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  • 1
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    Electronic Resource
    Springer
    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1213-1223 
    ISSN: 0392-6737
    Keywords: Optoelectronic devices ; Other solid inorganic materials ; Electron states in low-dimensional structures (superlattices, quantum well-structures and multilayers) ; Quantum optics ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary The properties and preliminar applications of porous-silicon (p-Si) microcavities are here reported. These structures are based on a planar resonator formed by two narrow-band high-reflectance distributed Bragg reflectors separated by a thin active optical layer, all of which are made of p-Si layers. The accurate control of the electrochemical dissolution of Si lets us realize p-Si multilayers with the desired refractive indices sequence. Large improvements of the emission properties of p-Si microcavities with respect to standard p-Si samples are observed: 1) increased emission intensity, 2) spectral narrowing of the emission band, and 3) high directionality in the emission pattern. Resonant-cavity light-emitting diodes with higher efficiencies and stabilities with respect to standard p-Si/metal devices are demonstrated. Reflectivity changes due to absorption saturation have been observed.
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  • 2
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1121-1129 
    ISSN: 0392-6737
    Keywords: Optoelectronic devices ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary We present a theoretical study of two infinite wires of Si with a different lateral size. The analysis is based on the linear muffin tin orbitals method in the atomic sphere approximation (LMTO-ASA). We consider free, partially and totally H-covered [001] Si quantum wires with rectangular cross-section. The results of this investigation prove the quantum wire nature of porous Si and interpret many of its physical features. In particular we show thata) as expected quantum confinement originates the opening of the LDA gap;b) the gap opening effect is asymmetric: 1/3 of the widening is in the valence band, while 2/3 in the conduction band;c) the near band gap states originate from Si atoms located at the center of the wire;d) the confinement is enhanced in the case of free surfaces;e) the imaginary part of the dielectric function shows a low-energy side structure strongly anisotropic, identified as responsible of the luminescence transition;f) the presence of dangling bonds destroys the luminescence properties;g) in spite of featurec), all Si atoms are collectively involved in the luminescence transition;h) the shift detected by the Si L2, 3VV Auger signal is due to H-interaction effect and is not a measure of the quantum confinement effect;i) the Si atoms probed by the Si L2, 3VV Auger are bonded with H and H2.
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  • 3
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1131-1148 
    ISSN: 0392-6737
    Keywords: Optoelectronic devices ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary In this work we demonstrate that efficient light emission at 1.54 μm can be achieved when Er ions are incorporated into crystalline Si or in heavily oxygen-doped amorphous and polycrystalline Si films (SIPOS). We have found that temperature quenching of photo- and electroluminescence, which is the major limitation towards the achievement of room temperature luminescence, can be strongly reduced by codoping these films with oxygen. This impurity is already present in as-prepared SIPOS and it is introduced by ion-implantation in crystalline Si. Er luminescence is obtained under both optical and electrical excitation and we demonstrate that excitation occurs through a carrier-mediated process. Electrical excitation is obtained by incorporating Er in properly designed device structures. It is found that this excitation can occur both through the recombination of hole-electron pairs and through impact excitation of the Er ions by hot electrons. These two mechanisms have different efficiencies and impact excitation is shown to prevail at room temperature. These data are presented and possible future developments are discussed.
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  • 4
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1111-1119 
    ISSN: 0392-6737
    Keywords: Optoelectronic devices ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary The striking optical properties of porous silicon (PS) show a twofold aspect typical of an ordered and a disordered material, respectively. Raman, electron microscopy, and resonant photoluminescence studies indicate that the light emission originates from crystalline regions. On the contrary, several features, like the non-exponential decay of photoluminescence (PL), the broad emission spectrum, the photoluminescence fatigue under light exposure etc. are typical of a disordered material and reminiscent of similar effects founde.g. in amorphous semiconductors. These twoapparently conflicting aspects have for a long time hindered the understanding of the basic light emission mechanism. In this paper we report new optical data showing that disorder in porous silicon leads to strong carrier localisation. Light emission in PS is suggested to occur through transitions involving localized states.
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  • 5
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1159-1165 
    ISSN: 0392-6737
    Keywords: Optoelectronic devices ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary Porous silicon is an attractive material for silicon optoelectronics. The great advantage of porous silicon lies on the simple way of production which makes silicon nanostructures easily available. After several papers have been published on this topic, we are able to identify some disadvantages connected to the porous nature of the material and to the method of fabrication. Other dry processes can be used to produce Si nanostructures. In this paper we present a method fully compatible with the standard semiconductor technology. The optical and structural properties of the nanocrystalline films so far obtained are presented, together with some promising results indicating good electrical properties.
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  • 6
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1167-1177 
    ISSN: 0392-6737
    Keywords: Optoelectronic devices ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary We report room temperature time-resolved photoluminescence (PL) and temperature dependence of continuous wave (cw) PL studies of high fluence (from 3·1016 to 3·1017 cm−2) Si+-implanted thermal SiO2 layers after annealing at high temperature (T=1000°C). Such measurements were related to TEM analysis of samples. Nancocrystals were observed at TEM only a samples implanted at higher fluence. In these samples a near infrared PL signal peaked at approximately 1.5 eV with decay time of about 100 μs is present. Besides, in all samples a light emission is present in the green region of the spectrum. The intensity of the emission shows large variations with ion fluence, and is characterized by 0.4, 2 and 7 ns decay times.
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  • 7
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 337-340 
    ISSN: 0392-6737
    Keywords: Atoms and molecules ; Magnetic ordered materials: other intrinsic properties ; Magnetomechanical and magnetoelectric effects, magnetostriction ; Mössbauer effect: other γ-ray spectroscopy ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary The high-energy heavy-ion irradiation of magnetic materials induces not only amorphous matter in the ion tracks but also improvement or even creation of new magnetic properties in a stressed shell surrounding the track core. Two examples are presented in this paper: magnetization creation in the spinel ZnFe2O4 after Kr, Xe and Pb irradiations and trapping of magnetic domains in another spinel, the magnetite Fe3O4, after lead irradiation.
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  • 8
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 359-363 
    ISSN: 0392-6737
    Keywords: X- and γ-rays instruments and techniques ; γ-rays ; Mössbauer effect ; other γ-ray spectroscopy ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary In the present work we report an investigation on cultures of the human osteosarcoma cell line «MG-63» and the human osteoblastic cell line «HOBIT». We have examined the combined effects of hematin and 14.4keV gamma-radiation from a Mössbauer source. Preliminary results seem to confirm the trend already observed for the bone marrow system. Different degrees of growth inhibition were observed when hematin alone and hematin plus gamma-rays were administered to the cultures. It was previously found that hematin has no toxic effects on normal cells up to a concentration of 10−4 M, but the same concentration produces various degrees of inhibition on cultures of tumor cells. While no significant effect could be attributed to irradiation alone, hematin plus irradiations show a larger inhibition than that expected for pure additive effects.
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  • 9
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 381-384 
    ISSN: 0392-6737
    Keywords: Mössbauer effect ; other γ-ray spectroscopy ; Phonons and vibrations in crystal lattices ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary The phonon energy spectra of a polycrystalline α-Fe foil were observed at 150 K and 300 K by using the nuclear resonant scattering of synchrotron radiation. In each spectrum, inelastic scattering was observed at both sides of the elastic peak. It was found that the ratio of the elastic-scattering component and the asymmetry of the intensity of the side bands observed at 150 K are larger than those observed at 300 K, respectively. The observed temperature-dependent spectra are in good agreement with the spectra calculated from the phonon energy distribution function. One of the advantageous features of this method is that the excitation of only a specific element is possible. Our results show that this method is applicable to the study of lattice dynamics and opens a new field of the nuclear resonant scattering spectroscopy.
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  • 10
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 163-180 
    ISSN: 0392-6737
    Keywords: Fine particle systems ; PACS 76.80 ; Mössbauer effect ; other γ-ray spectroscopy ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary Mössbauer spectroscopy is well known to be a very sensitive technique for studying small magnetic particles: small variations in the dynamic properties often manifest themselves as rather large changes in the spectra. However, anay detailed investigation is limited by the complexity of the phenomena and also by the line shape problem. As a result, variations in Mössbauer features between samples can always be interpreted in several ways. Utilization of other techniques to support the conclusions in indispensable. This will be emphasized in the case of γ-Fe2O3 nanoparticles, the dynamic properties of which have been studied over a very wide time range using measurements of the zero-field-cooled magnetization, thermoremanent magnetization, and a.c. susceptibility at various frequencies, in addition to Mössbauer spectroscopy. After a survey of the basic laws of superparamagnetic relaxation and the effects of interparticle interactions, this paper will show how the approximations usually made for interpreting Mössbauer data can lead to misinterpretation of the phenomena.
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  • 11
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 221-225 
    ISSN: 0392-6737
    Keywords: Radiolysis, dissociation and ionization by X-ray, γ-ray and particle radiation ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary The final product of the gamma-radiolysis of tetralithium iron (III) trioxalate chloride nonahydrate has been identified by Mössbauer spectroscopy as FeC2O4·2H2O. The radiolytic decomposition proceeds as a first-order process due to the original compound depletion and to the radiolytic stability of the ferrous compound. Chemical calibration of the relative peaks areas of the two iron species indicates that the correspondingf-factors ratio is unaffected by the radiolysis.
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  • 12
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 243-246 
    ISSN: 0392-6737
    Keywords: Mösbauer effect ; other γ-ray spectroscopy ; Fe and its alloys ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary We report on low-temperature (4.2 K)57Fe Mössbauer studies of the ternary alloy system Fe(Sb1−x Te x )2 for 0.5≤x≤1.0. The Mössbauer spectra are electric-quadrupole doublets for all the specimens, indicating a non-magnetic character. The quadrupole splitting decreases with the increase in tellurium concentration. FeTe2 has also been studied in external magnetic fields up to 6T. These experiments show that the electric-field gradient in this alloy is negative and has an asymmetry parameter of η ≈0.7.
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  • 13
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 227-230 
    ISSN: 0392-6737
    Keywords: Mössbauer spectra ; Mössbauer effect ; other γ-ray spectroscopy ; Crystalline state (including molecular motions in solids) ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary C60 (Buckminsterfullerene) is isolated from organic solvents above 260 K as an f.c.c. solid with complete orientational disorder. The rotational dynamics are diffuse and isotropic, with a short (12 ps) correlation time at 300 K. Below 260 K, the solid forms in a simple cubic lattice withPa3 symmetry. The librational motion occurs by activated jumps with a correlation time of about 60 ns at 200 K. To gain further insight into the dynamics of C60, the compound C60Fe(CO)4 (I) (generously made available to us by A. Stephens and M. Green of Oxford University) has been studied by57Fe Mössbauer spectroscopy. As expected, the resonance at 90 K consists of a doublet with an isomer shift (relative to metallic iron) of 0.034(1) mm s−1 and a quadrupole splitting of 1.607(5) mm s−1. There is no significant temperature-dependent, intensity asymmetry of the doublet. The temperature dependence of the effect magnitude is well fit by a linear regression over the range 85〈T〈210 K. To elucidate the relationship of these results to the effect of the C60 moiety in I, further lattice dynamical Mössbauer studies have been carried out on (maleic anhydride) Fe(CO)4 (II), one of the few isolatable tetracarbonyl complexes of iron. For (II), the quadrupole splitting is 1.371(5) mm s−1 at 90 K, and the temperature, dependence of the isomer shift is smaller than it is for (I), while the temperature dependence of the recoil-free fraction is significantly larger in (I) than in (II).
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  • 14
    ISSN: 0392-6737
    Keywords: Mössbauer effect ; other γ-ray spectroscopy ; Electrochemical devices ; Crystal symmetry: models, space groups and crystalline systems and classes ; Electron microscopy and other methods ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary We present here a study carried out on In16Sn4S32 and In16Fe8S32 spinels. Electronic and local environment changes of Sn and Fe are discussed from recorded Mössbauer parameters. In the case of the tin thiospinel, a reduction process from SnIV to SnII is obvious till an amount of 8 inserted Li. For the iron thiospinel a migration of iron atoms from the octahedral to the tetrahedral sites is observed. In the region of higher lithium amounts (10– Li), in both spinels a further environment appears indicating an increase of covalency.
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  • 15
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1149-1157 
    ISSN: 0392-6737
    Keywords: Optoelectronic devices ; Other solid inorganic materials ; Time-resolved optical spectroscopies and other ultrafast optical measurements in condensed matter ; Interfaces ; heterostructures ; nanostructures ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary We report the observation of strong red- and blue-light emission in free-standing porous-silicon samples prepared fromn + substrates at different anodization current densities. The surface morphology of the free-standing samples has been analyzed by means of atomic-force microscopy. Upon excitation with nanosecond pulses at room temperature, both blue and red luminescence bands appear, peaked around 3.2 and 2.0 eV, respectively. An extensive study of the time-resolved behavior of the photoluminescence signal reveals different dynamical features for the two spectral regions. The observed long decay time (several μs) of the red band reflects the predominant effect of non-radiative processes and is consistent with models based on excition diffusion through the interconnected silicon nanocrystals (quantum dots) skeleton. The relatively fast blue-band decay time (≈400 ns) is shown to be related to non-radiative recombination through trap states at the silicon nanocrystal surface.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1179-1186 
    ISSN: 0392-6737
    Keywords: Methods of deposition of films and coatings ; film growth and epitaxy ; Electrochemistry and electrophoresis ; Surface and interface chemistry ; Infrared and Raman spectra and scattering ; Photoluminescence ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary Porous-silicon layers were prepared by anodic oxidation of mono- and multi-crystalline Si substrates,n + andp-doped, in aqueous HF solutions containing surfactants. The resulting samples show a bright red-orange photoluminescence: PL spectra and uniformity are analysed as a function of surfactants kind and concentration. Moreover, the results of Raman spectroscopy are discussed in terms of current theories.
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  • 17
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1225-1232 
    ISSN: 0392-6737
    Keywords: Methods of deposition of films and coatings ; film growth and epitaxy ; Surface treatments ; Optical constants: refractive index, complex dielectric constant, absorption, reflection and transmission coefficients, emissivity ; Photoelectric conversion: solar cells and arrays ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary Porous silicon was formed on multicrystalline Si substrates by stain etching in aqueous HF/HNO3 solutions. In this work optical and electrical properties of the resulting films are discussed as a function of process parameters. Porous-Si films have been shown to be able to reduce surface reflectance to 3% in 350–700 nm wavelength range and their application in anti-reflection coating of photovoltaic solar cells has been demonstrated, obtaining (10×10) cm2 multicrystalline Si solar cells with efficiency approaching 12% under standard AM 1.5 simulated sunlight.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1233-1239 
    ISSN: 0392-6737
    Keywords: Optoelectronic devices ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary A first structural investigation, carried out by transmission electron microscopy on porous-silicon samples fromp +, 〈111〉-oriented substrates is presented. The samples, which show intense visible room temperature luminescence, are composed by an interconnected network of crystalline nanostructures. Evidences of the pores propagation along the 〈100〉 directions are provided. The optical and morphological characteristics of the investigated samples are found to be much similar to those of samples coming fromp-type, non-degenerate, 〈100〉-oriented substrates rather than those obtained from 〈100〉 substrates with comparable resistivity. This striking effect is explained by invoking different etch-limiting mechanisms during pore formation. Their relative weights are proposed to depend on the crystallographic orientation of the silicon specimen subjected to etching.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 263-268 
    ISSN: 0392-6737
    Keywords: Spin arrangements in magnetically ordered materials (including neutron and spin-polarized electron studies, synchrotron-source X-ray scattering, etc.) ; Critical-point effects, specific heats short-range order ; Antiferromagnetics ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary Mössbauer measurements have been made on two kinds of spin-glass (SG) systems: one is the magnetically non-diluted mixed compound Fe0.5Mn0.5TiO3 with the SG-freezing temperatureT SG=21.5K, and the other is the diluted one Fe0.2Mg0.8TiO3 withT SG=6K. We have shown that the temperature variation of the Mössbauer spectrum of Fe0.2Mg0.8TiO3 above and around itsT SG is essentially different from that of Fe0.5Mn0.5TiO3: the former is typical of a cluster-glass and the latter of an ordinary spin-glass. The present work has clearly demonstrated that the Mössbauer spectroscopy is the most useful and unique technique to distinguish a cluster-glass from an ordinary spin-glass.
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  • 20
    ISSN: 0392-6737
    Keywords: Mössbauer effect ; other γ-ray spectroscopy ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary Sediment cores with different sub-bottom depths (I: 45 cm and II: 700 cm) from the Peru Basin have been investigated. From the depth profile of the relative amount of Fe(II) a redox zone is obtained which correlates with the organic carbon flux into the sediment (core I). Mössbauer parameters suggest that the iron in the sediments is mainly contained in clay minerals and to varying extent also in goethite.
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  • 21
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 371-374 
    ISSN: 0392-6737
    Keywords: X-ray ; Mössbauer and other γ-ray spectroscopic analysis methods ; Molecular biophysics ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary The Rayleigh scattering of Mössbauer radiation has been measured on highly oriented fibres of Na-hyaluronate at different hydration levels. The elastic-and inelastic-scattering intensities, measured as a function of the scattering vectorQ, have provided information on the dynamic structuring of the water molecules to the polysaccharidic chains.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 385-388 
    ISSN: 0392-6737
    Keywords: Mössbauer effect ; other ψ-ray spectroscopy ; Strong field excitation of optical transitions in quantum systems multiphonon processes ; dynamic Stark shift ; Effects of internal magnetic fields ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary We have studied the time dependence of Mössbauer absorption in a magnetically soft sample of Fe18Ni82 permalloy under the influence of a radio-frequency (r.f.) magnetic field. Absorption was measured as a function of the r.f. field phase at specific gamma-ray energies. We have shown that measuring the time dependence of absorption makes it possible to differentiate between purely magnetic and magnetoacoustic modulation mechanisms even in cases where clear distinction is not visible in conventional energy domain spectra.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 145-161 
    ISSN: 0392-6737
    Keywords: Metal-insulator transitions ; High-pressure and shock-wave effects in solids ; Mössbauer effect ; other γ-ray spectroscopy ; Transition-metal compounds ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary Most previous studies of magnetism in various compounds under extreme conditions have been conducted over a wide pressure range at room temperature or over a wide range of cryogenic temperatures at pressures below 20 GPa (200 kbar). We present some of the most recent studies of magnetism over an extended range of temperatures and pressures far beyond 20 GPa,i.e. in regions of pressure-temperature (P-T) space where magnetism has been largely unexplored. Recent techniques have permitted investigations of magnetism in selected 3d transition metal compounds in regions ofP-T where physical properties may be drastically modified; related effects have often been seen in selected doping studies at ambient pressures. We present57Fe and129I Mössbauer isotope studies covering the range 300–4 K to sub-megabar pressures in compounds such as Sr2FeO4, LaFeO3 and FeI2, representative of a broad class of 3d transition metal compounds. At ambient pressure the electronic structure of the transition metal atom in these antiferromagnetic insulators extends from 3d 4 to 3d 6 and has a distinct influence on the pressure evolution of their magnetic properties. Mössbauer studies of these compounds are considered in conjunction with available structural and electrical transport data at pressure.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 299-304 
    ISSN: 0392-6737
    Keywords: Layer structures: multilayers, and superlattices (growth structure, and nonelectronic properties) ; Magnetism in interface structures (including layer and superlattice structures) ; Mössbauer effect ; other γ-ray spectroscopy ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary The synthesis of a new BCT Fe phase was performed in Fe/Ir(100) superlattices grown by MBE. Magnetic properties of57Fe/Ir(100) superlattices with 4 ml Fe and variable Ir thickness (2–30 Å) are investigated by57Fe conversion electron Mössbauer spectroscopy in the 4.2–300 K temperature range. Two spectral components are evidence, related, respectively, to Fe atoms involved in the central part of the iron layers and at the interface between iron and iridium layers. The appearance of a high magnetic hyperfine splitting in the iron BCT structure above a volume threshold of 12 Å3 is evidenced. Marked differences are observed between the mean magnetic properties and the local ones suggesting strong relaxation effects.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 259-262 
    ISSN: 0392-6737
    Keywords: Mössbauer effect, other γ-ray spectroscopy ; Spin arrangements in magnetically ordered materials (including neutron and spin-polarized electron studies, synchrotron-source X-ray scattering, etc.) ; X-ray Mössbuer and other γ-ray spectroscopic analysis methods ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary A thermodynamic calculation of the Fe−Cr−Ni phase diagram suggests that the composition 30 at.%Cr-5 at.%Ni is expected to be found inside the spinodal line, whereas 16 at.%Cr-5 at.%Ni is expected outside at 723 K. These two alloys have been thermally aged for time periods up to 40 minutes at 723K. A significant broadening of the magnetic-hyperfine-field distribution indicates that Fe-30 at.%Cr-5 at.%Ni undergoes typical spinodal decomposition in agreement with the calculation. Spinodal decomposition is distinguished from nucleation-growth by a detailed analysis of the magnetic-hyperfine-field distribution.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 137-144 
    ISSN: 0392-6737
    Keywords: Intrinsic properties of magnetically ordered materials ; Magnetic films and multilayers ; Nuclear magnetic resonance and relaxation ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary Man-made low-dimensional magnetic systems including surfaces, interfaces and multilayers, have attracted a great amount of attention in the past decade because, as expected, the lowered symmetry and coordination number offer a variety of opportunities for inducing new and exotic phenomena and so hold out the promise of new device applications. Local spin density functional (LSDF)ab initio electronic-structure calculations employing the full-potential-linearized augmented-plane-wave (FLAPW) method have played a key role in the development of this exciting field by not only providing a clearer understanding of the experimental observations but also predicting new systems with desired properties. One of the striking successes of theory in the last decade has been the calculation of hyperfine fields at surfaces and interfaces. Concurrently, several groups have followed the pioneering work of Korecki and Gradmann and have measured hyperfine fields at surfaces and interfaces. In this paper, we review new features of hyperfine-interaction investigations in man-made materials which emphasizes how the close interplay of theoretical determinations and experiment are essential because the hyperfine field is not proportional to the magnetization and so interpretations of experiment are totally dependent on theory.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 181-198 
    ISSN: 0392-6737
    Keywords: Impurities: concentration, distribution, and gradients ; Doping and impurity implantation in germanium and silicon ; Interaction between different crystal defects ; gettering effect ; Calculations of total electronic binding energy ; Elemental semiconductors ; Mössbauer effect ; other γ-ray spectroscopy ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary Experimental results are presented on the study of Sb-H complexes in crystalline silicon, employing119Sb→119Sn source Mössbauer spectroscopy and a low-energy H implantation technique. In addition to a visible component, we observe a large decrease of the Mössbauer intensity associated with the trapping of hydrogen, even at low temperatures. This is interpreted as the formation of a component with a negligible recoilless fraction. The different Mössbauer components were studied as a function of H dose, H-implantation temperature and annealing temperature. The data show that the visible component is associated with the well-known SbH complex, whereas the invisible component is associated with the formation of SbH n (n≥2) complexes. We show that these complexes are in thermal equilibrium with a larger hydrogen reservoir (H 2 * ), which governs their thermal stability. No Sb-H complexes are observed inp-type Si after H-implantation, in agreement with the current belief that hydrogen has a deep donor level in the gap. The microscopic structure of the various Sb-H and Sn-H complexes was studied with first-principles calculations using the pseudopotentialdensity-functional approach. The structure of the Sb-H complex is found to be similar to the P-H complex, with the H in an antibonding site of a Si atom neighbouring the Sb impurity. For SbH2 three configurations are found with energies differing by less than ≈ 0.1 eV. We find that the reaction SbH+H≠SbH2 is exothermic. We argue that the SbH2 complexes are shallow donors, irrespective of the structure. Therefore, the formation of SbH2 may depassivate the sample.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1187-1196 
    ISSN: 0392-6737
    Keywords: Optoelectronic devices ; Conference proceedings
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    Topics: Physics
    Notes: Summary In this paper we report on the frequency dependence of the AC conductivity of porous silicon in the range 10 Hz-100 kHz. Two types of testing devices have been fabricated on three different series of samples formed electrochemically using as a starting materialptype,n −-type andn +-type silicon substrates. For frequencies less than 20-40 kHz the conductivity is found to follow a sublinear frequency dependence. This behaviour is typical of a carrier transport mechanism determined by an anomalous diffusion process. At higher frequencies we find that surface states influence the transport mechanism. This suggests a double-channel transport mechanism: one related to porous-silicon “volume” properties and the other more connected to the “surface” itself.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1197-1204 
    ISSN: 0392-6737
    Keywords: Optoelectronic devices ; Conference proceedings
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    Topics: Physics
    Notes: Summary I–V DC characteristics have been measured on metal/ porous-silicon structures. In particular, the measurements on metal/ free-standing porous-silicon film/metal devices confirmed the result, already obtained, that the metal/poroussilicon interface plays a crucial role in the transport of any device. Four-contacts measurements on free-standing layers showed that the current linearly depends on the voltage and that the conduction process is thermally activated, the activtion energy depending on the porous silicon film production parameters. Finally, annealing experiments performed in order to improve the conduction of rectifiyng contacts, are described.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 1205-1212 
    ISSN: 0392-6737
    Keywords: Optoelectronic devices ; Conference proceedings
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    Topics: Physics
    Notes: Summary Porous-silicon-based white-light-emitting devices are presented. The fabrication process on different substrates is described. The peculiarities of technological steps for device fabrication (porous-silicon formation and aluminum treatment) are underlined. Doping profile of the porous layer, current-voltage characteristics, time response, lifetime tests and electroluminescence emission spectrum of the device are presented. A model for electrical behaviour of Al/porous silicon Schottky junction is presented. Electroluminescence spectrum of the presented devices showed strong similarities with white emission from crystalline silicon junctions in the breakdown region.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 329-336 
    ISSN: 0392-6737
    Keywords: Kinetics of defect formation and annealing ; Alloys ; Mössbauer effect ; other γ-ray spectroscopy ; Conference proceedings
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    Topics: Physics
    Notes: Summary Point defects in annealed B2-phase FeAl samples in the range 47–53 at.% Fe were studied using57Fe Mössbauer spectroscopy. Spectra were analyzed using local environment models according to which point defects in atomic shells close to probe atoms induce shifts in the nuclear monopole interaction. For well-annealed samples, better results were obtained assuming only the presence of FeAl antisite and VFe vacancy defects, and not of AlFe antisite defects. Monopole interactions of57Fe probes on the Fe and Al sublattices having no defects in the first two shells were about +0.27 and −0.03 mm s−1, respectively, with respect to Fe in alpha-Fe metal. The shifts induced by FeAl and VFe defects in the first shells of Fe probes on the Fe and Al sublattices were −0.15 and −0.24 mm s−1, respectively, and, in the second shells, +0.06 and +0.011 mm s−1. In addition to structural defects needed to accommodate deviations from stoichiometry, annealed samples were found to contain several percents of FeAl and VFe defects due to lattice disorder, with greater disorder in Fe-deficient alloys.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 353-357 
    ISSN: 0392-6737
    Keywords: Mössbauer spectra ; Spectra ; photodissociation and photoionization of biomolecules ; bioluminescence ; Measurement of rate constants ; reaction cross-sections and activation energy ; Conference proceedings
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    Topics: Physics
    Notes: Summary Partial photodissociation of two carbonmonoxy-porphyrin complexes, a bridged and a fenced one, has been achieved. The results from monitoring the recombination point to an important influence of the solvent matrix on the recombination rates.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 375-379 
    ISSN: 0392-6737
    Keywords: Phonons and vibrations in crystal lattices ; Nuclear resonance fluorescence ; Synchrotrons ; Mössbauer effect ; other γ-ray spectroscopy ; Conference proceedings
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    Topics: Physics
    Notes: Summary The Nuclear-Resonance Beamline at ESRF is dedicated to the excitation of nuclear levels by synchrotron radiation. The source of radiation and optical elements are optimized to provide an intense, highly monochromatic, collimated and stable X-ray beam of small cross-section at the Mössbauer transition energies between 6 keV and 30 keV. The set-up of the beamline allows to perform studies in diffraction, small-angle scattering, forward scattering and incoherent scattering. Equipment is available to maintain the sample at variable temperature and magnetic field. Fast detectors and timing electronics serve to separate the delayed nuclear scattering from the «prompt» electronic scattering and to measure the time spectra of nuclear radiation with sub-nanosecond resolution. The general layout and the parameters of the beamline are reported. Typical domains of applications are discussed and illustrated by first experimental results.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 199-212 
    ISSN: 0392-6737
    Keywords: Molecular biophysics ; Nuclear quadrupole resonance (NQR) ; Mössbauer spectra ; Conference proceedings
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    Topics: Physics
    Notes: Summary A self-consistent description of the EPR spectra and of the Mössbauer spectra of the natural superoxide dismutase fromPropionibacterium shermanii with ferric iron as an active centre is presented. The spectra were measured atpH 6.5, 7.8 and 9.4. The theoretical approach is based on the use of the complete crystal field Hamiltonian for the high-spin ferric complexes with due regard for the terms of the fourth power of the electronic spin. It is shown that a SOD molecule can exist in two conformations. The low-pH conformation has predominantly trigonal symmetry, while the high-pH conformation has the symmetry close to the «extreme rhombic». This interpretation is in full agreement with EXAFS structural data.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 305-311 
    ISSN: 0392-6737
    Keywords: Magnetic properties of monolayers and overlayers ; X-ray, Mössbauer and other γ-ray spectroscopic analysis methods ; Mass spectrometry (including, SIMS, multiphoton ionization and resonance ionization mass spectrometry) ; Conference proceedings
    Source: Springer Online Journal Archives 1860-2000
    Topics: Physics
    Notes: Summary The composition of differently prepared Langmuir-Blodgett multilayers of ferric arachidate has been investigated by means of absorption Mössbauer spectroscopy and heavy-ion-induced mass spectrometry. We found that the iron concentration in qualitatively good films is 3.5 times higher than the stoichiometric value. Antiferromagnetic ordering in this two-dimensional model substance can be observed when the Fe−Fe distance in the layers is about 0.3 nm or below. The area density of the iron atoms in the planes decreases with decreasingpH values of the subphase which also leads to a disappearance of the long-range magnetic ordering and to a decrease of the Debye temperature of the films which is linearly dependent on the iron concentration in the films.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 213-220 
    ISSN: 0392-6737
    Keywords: Mössbauer effect ; other γ-ray spectroscopy ; X- and γ-ray instruments and techniques ; Conference proceedings
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    Topics: Physics
    Notes: Summary The use of synchrotron radiation to excite low-lying nuclear resonances is a rapidly developing field showing great promise for hyperfine spectroscopy, phonon spectroscopy and kinetic studies, crystallography, and fundamental physics experiments. Recent technical advances in synchrotron sources, optics, and fast detectors have drastically increased signal rates and expanded the range of samples that can be studied. A typical experiment today uses a high-brightness synchrotron source having X-ray pulses well-separated in time, a meV-bandpass monochromator using perfect crystals of silicon or germanium, a sample containing resonant nuclei, and an avalanche photodiode timing detector. Both coherent and incoherent scattering can be observed; the coherent scattering is used for hyperfine spectroscopy and studies of diffraction interference phenomena, and the incoherent-scattering signal promises to be very useful for phonon spectroscopy and other studies of excitations in condensed systems. At this point seven nuclear isotopes have been used to resonantly scatter synchrotron radiation, but the number is rapidly increasing.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 231-235 
    ISSN: 0392-6737
    Keywords: Mössbauer spectra ; Structure, bonding, conformation, configuration and isomerism of biomolecules ; Conference proceedings
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    Topics: Physics
    Notes: Summary Using the possibility to produce61Co sources at the MAinz MIcrotron,61Ni Mössbauer spectroscopy was applied to different kinds of chemical problems. Measurements of isomer shifts andV zz values in some common compounds and compounds with unusual chemical bonding for comparison with band structure calculations, measurement of61Ni Mössbauer parameters in model compounds for hydrogenase and dehydrogenase with an active [NiS4] centre, and study of novel binary NiF3 compounds at helium temperature are presented.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 253-257 
    ISSN: 0392-6737
    Keywords: Mössbauer effect ; other γ-ray spectroscopy ; Fe and its alloys ; Conference proceedings
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    Topics: Physics
    Notes: Summary Magnetic properties of Fe nitrides have been re-examined by57Fe Mössbauer spectroscopy. Hyperfine magnetic fields for α″-Fe16N2 are 30, 31 and 39T at 298K, but the averaged hyperfine field is 33T and nearly equal to the value of pure α-Fe. σ-Fe2 N is an antiferromagnet below 9K having a small magnetic moment less than 0.1 μB, although γ′-Fe4N and ε-Fe3–2N are ferromagnets. ZnS-type FeN is non-magnetic at 4.2K. Mössbauer spectra obtained from NaCl-type FeN are complex and some Fe atoms in this nitride show a surprisingly large hyperfine magnetic field of 49T.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 269-273 
    ISSN: 0392-6737
    Keywords: Spin density waves ; Antiferromagnetics ; Mössbauer effect ; other γ-ray spectroscopy ; Conference proceedings
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    Topics: Physics
    Notes: Summary A new iterative procedure for a numerical analysis of Mössbauer spectra in terms of higher-order harmonics is used to study spin-and charge-density waves in single-crystal and polycrystalline samples of chromium and chromium-vanadium alloys.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 281-285 
    ISSN: 0392-6737
    Keywords: Fine particle systems ; Mössbauer effect ; other γ-ray spectroscopy ; Structural acoustics and vibration ; Conference proceedings
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    Topics: Physics
    Notes: Summary Iron particles, encapsulated by graphite layers, were produced by means of the Kratschmer arc discharge method in an iron pentacarbonyl atmosphere. The Mössbauer effect is dominated by the vibration of the particles as a whole. Superparamegnetism is dominant for iron oxide particles. No endohedral iron fullerenes were observed, contrary to a previous report.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 275-280 
    ISSN: 0392-6737
    Keywords: Mössbauer effect ; other γ-ray spectroscopy ; Magnetically ordered materials: other intrinsic properties ; Magnetic phase boundaries (including magnetic transitions, metamagnetism etc) ; Conference proceedings
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    Topics: Physics
    Notes: Summary Dilute57Fe Mössbauer-spectroscopy studies of RMn2X2 (X=Si and/or Ge, R=La, Ce, Pr, Nd, Sm, Eu and Gd) at 4.2 to 650 K yield the following results: Fe in RMn2X2 does not carry a magnetic moment. It reveals the magnetic order in the Mn and R sublattices through transferred hyperfine fields (∼100 kOe). The compounds LaMn2Si2, LaMn2Ge2, CeMn2Ge2, PrMn2Ge2, NdMn2Ge2 and SmMn2Ge2, known to be ferromagnets withT c=300–350 K, are antiferromagnetically ordered above their correspondingT c. TherT N values extend from 385 K (SmMn2Ge2) to 470 K (LaMn2Si2). At the ferromagnetic-antiferromagnetic phase transition, a sharp reorientation of the Mn magnetic moments relative to the crystalline axes occurs. In RMn2Si2−x Ge x with intermediatex values, the Ge is much more dominant in determining the magnetic properties of the Mn sublattice. While PrMn2Si2 is an antiferromagnet (T N=365 K) and PrMn2Ge2 is a ferromagnetantiferromagnet (T c=328 K,T N=415 K), we find that in PrMn2SiGe, the magnetic behaviour is similar to that in pure PrMn2Ge2,T c=305 K andT N=395 K.
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    Keywords: Phonons and vibrations in crystal lattices ; Solid-liquid transitions ; Thermodynamic properties and entropy ; Conference proceedings
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    Topics: Physics
    Notes: Summary Dynamic properties of ultrafine clusters of γ-Fe2O3 (ferric oxide, FO) were studied by Mössbauer spectroscopy and by thermodynamic analysis. The data obtained for FO clusters allowed the conclusion that dynamic properties of clusters as well as the decrease of melting point and the appearance of a gap between freezing and melting points depend on intracluster atomic mobility. Intracluster atomic mobility in FO clusters was shown to increase by the action of surfactants which decrease intercluster interactions. The increase in intracluster atomic mobility was suggested to proceed via formation of a solid-liquid state.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 293-297 
    ISSN: 0392-6737
    Keywords: Doping and impurity implantation in germanium and silicon ; Elasticity, elastic constants ; Crystal morphology and orientation ; Point defects (vacancies, interstitials, colour centres, etc.) and defect clusters ; Conference proceedings
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    Topics: Physics
    Notes: Summary We have shown through Mössbauer spectroscopy that the electric field gradient (EFG), associated with an atomic defect, is sensitive to the bending of ultrathin Si crystals. The changes in the EFG depend on the bending direction. A direct application is the derivation of the orientation of defects that are located in the crystal’s surface region. We have used this observation for determining the configuration of Co dimers in Si. Based on the bending experiments, the pair axis is found to point in the 〈110〉 direction with respect to the host lattice.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 313-317 
    ISSN: 0392-6737
    Keywords: Mössbauer spectra ; Magnetism in interface structures (including layer and superlattice structures) ; Superface and interface chemistry ; Conference proceedings
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    Topics: Physics
    Notes: Summary Surface chemical states of57Co2+ and119Sb5+ ions adsorbed on γ-Fe2O3 and NiFe2O4 were studied in the presence of the aqueous phase using the magnetic interaction between the substrates and57Fe2+ or119Sn4+ arising from the adsorbed species. Two chemical forms were observed for the57Co2+ adsorbed on γ-Fe2O3; one giving a peak in the high-field region and another giving a broad distribution in the lower fields, which were attributed to57Co2+ at surfaceB sites of the spinel structure of γ-Fe2O3 and57Co2+ species weakly bonded to the substrate, respectively. In case of the NiFe2O4 substrate, the latter species was dominant and was converted to the former by heating. Most of the119Sb5+ ions adsorbed on the γ-Fe2O3 and NiFe2O4 particles were found to have a certain magnetic interaction with the magnetically ordered ions of the substrates.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 319-323 
    ISSN: 0392-6737
    Keywords: Magnetism in interface structures (including layer and superlattice structures) ; Magnetic properties of monolayers and overlayers ; Interfacial magnetic properties ; Mössbauer effect ; other γ-ray spectroscopy ; Conference proceedings
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    Topics: Physics
    Notes: Summary A series of ultrathin Fe/Pt multilayers, prepared by magnetron sputtering, were studied by CEMS and transmission MS. The Fe-layer thickness varied from 3 to 12.5 Å and that of Pt from 5 Å to 39 Å. The 3 Å/9 Å Pt sample displays magnetic hyperfine structure at RT, while the 3 Fe/19 Pt sample is paramagnetic at RT, demonstrating the effect of interlayer interaction. Both samples display out-of-plane magnetic anisotropy with 39° angle with respect to the vertical for the former and nearly 0° angle for the latter. The analysis of the spectra of samples with thickness larger than one monolayer of Fe is done with components assigned to individual Fe monolayers. In all these cases a component appears with a hyperfine field larger by ∼ 10% at RT and 17% at L.He than the corresponding values of α-Fe. This component is attributed to the first monolayer below the Fe/Pt interface in accordance with similar results in the Fe/Pd system and with theoretical predictions.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 325-328 
    ISSN: 0392-6737
    Keywords: X-ray Mössbauer and other γ-ray spectroscopic analysis methods ; Metals and alloys ; Composition and phase identification ; Conference proceedings
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    Topics: Physics
    Notes: Summary The characterization of the corrosion products formed on an57Fe film onto a low alloy steel disc after 4 h and 8 h exposure to an artificially SO2-polluted atmosphere has been carried out by ICEMS/DCEMS. The corrosion products found are FeSO3·3H2O, FeSO4·nH2O, a third unidentified Fe2+ species, an amorphous Fe3+ oxyhydroxide and a second Fe3+ species which could correspond to superparamagnetic α-FeOOH or ferrihydrite. Although the DCEM spectra recorded at different electron energies do not show dramatic differences in the relative concentrations with depth, the results suggest that FeSO3·3H2O is preferentially located in the inner part of the corrosion layer whilst the outer part is richer in FeSO4·nH2O and Fe3+ species.
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  • 47
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    Keywords: Mössbauer effect ; other γ-ray spectroscopy ; Other topics in biophysics and medical physics ; Conference proceedings
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    Topics: Physics
    Notes: Summary This paper describes a preliminary investigation of the mechanisms of Fe(II) oxidation and storage of Fe(III) in the bacterioferritin ofEscherichia coli (EcBFR). Using Mössbauer spectroscopy to examine the initial oxidation of iron by EcBFR we have confirmed that this ferritin exhibits «ferroxidase» activity and have shown that dimeric and monomeric iron species are produced as intermediates. We compare the characteristics of ferroxidase activity in EcBFR with those of human H-chain ferritin (HuHF) and discuss the different Mössbauer parameters of their dimeric iron with reference to the structures of their di-metal sites. In addition, we present preliminary findings suggesting that after an initial «burst», the rate of oxidation is greatly reduced, possibly due to blockage of the ferroxidase centre by bound iron. A new component, not found in HuHF and probably representing a small cluster of Fe(III) atoms, is reported.
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  • 48
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    Keywords: Molecular dynamics and conformational changes ; Mössbauer effect ; other γ-ray spectroscopy ; Brillouin and Rayleigh scattering ; other light scattering ; Conference proceedings
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    Topics: Physics
    Notes: Summary The classical model system poly-L-glutamic acid (poly-Glu), was investigated in a disordered coil state (atpH=7.0) and in helix state (atpH=2.0) by the RSMR technique. By considering that the coil state of poly-Glu models unfolded (random coil) state and α-helix state models the fluctuating secondary structure (during consequent folding of protein), a comparative analysis of the dynamical properties of poly-Glu in different states with the dynamical properties of different proteins in the native state (α-helical myoglobin and HSA, partially β-sheet lysozyme) and in intermediate (molten globule) state (α-lactalbumin) was performed. This comparison brings some unpredicted results: native α-helical proteins behave close to random coil, native partially β-sheet proteins behave close to fluctuating secondary structure (α-helix) and the dynamic behaviour of molten-globule state (partially β-sheet α-lactalbumin) is not different from the behaviour of lysozyme and much more rigid than that of native α-helical proteins.
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    Il nuovo cimento della Società Italiana di Fisica 18 (1996), S. 107-136 
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    Keywords: Crystal and ligand fields ; Mossbauer effect ; other γ-ray spectroscopy ; Visible and ultraviolet spectra ; Conference proceedings
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    Topics: Physics
    Notes: Summary Coordination compounds of transition metal ions with open-shell electron configurations may exhibit dynamic electronic-structure phenomena, depending on the nature of the coordinating ligand sphere. The change of spin state with temperature («thermal spin-crossover»), light-induced electron transfer processes leading to long-lived metastable charge and spin states (e.g., «LIESST» effect), are some of the fascinating electronic games encountered in transition metal compounds, which are presently under extensive study by chemists and physicists. Mössbauer spectroscopy plays a dominant role in the investigation of such phenomena in iron compounds, as will be demonstrated in this paper. This work will focus on selected examples of «thermal spin-crossover» in iron(II) complexes and switching between different spin states by irradiation with light of different wavelength (LIESST effect), demonstrating that Mössbauer spectroscopy besides other physical techniques proves to be a highly elegant tool for following the spin state conversion and the concomitant changes of molecular and crystal structure properties. Finally, Mössbauer emission spectroscopy, both time integral and time differential, has been employed to generate and identify long-lived excited spin states by making use of the nuclear disintegration of57Co as an intrinsic molecular light source (NIESST=nuclear decay-induced excited-spin-state trapping). Lifetime measurements by optical techniques on LIESST states and by time-differential Mössbauer coincidence spectroscopy on NIESST states prove that the relaxation pathways in the mechanisms for LIESST and NIESST are identical.
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    European biophysics journal 24 (1996), S. 293-299 
    ISSN: 1432-1017
    Keywords: Phase transition ; NMR ; DSC ; X-ray diffraction ; Bonnet Transformation
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    Topics: Biology , Physics
    Notes: Abstract Ternary systems of palmitoyl-oleoyl-phosphatidylcholine (POPC) and the non-ionic surfactant C12EO2 (di-ethylene-oxide-mono-dodecyl-ether) in water have been studied with optical microscopy, NMR, DSC and X-rays from ambient temperatures to 45 °C. Below 29 °C the system is in the lamellar liquid crystalline state. Between 30 and 32 °C it transforms into a cubic Ia3d structure which converts into the cubic Pn3m phase at 39 °C. The transitions are fully reversible. An epitaxial relationship between all three phases was found, which is an elegant and convenient way to rearrange molecules from lamellar bilayers to a network of curved surfaces. The la3d (Q230) to Pn3m (Q224) transition occurs without measurable enthalpy change. This, together with the metric relation of 1.60 between the cubic lattice constants is strong evidence for a Bonnet transformation, where the structural changes occur without change in curvature. The potential significance of the cubic phases as intermediate structures for biological processes, e. g. transport across a bilayer or fusion of membranes, are discussed.
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    Environmental management 20 (1996), S. 523-539 
    ISSN: 1432-1009
    Keywords: Water control ; Floodplain ; Fisheries ; Bangladesh ; Chandpur
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    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract Bangladesh is a very flat delta built up by the Ganges—Brahmaputra—Meghna/Barak river systems. Because of its geographical location, floods cause huge destruction of lives and properties almost every year. Water control programs have been undertaken to enhance development through mitigating the threat of disasters. This structural approach to flood hazard has severely affected floodplain fisheries that supply the major share of protein to rural Bangladesh, as exemplified by the Chandpur Irrigation Project. Although the regulated environment of the Chandpur project has become favorable for closed-water cultured fish farming, the natural open-water fishery loss has been substantial. Results from research show that fish yields were better under preproject conditions. Under project conditions per capita fish consumption has dropped significantly, and the price of fish has risen beyond the means of the poor people, so that fish protein in the diet of poor people is gradually declining. Bangladesh is planning to expand water control facilities to the remaining flood-prone areas in the next 15–20 years. This will cause further loss of floodplain fisheries. If prices for closed-water fish remain beyond the buying power of the poor, alternative sources of cheap protein will be required.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 35-49 
    ISSN: 1572-8943
    Keywords: bone cement ; DSC ; kinetics
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Bone cements are widely used for the fixation of metallic prostheses in orthopaedics and to form replacements for skull defects in neurosurgery. Acrylic bone cements are based on a mixture of methyl methacrylate (MMA) and a fine powder of polymethyl methacrylate (PMMA). The polymerization of the bone cement occurs in contact with the bone and the prosthesis which act as the boundaries of a bulk polymerization reactor. The kinetic behaviour of the bone cement plays a fundamental role for the final performance of the implant. In this paper, the isothermal and non-isothermal polymerization behaviour of a commercial bone cement is described. A simple phenomenological model, accounting for the autoacceleration ffect, for a diffusion controlled termination mechanism and for the reaction between inhibitor and initiator, is proposed. The reaction kinetics is analysed by DSC. DSC data are used for the determination of the rates of polymerization under isothermal and non-isothermal conditions. The experimental data are processed to calculate the parameters of the proposed phenomenological kinetic model. The analytical and numerical details related to the integration of the model are discussed.
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  • 53
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    Journal of thermal analysis and calorimetry 47 (1996), S. 181-194 
    ISSN: 1572-8943
    Keywords: DSC ; gelatinization
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Data obtained by dynamic mechanical analysis and DSC analysis of durum wheat dough are presented and discussed. Doughs with water contents ranging from 45 to 55% (w/w) were subjected to sinusoidal shearing by means of a dynamic mechanical spectrometer (Rheometrics, RFS2) equipped with parallel plate geometry, 0.1 strain amplitude and 1 rad/min frequency. The tests were carried on in temperature sweep mode at a heating rate of 2°C min−1. Wheat samples with water contents in the range between 7.5 and 37.5% and doughs with 37.5% moisture content were mixed for different times and subjected to DSC analysis (Perkin-Elmer, DSC-7) at a heating rate of 20°C min−1. Dynamic mechanical analysis revealed that the relationship between the dynamic properties of the dough and the temperature was modified as the water content of the dough increased and was quite different from that for gluten. A similar response was observed in the course of temperature scans made by means of DSC. These experimental findings suggest that the water-starch interaction in the presence of a protein matrix is affected by the availability of water and that the protein system is a competitor with respect to starch.
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  • 54
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    Journal of thermal analysis and calorimetry 47 (1996), S. 543-557 
    ISSN: 1572-8943
    Keywords: compensation effect ; DSC ; kinetics ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Four computer programs as well as one demo-version for non-linear evaluation of kinetic data in thermal analysis and calorimetry, were presented. The multi-task program TA-kin meets all mathematical requirements for solving the numerical assignments. It is shown that the so-called compensation effect is due to the mathematical structure of the Arrhenius equation. Several applications of TA-kin to a lot of DSC- and TG-measurements and isoperibolic batch experiments as well as adiabatic semi batch experiments realized by precision calorimetry have been discussed.
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  • 55
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    Journal of thermal analysis and calorimetry 47 (1996), S. 685-695 
    ISSN: 1572-8943
    Keywords: DSC ; polymers ; resins ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The paper describes the co-curing studies of ethynyl and ethenyl end-capped imide resins. The effect of composition and chemical structure of ethenyl end-capped resins (nadicimides) on thermal behavior of ethynyl end-capped resins was evaluated using DSC and thermogravimetric analysis. An increase in char yield was observed on co-curing of few resin formulations. A mechanism has been proposed to account for this observation.
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  • 56
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1213-1228 
    ISSN: 1572-8943
    Keywords: cassava starch ; DSC ; starch thermal properties
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Order-disorder transitions were investigated in native cassava starch at intermediate moisture contents (35 to 60% wt. water), using Differential Scanning Calorimetry (DSC) and dynamic Wide Angle X-ray Diffractometry (WAXS) with a synchrotron radiation source. The gelatinization of granules occurs as a cooperative process, due to constraints induced in crystallites by the amorphous areas. Variations of water content (water volume fraction from 0.28 to 0.86) and heating rate (0.2–10
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  • 57
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1179-1200 
    ISSN: 1572-8943
    Keywords: DSC ; isothermal microcalorimetry ; retrogradation ; starch
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    Topics: Chemistry and Pharmacology
    Notes: Abstract In the present study, isothermal microcalorimetry was introduced as a tool to investigate properties of starch retrogradation during the first 24 h. The study was made on purified amylose and amylopectin from corn, as well as on native starches, such as wheat, potato, maize, waxy maize and amylomaize, differing in their amylose content. The results were obtained in the form ofP-t traces (thermal powervs. time), and integration of these traces gave a net exothermic enthalpy of reaction, caused by the crystallization of amylose and amylopectin. TheP-t traces reflected the quantities of amylose and amylopectin in the starch studied. Depending on the amylose content and the botanical source of the starch, the rate of crystallization of amylose was high and predominated over that of amylopectin during the first 5–10 h. The contribution from amylose crystallization to the measured exothermic enthalpy was very substantial during this period. After ∼10 h, amylose crystallized at a lower constant rate. During the first 24 h, amylopectin crystallized at a low steady rate. The exothermic enthalpies obtained by the isothermal microcalorimetric investigations during the first 24 h of retrogradation were generally low in relation to the endothermic melting enthalpies observed by differential scanning calorimetry (DSC) measurements after 24 h of storage. The discrepancies in enthalpy values between the two methods are discussed in relation to phase separation and the endothermic effects owing to the decrease in polymer-water interactions when polymer-rich regions in the starch gel separate. Besides the exothermic enthalpies obtained, theP-t traces also made it possible to study the initial gelation properties of amylose from different botanical sources. The present study further demonstrated that isothermal microcalorimetry can provide a possible way to investigate the antistaling effect of certain polar lipids, such as sodium dodecylsulphate (SDS) and 1-monolauroyl-rac-glycerol (GML), when added to starches of different botanical origin. The net exothermic heat of reaction for starch retrogradation during the first 24 h was decreased when GML or SDS was added to the starch gels. The recordedP-t traces also showed how the effect of the added lipid influenced different periods during the first 24 h of starch retrogradation, and that the effect depended mainly on the amylose content, the botanical source of the starch, and the type of lipid used. When GML or SDS was added to waxy maize, the isothermal microcalorimetric studies clearly indicated some interaction between amylopectin and the polar lipids. These results concerning the action of anti-staling agents are further discussed in relation to the helical inclusion complexes formed between amylose-polar lipid and amylopectin-polar lipid.
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  • 58
    ISSN: 1572-8943
    Keywords: cooling/heating rate ; DSC ; fragility parameter ; glass transition temperature ; sorbitol-fructose
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The glass transition temperatures of sorbitol and fructose were characterized by four points determined on DSC heating thermograms (onset, mid-point, peak and end-point), plus the limit fictive temperature. The variations of these temperature values, observed as functions of cooling and heating rates, were used to determine the fragility parameter, as defined by Angell [1] to characterize the temperature dependence of the dynamic behavior of glass-forming liquids in the temperature range above the glass transition. The apparent activation energy values, determined for the different temperatures studied, were similar for fructose and sorbitol. These values were compared to data obtained from other techniques, such as mechanical spectroscopy. The variations of the apparent activation values, observed in experiments involving cooling and heating at the same rate, slow cooling followed by rate-heating, or rate-cooling followed by fast heating, were explained by aging effects occurring during the heating step.
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  • 59
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1545-1565 
    ISSN: 1572-8943
    Keywords: cocoa butter ; fat crystallization ; DSC ; fat polymorphism ; fat structure ; fats ; lard ; milk fat ; triacylglycerols ; X-ray diffraction
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal behavior of three ural fats (displaying very different composition), cocoa butter (CB)2, lard, and a stearin obtained from anhydrous milk-fat (AMF) fractionation, were studied by both DSC and X-ray diffraction as a function of temperature (XRDT). To perform temperature explorations between −30
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    Journal of thermal analysis and calorimetry 46 (1996), S. 5-14 
    ISSN: 1572-8943
    Keywords: cadmium phenoxyacetate ; complexes ; DSC ; mercury(II) phenoxyacetate ; TG
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Solid cadmium and mercury(II) phenoxyacetates were prepared and investigated by DSC and TG techniques. The cadmium salt decomposed in two steps with the loss of 1.5 water molecules at first and the successive formation of CdCO3 as final product. Δdeh H * associated with the loss of one water molecule was compared with the corresponding values obtained for other phenoxyacetates previously studied and the obtained results were discussed. Anhydrous mercury(II) phenoxyacetate gave, on heating, HgCO3 which successively decomposed with the formation of gaseous products and a little amount of solid residue.
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    Journal of thermal analysis and calorimetry 46 (1996), S. 177-186 
    ISSN: 1572-8943
    Keywords: activation energy ; chalcogenide glass ; DSC
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Results of differential scanning calorimetry (DSC) at different heating rates on Se2Ge0.2Sb0.8 chalcogenide glass are reported and discussed. As the heating rate (α) changed, also the glass transition temperature (T g) and onset temperature of crystallization (T c) changed. As the value of the transition activation energyE t changed, the crystallization fraction (χ), heat flow (Δq and the crystallization peak temperature (T p) also changed. The value of the effective activation energy of crystallizationE c was calculated by means of six different methods. The Se2Ge0.2Sb0.8 chalcogenide glass has two crystallization mechanisms, a one-dimensional and an other surface crystallization growth. The average value ofE t for Se2Ge0.2Sb0.8 is equal to 194.95±3.9 kJ·mol−1 and the average value ofE c is equal to 164±3.3 kJ·mol−1.
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  • 62
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    Journal of thermal analysis and calorimetry 46 (1996), S. 237-243 
    ISSN: 1572-8943
    Keywords: DSC ; DTG ; polyacetylene films ; TMA
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Polyacetylene films irradiated byγ-rays up to 100 MRad were studied by means of TMA, DTG and DSC methods. It is shown that as the irradiation dose increases the concentration of topological branching knots into the polymer chains and theT g values decrease, the total mass loss and the enthalpy of the thermal isomerization reaction also decrease.
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  • 63
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    Journal of thermal analysis and calorimetry 46 (1996), S. 619-626 
    ISSN: 1572-8943
    Keywords: crystallization ; DSC ; filled polypropylene ; nucleation ; structural modification
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of high concentration of BaSO4 as nucleating agent on crystallization of fiber-forming polypropylene was studied by DSC. The work presents experimental and calculated values of melting and crystallization enthalpies of filled polypropylene and the influence on the formation of interface interactions between filler and polymers. These results show minimal interactions of components (BaSO4 and polypropylene) under experimental conditions.
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  • 64
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    Journal of thermal analysis and calorimetry 46 (1996), S. 643-679 
    ISSN: 1572-8943
    Keywords: DDTA ; DSC ; macromolecules
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This review traces the development of thermal analysis over the last 40 years as it was experienced and contributed to by the author. The article touches upon the beginning of calorimetry and thermal analysis of polymers, the development of differential scanning calorimetry (DSC), single run DSC and other special instrumentations, up to the recent addition of modulation to calorimetry. Many new words and phrases have been introduced to the field by the author and his students, leaving a trail of the varied interests one can have over 40 years. It began with “cold crystallization” and most recently the term “oriented, intermediate phase” was coined, creating in-between: “extended chain crystals,” the “irreversible thermodynamics of melting of polymer crystals,” “dynamic differential thermal analysis” (DDTA), “the rule of constant increase ofC p per mobile bead within a molecule at the glass transition temperature,” “superheating of polymer crystals,” “melting kinetics,” “crystallization during polymerization,” the “chain-folding principle, “molecular nucleation,” “rigid amorphous phase,” a “system of classifying molecules,” “macroconformations,” “amorphous defects,” “rules for the entropy of fusion based on molecular shape and flexibility,” “single-molecule single-crystals,” “a system of classifying phases and mesophases,” and “condis phase.”
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    Journal of thermal analysis and calorimetry 46 (1996), S. 795-808 
    ISSN: 1572-8943
    Keywords: DSC ; kinetics ; liquid crystalline polymer ; optical transmittance ; polycarbosilane ; side-chain mesogen ; transition parameters
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This paper is concerned with an analysis of the thermodynamics and kinetics of mesophase formation by cooling from the isotropic state of side-chain liquid crystalline polycarbosilanes containing spacers in the range from 3 to 11 CH2-groups. The polymers are characterized by their thermotropic behaviour as far as temperature, enthalpy and entropy of the transitions are concerned. The kinetics was followed by optical and calorimetric methods. Longer spacer length leads to more perfect ordering in the mesophase, higher isotropization temperatures, and lower glass transition temperatures. The Avrami and Ozawa formalism to describe the transition kinetics to the mesophase from the isotropic state cannot be interpreted as the nucleation and growth mechanism known from crystallization.
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  • 66
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1201-1212 
    ISSN: 1572-8943
    Keywords: aging ; amylopectin ; DSC ; gels ; glass transition ; recrystallization ; retrogradation ; rice starch ; sugars
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermal characterization of gelatinized binary rice starch-water and ternary starch-sugar-water gels before and after aging was carried out using differential scanning calorimetry. The glass transition temperature of the maximally freeze-concentrated solution (T′g) in both fresh and aged gels was observed to decrease progressively with increasing sugar concentration. Aging of the gels generally shiftedT′g to higher temperatures, but had little or no effect on the ice melting peak temperature (T m). The presence of various sugars could either accelerate or retard starch (amylopectin) recrystallization, depending on the type and concentration of sugar, as well as on starch/water ratio. A hypothesis based on the dual antiplasticizing-plasticizing effects of sugars was postulated to explain the observed effects. Of the sugars studied, xylose and fructose appeared to display exceptional retardative and accelerative effects, respectively, on retrogradation.
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  • 67
    ISSN: 1572-8943
    Keywords: DSC ; gelatinisation ; potato starch
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Gelatinisation temperatures as a function of moisture content were determined for potato starch. The native starch was then hydrothermally treated at a temperature 3% (Kelvin degrees) below the gelatinisation peak temperature and at moisture levels varying from 20 to 67% (by weight). Gelatinisation temperatures, temperature ranges and enthalpy values were affected for all treated samples. However, two sample populations could be distinguished: those samples treated under ‘limited’ moisture conditions and other samples treated in the presence of ‘extragranular’ moisture. A two-step hydrothermal treatment further increased the gelatinisation temperature, but the effect of the second step was small in comparison to that of the first.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1299-1314 
    ISSN: 1572-8943
    Keywords: baked goods ; cookies ; crackers ; DSC ; pretzels ; starch
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    Topics: Chemistry and Pharmacology
    Notes: Abstract We describe an application of DSC as an analytical ‘fingerprinting’ method that has been used to characterize the thermal properties of wheat starch in low-moisture, wheat-flour-based baked products, including cookies, crackers, and pretzels. This use of DSC has enabled us to relate starch thermal properties, on the one hand, to starch structure, and on the other hand, to starch functionality, in terms of baking performance and finished-product quality.
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  • 69
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1339-1360 
    ISSN: 1572-8943
    Keywords: bread crumb ; bread dough ; DSC ; hydrocolloid ; mechanical properties ; pentosans ; protein
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The effects of hydrocolloids (guar and locust bean gums), soluble pentosans, and whey proteins on staling of bread crumb were investigated by means of DSC, rheometry, and image analyis. One current hypothesis, that these ingredients would behave as “water binders” and, at least the former two, as anti-staling agents, was indeed confirmed, although this action might be indirect. All the samples considered showed an exothermic DSC peak preceding the endotherm of the amylopectin fusion. According to a previous work, this signal was attributed to a water-dependent cross-linking process that would involve next-neighbouring polymer chains. To check the effect produced by molecular modifications that were expected to increase the water uptake of these ingredients, doughs containing added succinylated pentosans and whey proteins, and a polycarboxylate polymer, PEMULEN TR-1, were examined. These modifications enhanced starch retrogradation and yielded a firmer crumb. It was tentatively concluded that some direct interaction between these modified molecules and the crumb polymers might have taken place. In line with the food polymer science approach, the use of Time-Temperature-Transformation (TTT) diagrams is also discussed.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1513-1525 
    ISSN: 1572-8943
    Keywords: Β-lactoglobulin ; DSC ; protein modification ; thermal properties
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal properties of Β-lactoglobulin (Β-LG) were studied by differential scanning calorimetry (DSC) under different medium conditions.pH, neutral salts, protein perturbants, and polyols all affected the DSC characteristics of Β-LG. Acylation with fatty acids also changed the thermal properties, particularly peak width at half-height. The results suggest that the structural stability of Β-LG is controlled by non-covalent forces, particularly electrostatic and hydrophobic interactions. Disulfide bonds did not contribute to the thermal response of Β-LG. Fatty N-acyl-amino acids caused marked increases in thermal stability and decreases in denaturation enthalpy, and additional peaks were observed in the presence of some palmitoyl derivatives.
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    Journal of thermal analysis and calorimetry 46 (1996), S. 347-352 
    ISSN: 1572-8943
    Keywords: DSC ; optical densities ; thermal stability ; three-component interpolymer complexes
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A new type of three-component interpolymer complexes (3IPCM) formed by two similarly charged polyelectrolytes and an oppositely charged low molar mass compound was studied by DSC, NMR and X-ray methods. The low molar mass monobasic compounds in these complexes act as mediators. This type of complexes differs from earlier-obtained 3IPCM, which contained a dibasic low molar mass mediator. The present 3IPCM were obtained from two polymers (polyacrylic acid and sodium polyphosphate) and bases such as 4-vinylpyridine and 2-methyl-5-vinylpyridine.
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  • 72
    ISSN: 1572-8943
    Keywords: cure kinetics ; DSC ; epoxy resins ; gelation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract By employing differential scanning calorimetry (DSC) we have studied the kinetic of the cure reaction for a system containing a diglycidyl ether of bisphenol A (DGEBA) and 1,3-bisaminomethylcyclohexane (1,3-BAC) as a curing agent, using an isothermal approach over the temperature range of 60–110°C. We have determined the reached conversions at several cure temperatures and the reaction rates. The results showed that this cure reaction is autocatalytic. The experimental data were compared with the autocatalytic model proposed by Kamal, which includes two rate constants and two reaction orders. This model gives a good description of cure kinetics up to vitrification point. The activation energies for these rate constants were 44-57 kJ mol−1. From the gel time measurements the value obtained for the overall activation energy was 49.5 kJ mol−1.
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    Journal of thermal analysis and calorimetry 46 (1996), S. 465-470 
    ISSN: 1572-8943
    Keywords: ABS polymer ; DSC ; lifetime estimation ; thermooxidation
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The service life of ABS polymer, stabilized by 2-(3,5-di-tert-butyl-4-hydroxyanilino)-4,6-bis(octylthio)-1,3,5-triazine and containing 50% of a modifying rubber component, was estimated from oxidative induction times measured by DSC in isothermal mode in the temperature interval 140–170°C. The lifetime of ABS powder at the actual temperature of drying was predicted by linear extrapolation according to Arrhenius. However, the extrapolated value was much longer than the real lifetime determined from the long-term oven aging tests at 70 and 90°C, simulating the industrial drying process. The effect of changes in the apparent activation energy of oxidation due to antioxidant consumption during polymer aging is discussed.
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  • 74
    ISSN: 1572-8943
    Keywords: complexes ; DSC ; guest-host interactions ; X-ray
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    Topics: Chemistry and Pharmacology
    Notes: Abstract The stoichiometry of thermal decomposition and the thermochemistry were studied for [NiL4(NCS)2] (I) as a host complex, and for its clathrates of type [NiL4(NCS)2]·2G, where L=4-ethylpyridine and guest molecule G=1-methylnaphthalene in clathrate (II), 1-chloronaphthalene in (III) or 1-bromonaphthalene in (IV). For I, the loss of volatile components proceeds in three steps (−2L, −L, −L); the first steps for II–IV also involve the release of G (−2G, −2L). DSC and X-ray powder measurements indicated a phase transition in the host lattice, and allowed differentiation of the escape of G and L molecules. The enthalpy changes give the following sequence of thermodynamic stability for the studied chlathrates: I〉II〉III.
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    Journal of thermal analysis and calorimetry 46 (1996), S. 753-771 
    ISSN: 1572-8943
    Keywords: crystal-crystal transitions ; crystal forms ; DMA ; DSC ; Nylon M5T ; X-ray
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    Topics: Chemistry and Pharmacology
    Notes: Abstract Poly(2-methylpentamethylene terephthalamide) (Nylon M5T) is a new high temperature aromatic polyamide developed by Hoechst Celanese. In this paper thermal properties of Nylon M5T chips, as well as as-spun and drawn fibers were studied by DSC, DMA, hot stage microscopy and WAXS.T g of the fully amorphous Nylon M5T is 143°C when measured by DSC;T g increases with crystallinity to 151°C. The temperature dependence of the solid and melt specific heat capacities has also been determined. The heat capacity increase at the glass transition of the amorphous polymer is 103.9 J °C−1 mol−1.T g by DMA for the as-spun fiber is 155°C, for a drawn fiber is 180°C. Three secondary transitions were observed by DMA in addition to the glass transition. These correspond to a local mode relaxation of the methylene groups at −120°C, onset of rotation of the amide-groups at −65°C and the onset of the rotation of the phenylenegroups (at 63°C). The crystallinity of Nylon M5T strongly depends on the rate of cooling from the melt. The isothermal crystallization data are melt temperature dependent: two-dimensional crystallization takes place when the samples are crystallized from higher melt temperatures, and this phase changes into a spherulitic structure during cooling to room temperature. Spherulitic crystallization occurs when lower melt temperatures are used. This polymer has three crystal forms as indicated by DSC, DMA and WAXS data. The crystal to crystal transitions are clearly visible when amorphous samples are heated in the DSC, or the DMA curves of as-spun fibers are recorded. It is experimentally shown that a considerable melting of the lower temperature crystal forms takes place during the crystal to crystal transitions. The equilibrium melting point as measured by the Hoffman-Weeks method, has been determined to be 339°C.
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    Journal of thermal analysis and calorimetry 46 (1996), S. 871-878 
    ISSN: 1572-8943
    Keywords: DSC ; melting point ; polyethylene ; Raman-active longitudinal acoustical mode ; semi-crystalline polymers
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    Topics: Chemistry and Pharmacology
    Notes: Abstract This is a study for criteria to judge the melting point of semi-crystalline polymers from the DSC endotherm for polymer melting. Beyond standard indium DSC melting results an evaluation has been made on a series of polyethylenes for which crystal sizes were measured and predicted from Raman LAM analysis. The results confirm the conclusion of Prof. Wunderlich that the DSC content of melting is the proper basis of reporting melting points.
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    Journal of thermal analysis and calorimetry 46 (1996), S. 893-903 
    ISSN: 1572-8943
    Keywords: cold crystallization ; DSC ; heat capacity ; modulated temperature DSC ; poly(ethylene terephtalate)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The modulated temperature differential scanning calorimetric method (MT-DSC) yields three temperature dependent signals, an underlying heat capacity curve from the underlying heat flow rate (corresponding to the conventional DSC signal), and a complex heat capacity curve with a real part (storage heat capacity) and an imaginary part (loss heat capacity). These curves have been measured in the cold crystallization region for poly(ethylene terephtalate) with a modified Perkin-Elmer DSC-7. The underlying curve shows the well known large exothermic crystallization peak. The storage heat capacity shows a step change which reproduces the change in heat capacity during crystallization. This curve may be used as baseline, to separate the crystallization heat flow rate from the underlying heat flow rate curve. The loss heat capacity curve exhibits a small exothermic peak at the temperature of the step change of the storage curve. It could be caused by changes of the molecular mobility during crystallization.
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1251-1258 
    ISSN: 1572-8943
    Keywords: boiling points ; DSC ; TGA ; vapour pressure
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    Topics: Chemistry and Pharmacology
    Notes: Abstract A TGA instrument has been adapted for rapid measurement of boiling points and vapour pressure at temperatures from ambient up to 400°C and pressures from ambient down to 20 mm Hg. Samples were contained in sealed holders having a laser-drilled aperture. Several organic liquids in the 100 to 300 gMW range showed good agreement with reference vapour pressure data. Sample mass, heating rate, and use of inert diluents were important variables affecting accuracy of vapour pressure measurements.
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    Journal of thermal analysis and calorimetry 47 (1996), S. 957-973 
    ISSN: 1572-8943
    Keywords: DSC ; Gibbs energy ; liquid crystalline polyethers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A series of polyethers have been synthesized from 1-(4-hydroxy-4′-biphenyl)-2-(4-hydroxyphenyl)propane and α, Ω-dibromoalkanes having different numbers of methylene units [TPPs]. Both odd- and even-numbered TPPs [TPP(n=odd)s and TPP(n=even)s) exhibit multiple transitions during cooling and heating and they show little supercooling dependence, indicating close-to-equilibrium nature of these transitions. Combining the structural characterization obtainedvia wide angle X-ray diffraction powder and fiber patterns at different temperatures and the morphological observations from microscopy techniques, not only the nematic liquid crystalline phase but also highly ordered smecticF, smectic crystalG andH phases have been identified. The phase diagrams for both TPP(n=odd)s and TPP(n=even)s have been constructed [1–3]. Thermodynamic properties (enthalpy and entropy changes) during these transitions are studied based on differential scanning calorimetry experiments. The contributions of the mesogenic groups and methylene units to each ordering process can be separated and they indicate the characteristics of these processes thereby providing estimations of the transition types.
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  • 80
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1743-1753 
    ISSN: 1572-8943
    Keywords: DSC ; HSM ; oxazepam ; PEG 4000 ; solid dispersion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A thermal study using DSC and Hot Stage Microscopy (HSM) was carried out to investigate the interaction in solid state of the binary system PEG 4000 — oxazepam, and to establish their phase diagram. The eutectic composition, which melting occurs at lower temperature as compared with the pure components, has been determined. The results obtained by DSC and HSM have indicated that PEG 4000 — oxazepam mixtures displays no obvious incompatibilities, and that the system shows a typical eutectic behaviour. However because of the closeness of the melting of PEG 4000 to the eutectic temperature, it was difficult to determine precisely the eutectic composition and temperature on the basis of DSC measurements alone. The use of heats of fusion corresponding to physical mixtures allowed an estimation of the eutectic composition at 6% w/w oxazepam. Additional information of temperature (57.6
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  • 81
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1755-1758 
    ISSN: 1572-8943
    Keywords: combustion calorimetry ; DSC ; sulphamide type compounds
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Two compounds of sulphamide type:p-amino-benzene sulphonamide (I) and 3,4-dimethylisoxazol 5-sulphanylamide (II) were studied by combustion calorimetry and by differential scanning calorimetry (DSC). The enthalpies in solid state at 298,15 K of combustion, δc H m o (I)=-2788,5±1,6 kJ mol−1, δc H m o (II)=-5036±3,8 kJ mol−1 and of formation, δf H m o (I)=-458,3±1,6 kJ mol−1, δfH m o (II)=-180,1±3,8 kJ mol−1 were determined. The thermal effects concerning the melting and phase transition of this compounds were also measured.
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  • 82
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    Journal of thermal analysis and calorimetry 47 (1996), S. 1787-1803 
    ISSN: 1572-8943
    Keywords: DSC ; food components ; food microbiology ; food quality
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimetry (DSC) is the most widely used thermal analytical technique in food research and it has a great utility in quality assurance of food. Proteins are the most studied food components by thermal analysis including studies on conformation changes of food proteins as affected by various environmental factors, thermal denaturation of tissue proteins, food enzymes and enzyme preparations for the food industry, as well as effects of various additives on their thermal properties. Freezing-induced denaturation of food proteins and the effect of cryoprotectants are also monitored by DSC. Polymer characterization based on DSC of polysaccharides, gelatinization behaviour of starches and interaction of starch with other food components can be determined, and phase transitions during baking processes can be studied by DSC. Studies on crystallization and melting behaviour of fats observed by DSC indicate changes in lipid composition or help characterizing products. Thermal oxidative decomposition of edible oils examined by DSC can be used for predicting oil stability. Using DSC in the freezing range has a great potential for measuring and modelling frozen food thermal properties, and to estimate the state of water in foods and food ingredients. Research in food microbiology utilizes DSC in better understanding thermoadaptive mechanisms or heat killing of food-borne microorganisms. Isothermic microcalorimetric techniques provide informative data regarding microbial growth and microbial metabolism.
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  • 83
    ISSN: 1572-8943
    Keywords: DSC ; pharmaceutical technology ; polymer
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract In the present study, the effect of the molecular weight and thermal treatments on commercial polyethylene glycols (PEG) samples used in the pharmaceutical processing technology, has been analyzed using DSC and HSM. The molecular weight of these polymers range from 1500 to 200000. Thermal investigations on the melting behavior of original PEG samples (as received from the manufacturer) showed only one single melting DSC endotherm effect before 373 K. This fact was associated to the presence of only one type of polymeric chain. Using standard conditions, PEG samples were solidified from the melt at 373 K, either by flash cooling (using liquid nitrogen and an ice bath) and by slow cooling, soaked and by slow cooling at room temperature. They were further studied by DSC. It was found that after cooling, PEG with molecular weight 1500 and 15000 showed DSC thermograms with a single endothermic peak. However, thermograms for PEG 4000 and 6000 produced a splitted melting endotherm. This fact was attributed to the presence of two types of chains, that are the folded and extended chains. Ageing time influences also the shape of the DSC endothermal effects. It was concluded that the endotherms obtained after heating these PEG indicate that the thermal history determine the structure (extended or folded chain type forms) and the degree of crystallinity, as evidenced by changes in heat of fusion values, melting points and structures after crystallization. The relationships between melting enthalpies and melting points, as deduced from DSC diagrams, with molecular weight of the polymers are also presented.
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  • 84
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1081-1092 
    ISSN: 1572-8943
    Keywords: chemical ionization MS ; constrained dye ; DSC ; dye-amylose inclusion complex ; Tandem MS ; TGA ; Thermal Desorption MS
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal properties of a dye molecule (guest) inside the cavity of a host amylose helix were studied by TGA, DSC, and Thermal Desorption MS. The results show that the degradation temperature of dye shifts to a higher temperature by approximately 20°C.
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  • 85
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1093-1111 
    ISSN: 1572-8943
    Keywords: conformational disorder ; crystal ; DSC ; glass ; glass transition ; heat capacity ; melting transition ; tetra[methyleneoxycarbonyl (2,4,4-trimethyl) pentyl] methane
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Quantitative thermal analysis was carried out for tetra[methyleneoxycarbonyl(2,4,4-trimethyl)pentyl]methane. The ester has a glass transition temperature of 219 K and a melting temperature of 304 K. The heat of fusion is 51.3 kJ mol−1, and the increase in heat capacity at the glass transition is 250 J K−1 mol−1. The measured and calculated heat capacities of the solid and liquid states from 130 to 420 K are reported and a discussion of the glass and melting transitions is presented. The computation of the heat capacity made use of the Advanced Thermal Analysis System, ATHAS, using an approximate group-vibration spectrum and a Tarasov treatment of the skeletal vibrations. The experimental and calculated heat capacities of the solid ester were compared over the whole temperature range to detect changes in order and the presence of large-amplitude motion. An addition scheme for heat capacities of this and related esters was developed and used for the extrapolation of the heat capacity of the liquid state for this ester. The liquid heat capacity for the title ester is well represented by 691.1+1.668T [J K−1 mol−1]. A deficit in the entropy and enthalpy of fusion was observed relative to values estimated from empirical addition schemes, but no gradual disordering was noted outside the transition region. The final interpretation of this deficit of conformational entropy needs structure and mobility analysis by solid state13C NMR and X-ray diffraction. These analyses are reported in part II of this investigation.
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  • 86
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1113-1132 
    ISSN: 1572-8943
    Keywords: chiral molecule ; conformational disorder and motion ; crystal ; DSC ; heat capacity ; γ-gauche effect ; glass ; glass transition ; melting transition ; molecular mechanics computations ; tetra[methyleneoxycarbonyl (2,4,4-trimethyl) pentyl] methane ; solid state13C NMR ; X-ray diffraction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The symmetric neopolyol ester tetra[methyleneoxycarbonyl(2,4,4-trirnethyl)pentyl]methane (MOCPM) has been studied by variable-temperature solid-state13C NMR and X-ray powder diffraction and compared to molecular mechanics calculations of the molecular structure. Between melting and glass transition temperatures the material is semicrystalline, consisting of two conformationally and motionally distinguishable phases. The more mobile phase is liquid-like and is, thus attributed to an amorphous phase (≈16%). The branches of the molecules in the crystal exhibit two conformationally distinguishable behaviors. In one, the branches are well ordered (≈56%), in the other, the branches are conformationally disordered (≈28%). Different branches of the same molecule may show different conformational order. This unique character of the rigid phase is the reason for the deficit of the entropy of fusion observed earlier by DSC. In the melt, solid state NMR can identify two bonds that are rotationally immobile, even though the molecules as a whole have liquid-like mobility. This partial rigidity of the branches accounts quantitatively for the observed increase in heat capacity at the glass transition. The reason for this unique behavior of MOCPM, a small molecule, is the existence of one chiral centers in each of the four arms of the molecule. A statistical model assuming that at least two of the chiral centers must fit into the order of the crystal can explain the crystallization behavior and would require 12.5% amorphous phase, 28.1% conformational disorder, and 59.4% crystallinity, close to the observed maximum perfection.
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  • 87
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1177-1189 
    ISSN: 1572-8943
    Keywords: DSC ; mercury porosimetry ; pore size distribution ; porous glass ; thermoporosimetry ; water
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The pore size distributions (PSDs) of microporous glass, which were controlled by acid leaching subsequent to phase separation of CaO-Al2O3-B2O3-SiO2 glass, were determined via both mercury porosimetry and thermoporosimetry (thermal porosimetry). As a result, the pore radii, the cumulative pore volumes, and the surface areas determined via thermoporosimetry were in good agreement with those determined via mercury porosimetry. It was revealed that thermoporosimetry could be applied to pore structure analysis for porous materials having pore sizes at least up to 58 nm in radius.
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  • 88
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1339-1347 
    ISSN: 1572-8943
    Keywords: boehmite ; DSC ; gibbsite
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The dehydroxylation of gibbsite into boehmite was investigated by means of DSC analysis under non-isothermal conditions in the temperature range 453–673 K at heating rates from 2.5 to 20.0 K min−1. Mathematical analysis of the experimental DSC curves revealed the mechanism and kinetics of the gibbsite dehydroxylation process. The kinetic curvesα=f(t) andα=f(T) are sigmoidal in shape; their inflection points and the νm point of the curvesν=f(T) andν=f(T) are interrelated and are defined by the concept of a stationary point. The activation energy for the first stage of gibbsite dehydroxylation in the temperature range 453–673 K is 132.92±8.33–142.26±8.33 kJ mol−1.
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  • 89
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    Journal of thermal analysis and calorimetry 46 (1996), S. 1541-1550 
    ISSN: 1572-8943
    Keywords: DSC ; FTIR ; grafting ; IDSC ; kinetic parameters ; polymerization ; TG ; thermodynamic parameters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal polymerization of pentabromobenzyl (mono)acrylate (PBB-MA) on the surface of the inorganic fillers Mg(OH)2 and CaCO3 was studied. FTIR spectroscopy and extraction of the polymer in bromobenzene show that polypentabromobenzyl acrylate (PBB-PA) was mostly grafted on the surface of Mg(OH)2. Thermal analysis (TG, DSC, isothermal DSC (IDSC)) demonstrated an increase in polymerization starting temperature, and differences in polymerization enthalpy and apparent activation energy when an inorganic filler is added. These differences depend on the chemical composition of the filler used.
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  • 90
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    Journal of thermal analysis and calorimetry 47 (1996), S. 117-121 
    ISSN: 1572-8943
    Keywords: baseline ; DSC ; heat of fusion ; polyethylene
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A technique is proposed for improving the accuracy of the heat of fusion of semicrystalline polymers by DSC. The results of three commercially available instruments are compared.
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  • 91
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    Journal of thermal analysis and calorimetry 47 (1996), S. 195-213 
    ISSN: 1572-8943
    Keywords: DMA ; DSC ; rheological impacts ; thermomechanical properties
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Thermomechanical properties of bread components can be used to characterize various events that have direct rheological impacts. The objective is to observe changes that occur during staling and toughening of a bread or similar products. In this article, characterization of bread polymers, starch and gluten, were examined by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA).
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  • 92
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    Journal of thermal analysis and calorimetry 47 (1996), S. 445-452 
    ISSN: 1572-8943
    Keywords: catalysts ; catalyst activity ; catalyst deactivation ; DSC ; gas reactions ; kinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Gas reactions, catalyzed by solid catalysts, can be measured by DSC. In the experimental set-up an open sample pan with catalyst (powder or pellet) is placed on the sample side of the DSC sensor. The reactive gas mixture flows through the cell and reacts on the catalyst surface. The heat effect, caused by this reaction, results into a DSC signal. The calibration procedure is described for quantitative evaluation of the DSC measurements. For illustration four different reaction systems are discussed.
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  • 93
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    Journal of thermal analysis and calorimetry 47 (1996), S. 503-514 
    ISSN: 1572-8943
    Keywords: cardiac myosin ; DSC ; flexibility of myosin heads ; spin-labelling
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Conventional and saturation transfer electron paramagnetic resonance spectroscopy (EPR and ST EPR) and differential scanning calorimetry (DSC) were used to study the motional dynamics and segmental flexibility of cardiac myosins. Cardiac myosins isolated from bovine and human heart muscle were spin-labelled with isothiocyanate- or maleimide-based probe molecules at the reactive sulfhydryl sites (Cys-697 and Cys-707) of the motor domain. The maleimide probe molecules attached to human cardiac myosin rotated with an effective rotational correlation time of 33 ns which was at least eight times shorter than the rotational correlation time of the same label on skeletal myosin (260 ns). In the presence of MgADP and MgADP plus orthovanadate, flexibility changes in the multisubunit structure of myosins were detected, but this did not lead to changes of the overall rotational property of the myosin heads. Significant difference in the internal flexibility was detected on myosin samples isolated from ischemic tissue, the rotational correlation time decreased to 25 ns. DSC measurements supported the view that addition of nucleotides produced additional loosening in the multisubunit structure of cardiac myosin. It is postulated that there is an intersite communication between the nucleotide binding domain and the 20 kDa subunit where the reactive thiol sites are located.
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  • 94
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    Journal of thermal analysis and calorimetry 47 (1996), S. 765-774 
    ISSN: 1572-8943
    Keywords: calcium aluminates ; cement ; DSC
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Differential scanning calorimeter (DSC) has been used to study the dehydration characteristics of hydrated calcium aluminates such as CA, CA2 and C12A7 where C and A stand for CaO and Al2O3 respectively. Dehydration of CAH10 and C2AH8 (whereH=H2O) occur ∼ at 160–180°C and 200–280°C respectively. These two phases are unstable and ultimately get transformed to AH3 and C3AH6. Dehydration of AH3 and C3AH6 occur between 290 and 350°C and overlap at lower scanning rate. The activation energy for dehydration of the stable AH3 and C2AH6 phases has been found to be 107.16 and 35.58 kJ mol−1 respectively. The compressive strength of the hydrated calcium aluminates has been determined. The result shows that in the case of CA, almost 90% of ultimate strength has been attained in 1 day whereas in CA2, ultimate strength has been attained in 14 days and in C12A7 in 1 day. DSC results have been correlated with the rate of strength developments.
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  • 95
    ISSN: 1572-8943
    Keywords: crown-ethers (CE) ; 12-C-4 ; 15-C-5 ; DC 18-C-6anti ; DC 18-C-6syn ; DSC ; LiAlH4-CE complexes ; glass-transition ; solvates
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The thermal behaviour of complexes [Li+-EC](AlH4)− withEC=12-C-4, 15-C-5, DC 18-C-6 (cis-anti-cis andcis-syn-cis isomers) was investigated by Differential Scanning Calorimetry (DSC). These complexes were prepared as solids from benzene solutions. Pure EC and several solvated species [Li+-EC](AlH4)−·nC6H6 (EC=15-C-5, DC 18-C-6syn) were also studied. DSC has revealed various phenomena. Solid-solid transitions were observed before melting for [Li+-EC](AlH4)− withEC=12-C-4 and 15-C-5. They are probably explained by small molecular modifications strongly dependent on the thermal history of the sample. A glass-transition was found for the pure crown-ether DC 18-C-6anti, the complex [Li+-EC](A1H4)− withEC=DC-18-C-6anti and the two solvates mentioned above.
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  • 96
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    Journal of thermal analysis and calorimetry 47 (1996), S. 887-896 
    ISSN: 1572-8943
    Keywords: compensation temperature ; DSC ; fictive temperature ; poly(ethylene terephthalate) ; thermally stimulated depolarization current
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract This work deals with a comparison of data obtained from differential scanning calorimetry (DSC) and thermally stimulated depolarization current (TSDC) investigations. Measurements were performed on various poly(ethylene terephthalate) films: a wholly amorphous, a thermally crystallized and drawn samples. For each specimen, the TSDC complex spectra, resolved into elementary ones, led to the determination of the classical compensation temperature (T c ). The glass transition temperature (T g) and the fictive equilibrium temperature (T f) were determined by means of DSC. It appears thatT c is different fromT g and very close toT f.
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  • 97
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    Journal of thermal analysis and calorimetry 47 (1996), S. 931-939 
    ISSN: 1572-8943
    Keywords: DSC ; isothermal melt crystallization ; kinetic parameters ; Mathematica® ; new kinetic model ; poly(L-lactic acid)
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A DSC study was carried out of the isothermal melt crystallization kinetics of poly(L-lactic acid), PLLA, at 110, 115, 120, 125 and 130
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  • 98
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    Environmental biology of fishes 45 (1996), S. 219-235 
    ISSN: 1573-5133
    Keywords: Ecology ; Behaviour ; Evolution ; Cichlids ; Fisheries ; Conservation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Synopsis Ecological conditions in tropical lacustrine systems are considered by focusing on the evolution, maintenance, exploitation and vulnerability of fish communities in the African Great Lakes. The exceptionally high biodiversities in the littoral/sublittoral zones of the very ancient, deep, clear, permanently stratified rift lakes Tanganyika and Malawi, are contrasted with the simpler systems in their pelagic zones, also with biodiversity in the much younger, shallower Victoria, the world's largest tropical lake.
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  • 99
    ISSN: 1573-1111
    Keywords: Biliar acid ; 2-hydroxypropyl-β-cyclodextrin ; interaction studies ; IR ; NMR ; DSC ; XRD
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The interaction of two biliar acids (chenodeoxycholic acid and cholic acid) with 2-hydroxypropyl-β-cyclodextrin (HPβCD) in solution and in the solid state was studied using different techniques. The formation of an inclusion complex with a 1:1 stoichiometry was suggested by the phase solubility studies. Both differential scanning calorimetry and X-ray diffractometry exhibited the amorphous state of the complex. The inclusion of both biliar acids into the HPβCD cavity was confirmed by the13C-NMR studies. Cholic acid showed a weaker affinity with respect to chenodeoxycholic acid probably owing to the presence of a hydroxyl group onC(12) (12α) close to the complexation site.
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