Über Sesquiselenide der Lanthanoide: Einkristalle von Ce2Se3 im C‐, Gd2Se3 im U‐ und Lu2Se3 im Z‐Typ

On Sesquiselenides of the Lanthanoids: Single Crystals of C‐type Ce₂Se₃, U‐type Gd₂Se₃, and Z‐type Lu₂Se₃ Single crystals of lanthanoid sesquiselenides (M₂Se₃; here: M = Ce, Gd, Lu) are accessible through conversion of the elements (lanthanoid and selenium) in molar ratios of 2:3 within seven days at 850 °C from evacuated silica ampoules if equimolar amounts of NaCl serve as a flux. In the case of Ce₂Se₃ (a = 897.74(6) pm) und Gd₂Se₃ (a = 872.56(5) pm) the cubic C‐type (I4¯3d, Z = 5.333) forms as dark red beads, whereas the orthorhombic Z‐type (Fddd, Z = 16) emerges for Lu₂Se₃ (a = 1125.1(1), b = 798.06(8), c = 2387.7(2) pm) as orange‐yellow bricks. Upon oxidation of monochloride hydrides (MClH_x or A_yMClH_x; M = Ce, Gd, Lu; x = 1; A = Li, Na; y = 0.5) with selenium in arc‐welded tantalum ampoules the same main products appear with C‐Ce₂Se₃ and Z‐Lu₂Se₃, even with a surplus of NaCl or LiCl as fluxing agent. In the case of Gd₂Se₃, however, black‐red needles of the orthorhombic U‐type (Pnma, Z = 4; a = 1118.2(1), b = 403.48(4); c = 1097.1(1) pm) are yielded instead of C‐Gd₂Se₃. C‐Ce₂Se₃ crystallizes in a cation‐deficient Th₃P₄‐type structure (Ce₂S₃ type) according to Ce_2.667□_0.333Se₄ (Z = 4) or with Z = 5.333 for the empirical formula Ce₂Se₃. Here, Ce³⁺ is coordinated by eight Se^2— anions trigon‐dodecahedrally. In U‐Gd₂Se₃ (U₂S₃ type) two crystallographically independent Gd³⁺ cations with coordination numbers of 7 (Gd1) and 7+1 (Gd2), respectively, are present, exhibiting mono‐ or bicapped trigonal prisms as coordination polyhedra. The crystal structure of Z‐Lu₂Se₃ (Sc₂S₃ type) shows two different Lu³⁺ cations as well, which now both reside in octahedral coordination of six Se^2— anions each.     

Structural and electrical characterization of PZT on gold for micromachined piezoelectric membranes

Piezoelectric membranes have been fabricated that incorporate a gold bottom electrode with an adhesion layer of titanium–tungsten (10:90 wt. %). For solution-deposited acetic acid based lead zirconate titanate (HoAc-PZT) with a Zr:Ti ratio of 40:60, the film’s average piezoelectric coefficient, e₃₁, is -5.31 C/m², with a dielectric constant of 814 at 200 Hz, which is similar to values for platinum bottom electrodes. The PZT structure remains columnar on both types of bottom electrodes. Initial fabrication attempts resulted in cracking that initiated in the PZT layer of the structure. X-ray photoelectron spectroscopy was utilized to establish how processing affects diffusion throughout the composite membrane structure. Crack-free membranes were fabricated and tested. This paper discusses the performance properties and piezoelectric fatigue results for these membranes. PACS 77.84.-s; 77.84.Lf     

Mixtures of charged colloid and neutral polymer: influence of electrostatic interactions on demixing and interfacial tension

The equilibrium phase behavior of a binary mixture of charged colloids and neutral, nonadsorbing polymers is studied within free-volume theory. A model mixture of charged hard-sphere macroions and ideal, coarse-grained, effective-sphere polymers is mapped first onto a binary hard-sphere mixture with nonadditive diameters and then onto an effective Asakura-Oosawa model [S. Asakura and F. Oosawa, J. Chem. Phys. 22, 1255 (1954)]. The effective model is defined by a single dimensionless parameter-the ratio of the polymer diameter to the effective colloid diameter. For high salt-to-counterion concentration ratios, a free-volume approximation for the free energy is used to compute the fluid phase diagram, which describes demixing into colloid-rich (liquid) and colloid-poor (vapor) phases. Increasing the range of electrostatic interactions shifts the demixing binodal toward higher polymer concentration, stabilizing the mixture. The enhanced stability is attributed to a weakening of polymer depletion-induced attraction between electrostatically repelling macroions. Comparison with predictions of density-functional theory reveals a corresponding increase in the liquid-vapor interfacial tension. The predicted trends in phase stability are consistent with observed behavior of protein-polysaccharide mixtures in food colloids.