Influence of a continuous quenching procedure on the initial stages of spinodal decomposition

Instead of the standard assumption in the theory of phase separation where an instantaneous quench from an initial equilibrium state to the final state in the two-phase region is assumed, we consider the more realistic situation that the change of the external control parameter (e.g. temperature) can only be performed with finite rates. During the initial stages of spinodal decomposition the system then has some memory of the states intermediate between the initial and the final one. This influence of the finite quench rate in continuous quenching procedures is studied within the linearized theory of spinodal decomposition, with the Langer-Baron-Miller decoupling, and with Monte Carlo simulations. Both the case of thermally activated mobilities (applicable to solid metallic alloys) and the case of nearly temperature-independent mobilities (applicable to fluid polymer mixtures) are treated, and possible experimental applications are discussed. We find drastic deviations from the standard instantaneous quench situations in all cases of experimental interest.     

Structure and Thermal Stability of La0.10WO3+y; A Hexagonal Tungsten Bronze Related Phase Formed at High Pressure

The structure and thermal stability of a hexagonal tungsten bronze (HTB) related compound, La_xWO_3+y with x≈0.10 and y≈0.15, has been studied by X-ray diffraction, thermal analysis, and electron microscopy. The structure was refined by the Rietveld method from X-ray powder diffractometer data of a La_0.10WO₃ sample prepared at T=1250°C and P=25 kbar, which consisted of two tungsten bronze related phases in 1:1 proportion. The unit cell dimensions are as follows: La_0.108WO_3+y (y≈0.16), a=7.40890(5), and c=3.79329(4) Å (HTB-related structure); La_0.091WO₃, a=3.82458(6) Å (cubic perovskite tungsten bronze (PTB) structure). The lanthanum atoms in La_0.108WO_3+y are located on the hexagonal axis and statistically distributed on two sites close to the tungsten atom plane. Thermal stability studies of the La_0.10WO₃ sample in an argon atmosphere under ambient pressure conditions revealed that the HTB-related compound is metastable, decomposing to the stable PTB-type structure and WO₃. It was also found from the TG experiments in argon and oxygen that additional oxygen atoms (y) are present in the structure, thus forming a lanthanum tungsten oxide of the above composition. The electron diffraction and microanalysis studies confirmed that crystals of the HTB- and PTB-type structures were formed, with a lanthanum content of x≈0.1.     

An investigation of the structure of butadiene by high resolution infra-red and raman spectroscopy

The rotational Raman spectra of butadiene and butadiene-d₆ are found to consist of discrete lines having small ≈0·4 cm⁻¹) yet almost constant spacings, as would be expected for symmetric or nearly symmetric top molecules. An infra-red absorption band (Type C) of butadiene at 908 cm⁻¹ is observed to have a spacing of about 2·5 cm⁻¹. Both the Raman and infra-red spectra provide evidence for the trans structure of the butadiene molecule. From the rotational constants A″ and ″ the following structural parameters were obtained: C=C---C) = 122·9 ± 0·5° rC---C) = 1·47₆ ± 0·010 Å dy]somewhat shorter than recently determined from electron-diffraction experiments).     

Preparation-Proprietes physico-chimiques enthalpie de formation de l'hydrure d'aluminium AlH3α′

Résumé L'hydrure d'aluminium AlH₃- a été obtenu par action de LiAlH₄ sur AlCl₃ ou ZnCl₂ dans l'éther éthylique. La décomposition thermique a été étudiée par thermogravimé trie sous pression réduite (10^–2 torr). La capacité calorifique molaire à 298 K, l'enthalpie de décomposition, ainsi que l'enthalpie de formation ont été déterminées avec un microcalorimètre Calvet.

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Aluminium hydride,-AlH₃, was prepared by reaction of LiAlH₄ on A1C1₃ or ZnCl₂ in diethyl ether. Thermogravimetry was used to investigate its thermal decomposition under low pressure (10^–2 torr). The molar heat capacity at 298 K, the heat of decomposition, and the heat of formation, were measured with a Calvet microcalorimeter.

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Zusammenfassung Aluminiumhydrid AlH₃- wurde durch Einwirkung von LiAlH₄ auf AlCl₃ oder ZnCl₂ in DiÄthylether hergestellt. Die Thermo gravimetrie wurde zur Untersuchung der thermischen Zersetzung bei niedrigem Druck (10^–2 torr) herangezogen. Die molare WÄrmekapazitÄt bei 298 K, die Zersetzungsenthalpie sowie die Bildungsenthalpie wurden mit einem Calvet-Mikrokalorimeter bestimmt.

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— - l₃ LiAlH₄ ll₃ ZnCl₂ . (10^–2 ) . 298 , .

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Ce travail a été effectué dans le cadre d'un contrat de recherches passé par le laboratoire de Thermochimie Minérale avec la Direction des Recherches et Moyen d'Essai. Nous remercions bien vivement cet organisme de l'aide qu'il nous a apportée.     

CHEMICALLY MODIFIED PHOTOSYNTHETIC BACTERIAL REACTION CENTERS: CIRCULAR DICHROISM, RAMAN RESONANCE, LOW TEMPERATURE ABSORPTION, FLUORESCENCE AND ODMR SPECTRA AND POLYPEPTIDE COMPOSITION OF BOROHYDRIDE TREATED REACTION CENTERS FROM Rhodobacter sphaeroides R26

Abstract— Reaction centers from Rhodobacter sphaeroides have been modified by treatment with sodium borohydride similar to the original procedure [Ditson et al., Biochim. Biophys. Acta 766 , 623 (1984)], and investigated spectroscopically and by gel electrophoresis.
(1) Low temperature (1.2 K) absorption, fluorescence, absorption- and fluorescence-detected ODMR, and microwave-induced singlet-triplet absorption difference spectra (MIA) suggest that the treatment produces a spectroscopically homogeneous preparation with one of the 'additional' bacteriochlorophylls being removed. The modification does not alter the zero field splitting parameters of the primary donor triplet (^TP870).
(2) From the circular dichroism and Raman resonance spectra in the1500–1800 cm^-1 region, the removed pigment is assigned to Bchl_M, e.g. the "extra" Bchl on the "inactive" M-branch.
(3) A strong coupling among all pigment molecules is deduced from the circular dichroism spectra, because pronounced band-shifts and/or intensity changes occur in the spectral components assigned to all pigments. This is supported by distinct differences among the MIA spectra of untreated and modified reaction centers, as well as by Raman resonance.
(4) The modification is accompanied by partial proteolytic cleavage of the M-subunit. The preparation is thus spectroscopically homogeneous, but biochemically heterogenous.