-principles calculation of dynamic processes of atoms and molecules on solid-state surfaces. Several recent achievements on nanotechnology and nanoscience are roughly sketched.
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  • 95
    ISSN: 1573-4935
    Keywords: erythrocyte ; macrophage ; oxidation ; mouse
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Membrane protein modification can change cell surface properties which canbe correlated with altered macrophage-erythrocyte interactions. Mouseerythrocytes were incubated in phosphate buffer for different times toinduce protein modification. Mouse erythrocyte membrane changes wereanalyzed by infrared analyses and gel electrophoresis. Proteolyticdigestion of membrane proteins was observed. After 22 hours preliminaryincubation, the number of erythrocytes adhering to a monolayer ofmacrophages reached a maximum, the majority of which had not beenphagocytosed. Most of the erythrocytes incubated for 40 hours underwentphagocytosis after adhesion to the macrophages.
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  • 96
    ISSN: 1573-4978
    Keywords: chromatin ; DNA ; DSC ; thermal denaturation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The thermal denaturation of calf thymus total chromatin and of fractions enriched in heterochromatin or euchromatin, has been investigated by differential scanning calorimetry and compared to that of calf thymus DNA and DNA-histone complexes. In our experimental conditions, chromatin melts in three thermal transitions: the main one, assigned to separation of the DNA double helix, occurs at 83 °C, while the other two occur at 63 °C and 74 °C. The data show that: (a) the transition enthalpy for denaturation of DNA in the total chromatin and in DNA-histone complexes is nearly the same as that of DNA in solution; (b) the transition at 63 °C is present in the thermogram of the heterocromatin enriched fraction, while it is completely absent in that of the euchromatin enriched one. The results suggest that this transition can be attributed to the higher order structures of heterochromatin.
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  • 97
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    Oxidation of metals 53 (2000), S. 1-23 
    ISSN: 1573-4889
    Keywords: Aluminum ; SEM ; oxidation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Fine powders of aluminum were produced in a pilot-plant, inert-gas atomizerwith a “confined-design” nozzle, which operated vertically upward. Argonand helium at 1.85 MPa and nitrogen at 1.56 MPa were used as the atomizingagent. The morphology of the powder particles was examined by SEM. Powderswere sieved dry and wet. The Sauter mean diameter of the powders varied from20.70 to 10.25 μm depending on the atomizing gas. The distribution ofsizes was bimodal. The mean thickness of oxide on the surface of the powderwas calculated from the total oxygen contents of powder samples (determinedby a Leco analyzer). In addition, ESCA measurements and BET tests werecarried out for surface-oxide thickness and area measurements,respectively. The finest powder produced under helium incorporated thinnersurface-oxide layers than the coarser ones produced under argon andnitrogen. This was due to differences in physical properties (such asdensity, thermal conductivity) and flow properties (such as gasvelocity and relative velocity) of the atomizing gases used, i.e., helium,argon, and nitrogen. The oxide was very irregular in thickness in thecoarse-size range of the Al powders produced under argon and nitrogen. Thiswas presumably because of the high- and low-temperature oxidation ofaluminum droplets during the atomization and subsequent solidification andcooling periods leading to the rough surfaces observed with SEMinvestigation in the present work.
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  • 98
    ISSN: 1573-4889
    Keywords: γ-TiAl-based intermetallic alloy ; oxidation ; microstructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The influence of microstructure of the two-phase alloyTi–46Al–1Cr–0.2Si on the oxidation behavior in air between600 and 900°C was studied. The oxidation rate, type of scale, and scalespallation resistance were strongly affected by the type of microstructure,i.e., lamellar in as-cast material and duplex after extrusion at1300°C. The oxidation rate was affected by the size and distribution ofthe α2-Ti3Al phase, being faster for the extrudedmaterial with coarse α2-Ti3Al. The type of oxide scaledetermines the spalling resistance. Cast material developed a uniform scalethat spalled off after short exposure times at 800 and 900°C when a criticalthickness was reached. The extruded material presented a heterogeneous scalewith predominant thick regions formed on γ-TiAl-α2-Ti3Algrains and thin scale regions formed on γ-TiAl grains. Thistype of scale could permit an easier relaxation in the matrix of stressesgenerated by both thermal-expansion mismatch between scale and alloy andoxide growth, resulting in a higher spallation resistance.
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  • 99
    ISSN: 1573-4889
    Keywords: Fe–Cr–Al alloy ; oxidation ; molybdenum ; breakaway oxidation ; transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract Thin foils of Fe–20Cr–5Al alloys are susceptible to breakawayoxidation once the aluminum content of the substrate has fallen below somecritical value. The combined addition of 0.1 wt.% lanthanum and 0, 1, or 2wt% molybdenum has a beneficial effect on the high-temperature oxidation ofsuch foils. Lanthanum has the well-known reactive-element effect on adhesionof the protective alumina scale, thereby increasing the time to onset ofbreakaway oxidation, while, for alloys containing molybdenum, breakawayoxide spreads relatively slowly over the specimen in comparison to alloysthat contain no molybdenum. In particular, molybdenum-containing alloys areable to develop a protective Cr2O3 layer at the breakawayoxide–substrate interface. Conversely, molybdenum-free alloys form aninternal-oxide zone in the substrate adjacent to this interface, rather thana Cr2O3 layer, so breakaway oxide spreads rapidly. A martensitic phase isobserved in the substrate adjacent to the breakaway oxide formed on Fe–20Cr–5Al–La specimens, which means that theα-phase has transferred to the γ -phase at the temperature ofthe oxidation test (1150°C). Conversely, α-phase is retained inthe molybdenum-containing alloy, even after breakaway takes place, sincemolybdenum, which is a strong ferrite former, is enriched in the alloyadjacent to areas of breakaway oxide. The diffusion rate of chromium isslower in the γ than in the α-phase so a continuouschromium-rich oxide layer, which is effective in inhibiting breakawayoxide from spreading, cannot be established at the breakawayoxide–substrate interface for the molybdenum-free alloys.
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  • 100
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    Oxidation of metals 54 (2000), S. 189-209 
    ISSN: 1573-4889
    Keywords: oxidation ; β-FeAlCr ; coatings ; magnetron sputter-deposition ; ridge-type oxide ; Al2O3 phase transformation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract β-FeAl coatings containing various Cr contents of 6.5–45 wt.%were produced with a closed-field, unbalanced magnetron sputter (CFUMS)deposition technique. Cyclic oxidation tests at 1100°C in air for100 1-hr cycles and isothermal exposures at 1000°C in pure O2 for100 hr were carried out with the coatings and an as-cast FeAlspecimen. All of the coatings showed good scale-spallation resistanceduring cyclic oxidation and the coating with 6.5 wt.% Cr exhibited thelowest oxidation rates in both cyclic and isothermal oxidationexposures. After oxidation, fine-grain ridge-type oxide scales formed onthe coatings, while the oxide scale formed on the cast FeAl showed alarge quantity of θ-Al2O3 blades and large interfacial voids on thebase–alloy surface. The transformation from θ to α-Al2O3was accelerated due to the presence of Cr in the coatings. The fasttransformation considerably reduced oxidation rates, suppressed fastoutward Al diffusion for the growth of a θ-Al2O3 scale, and preventedthe formation of interfacial voids that played a major role in causing thescale spallation.
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