A Study of Amorphous Precursors for PbZrO3-PbTiO3 Based Ceramic Materials

Amorphous precursors for PbZrO₃ and PbTiO₃ ceramics were prepared from lead acetate and the transition metaln-propoxide inn-propanol orn-butoxide inn-butanol and hydrolysed with an excess of water. According to GLC and TGA/EGA analyses, the type of alkoxide group influences distinctly the structure of heterometallic precursors, i.e., oxo or acetate bridging, and the amounts of hydroxyl and organic groups bound to the metal network. The local environments of metal atoms in the amorphous precursors were also studied by EXAFS. The analysis reveals that in Pb−Zr precursors alkoxide groups modify the coordination spheres of the zirconium atoms. Conversely, local environments of both lead and titanium atoms within the analysed range of 3.4 A depend weakly on the type of alkoxide used.     

Electrons ejected in resonant Raman scattering of X-rays on krypton

In the resonant Raman scattering of x-rays on krypton gas the ejected electrons were investigated by a proportional counter spectrometer. The cross sections for the process were determined for three energies of the incident photons (181 eV, 89 eV, and 33 eV below theK edge). The results agree with the theoretical predictions, thus independently confirming the theory that has so far only been tested by scattered photon data. From the cross sections the width of theK-shell excited state of krypton is extracted asΓ _K =(2.75±0.10) eV.     

TheK-shell fluorescence yield of germanium

TheK-shell fluorescence yield of germanium has been determined asω _K=0.570±0.003 by the modified proportional counter technique using a special wall-less proportional counter filled with methane and small admixture of germanium hydride GeH₄. The required ratio of the total photoabsorption to the absorption in theK-shell has been obtained from the separate study of the energy dependence of the X-ray absorption in germanium.     

Structural evolution from the sol to the PbZrO<Subscript>3</Subscript> precursor powders prepared by an alkoxide-based sol–gel route

PbZrO₃ powders have been prepared by an alkoxide-based sol–gel route, starting from lead acetate, zirconium n-butoxide, and n-butanol as a solvent, and hydrolysed with different amounts of water in neutral and alkaline medium. The local environment of Zr and Pb atoms was pursued from the sol to the dried (150 °C) and heated (400 °C) powders, by extended x-ray absorption fine structure (EXAFS). The analysis of the sol revealed links between Pb and Zr, and even more links between Zr and Zr. The metal neighbourhoods in the dried powders are not influenced by the hydrolysis conditions. Pb-Zr correlations are gradually lost from the sol to the dried and heated powders, while the loss of Zr–Zr correlations is considerably lower.     

The solution structures and dynamics and the solid-state structures of substituted cyclopentadienyltitanium(IV) trifluorides

Organotitanium fluorides (C5Me4R)TiF3 (R = H, Me, Et) sublimate with formation of crystalline dimers. From solution, we obtained crystals of dimers and tetramers. The tetramer [{(C5Me5)TiF3}4] irreversibly dissociates in the solid state to dimers (DeltaH = 8.33 kcal mol(-1)). The variable-temperature (1)H and (19)F NMR spectroscopy measurements of the toluene-d(8) solution of [{(C5Me5)TiF3}2] revealed at 202 K one monomeric, two dimeric (with C2h and Cs symmetry), two tetrameric (with D2 and C2v symmetry), and two trimeric (both C2 symmetry) molecules. With the increase in temperature and dilution of the solution, the composition of the solution shifts to the smaller molecules. The thermodynamic and activation parameters for the reversible dissociation of dimers to monomers in the solution are DeltaH = 9.2 kcal mol(-1), DeltaS = 24.2 cal mol(-1) K(-1), DeltaH(double dagger) = 12.2 kcal mol(-1), DeltaS(double dagger) = 9.7 cal mol(-1) K(-1). The dissociation path with a weakly double-bridged transition-state dimer was proposed. The thermodynamic parameters for the reversible dissociation of the C2v tetramer to the dimers in solution are DeltaH = 7.9 kcal mol(-1) and DeltaS = 26.8 cal mol(-1) K(-1). From both tetramers, the D2 molecule is 0.34(5) kcal mol(-1) lower in enthalpy and 6.5(5) cal mol(-1) K(-1) lower in entropy than the C2v molecule. The structures of both trimers were proposed. The low-temperature 19F NMR spectra of the CDCl3 solution of [{(C5Me5)TiF3}2] are consistent with equilibria of a monomer, two dimers (with C2h and Cs symmetry), and a trimer. The vapor pressure osmometric molecular mass determination of CDCl3 solution of [{(C5Me5)TiF3}2] at 302 K is consistent with the equilibrium of the dimer and the monomer.     

Combined bracketing methods for solving nonlinear equations

Several methods based on combinations of bisection, regula falsi, and parabolic interpolation has been developed. An interval bracketing ensures the global convergence while the combination with the parabolic interpolation increases the speed of the convergence. The proposed methods have been tested on a series of examples published in the literature and show good results.     

Structural evolution of the KTa0.6Nb0.4O3 alkoxide-based solutions: probing the transition metals local environment by X-ray absorption spectroscopy

The KTa_0.6Nb_0.4O₃ sols for chemical solution deposition of thin films were prepared from potassium acetate and transition metal ethoxides by the 2-methoxyethanol based route. The local environment of both transition metals after reflux times 1, 4, 24, and 48 h, whereby the crystallization behavior of the films was strongly affected, was monitored by extended X-ray absorption fine structure spectroscopy, at Ta L₃ and Nb K edges. The Ta species existed in the sols as monomers, remaining stable even with prolonged reflux time. The Ta–O–K correlations were confirmed in all cases. In contrast, the Nb-alkoxide formed dimers, with a gradual formation of oligomeric species with prolonged refluxing. The Nb–O–K correlations were present after all reflux times. The number of K neighbours around Nb increased upon refluxing, saturating at 24 h.     

Motional heterogeneity and phase separation of functionalized polyester polyurethanes

The polyester polyurethanes, PU based on isophoronediisocyanate, polycaprolactone, and 1,4-butanediol with different amounts of functional groups introduced into the hard segments via second chain extender, 2,2′-bis-(hydroxymethyl) propionic acid, were investigated by electron spin resonance, ESR, spin label method, wide-angle X-ray diffraction, WAXD, optical microscopy and differential scanning calorimetry, DSC. The objective of this study is to clarify the effect of functional groups on the motional heterogeneity, microphase separation and crystallisation of the polyurethanes. The concentration of carboxylic groups varied from 0 to 0.45 mmol g⁻¹. The temperature-dependent ESR spectra of spin labelled PU hard segments chain ends with stable nitroxide radical 2,2,6,6-tetramethyl-4-aminopiperidin-1-yloxyl are sensitive to the amount of functional groups attached to the hard segments. Composite ESR spectra of functionalized PU, with fast and slow component, suggest that PU hard segments are partitioned in two motionally different environments. According to the ratio of fast and slow component motional heterogeneity increases with an increase of functional groups up to 0.35 mmol g⁻¹ and above this concentration slow component decreases indicating higher degree of phase mixing and stronger effect of soft segments. Polarized micrographs and the extent of ordering from WAXD measurements reveal the changes of phase morphology with the carboxylic groups content in a similar way as shown from the motional behaviour of spin label on the segmental level. The degree of crystallinity and the separation of spherulitic rings are decreasing above a certain concentration of functional groups. The effect of functional groups in PU on the hard and soft segment mixing is discussed in terms of additional noncovalent interactions and chain structure which at critical level of interactions lead to a formation of more open hard segment structure accessible to interaction with the soft segment.