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The complementary structural studies of the double metal cyanide type catalysts for the ring opening polymerization of the oxiranes

Chruściel A., Hreczuch W., Czaja K., Ławniczak-Jabłońska K., Janik J.

Polimery

2016

T. 61, nr 6

421--432

The extensive complementary experimental studies of the double metal catalysts (DMC) with two kinds of the organic ligands were performed. The chemical justification of the observed TG/DSC (thermogravimetric analysis/differential scanning calorimetry) steps was proposed. Several organic ligand complexing states were found in both types of catalysts. X-ray absorption spectroscopy (XAS) analysis established that only Zn atoms are the active metallic centers in DMC catalyst regardless the used ligand. Cl atoms were detected near some of Zn atoms. Contrary to the common suppositions no significant amount of oxygen atoms was detected in the closest coordination spheres of Zn.

Przeprowadzono badania strukturalne katalizatorów dimetalocyjankowych (DMC) z dwoma rodzajami ligandów organicznych. Zaproponowano wyjaśnienie etapów przebiegu krzywych otrzymanych metodą analizy termograwimetrycznej i różnicowej kalorymetrii skaningowej (TG/DSC) badanych katalizatorów. Wykazano obecność kilku stopni związania ligandów w kompleksach DMC. Na podstawie wyników badań z wykorzystaniem absorpcji rentgenowskiej (XAS) stwierdzono, że centrum aktywne katalizatora stanowi atom cynku. W bezpośrednim sąsiedztwie atomów Zn wykryto obecność atomów Cl, natomiast w najbliższych sferach koordynacyjnych atomu Zn nie wykryto atomów tlenu.

Optical spectroscopy and local structure of the Nd3+ luminescence centres in glasses of the CaO-Ga2O3-GeO2 system

Padlyak B., Ryba-Romanowski W., Lisiecki R.

Optica Applicata

2008

Vol. 38, nr 1

189-202

Optical absorption and luminescence spectra as well as luminescence kinetics of the Nd3+ centres in glasses with Ca3Ga2Ge3O12:Nd composition, containing 0.2 and 1.0 wt% of the Nd2O3 were presented and analysed. The oscillator strengths and phenomenological intensity parameters omega t (omega 2, omega 4, and omega 6) were obtained using standard Judd-Ofelt theory. Calculated omega t parameters, radiative transitions rates, branching ratios and radiative lifetime for Nd3+ centres in the glass with Ca3Ga2Ge3O12 composition were analysed and compared with corresponding Nd3+ parameters in their crystalline analogue with garnet structure. Experimental lifetimes are compared with those calculated, and quantum efficiency of Nd3+ centres from 4F3/2 emitting level in the glass with Ca3Ga2Ge3O12 composition is estimated. Incorporation peculiarities and local structure of Nd3+ luminescence centres in the glass with Ca3Ga2Ge3O12 composition and corresponding Ca3Ga2Ge3O12:Nd3+ garnet laser crystals are considered. On the basis of extended X-ray absorption fine structure (EXAFS) spectra (L3-edge) of rare-earth elements analysis it has been shown that Nd3+ luminescence centres in the CaO-Ga2O3-GeO2 glass network occupy structural sites with the coordination number to oxygen N = 6.

Metody badania powierzchni cd.

Sarbak Z.

LAB Laboratoria, Aparatura, Badania

2003

R. 8, nr 1

13-16