Characterization of silicon nitride particles synthesized in an atmospheric-pressure convection-stabilized arc

Silicon nitride powders were synthesized in an atmospheric-pressure convection-stabilized arc using silicon and ammonia as reactants. The morphology and particle size distributions of the silicon nitride particles were characterized by SEM, TEM, and electron diffraction analyses. The silicon nitride particles collected in the plasma reactor were formed by either gas-condensed phase reactions or chemical vapor reactions. The morphologies of the particles formed by gas-condensed phase reactions consisted of -Si₃N₄ prisms, -Si₃N₄ matte, -Si₃N₄ needles, and spaghetti-like whiskers. For the homogeneously nucleated particles, the morphologies included dendrites, needles, platelets, and amorphous particles. Most of the particles formed were aggregates with particle size distributions ranging from 500 to 1500 Å depending on the location of injection of the reactants.     

Non-isothermal crystallization kinetics of recycled PET-Si3N4 nanocomposites

Poly(ethylene terephthalate) (PET) is an important industrial material and has been widely applied in consumer products. Due to its slow crystallization rate, nanoparticles are incorporated into PET to function as heterogeneous nucleating agents. In this study, the non-isothermal crystallization behavior of recycled PET-silicon nitride (Si₃N₄) nanocomposites was investigated by differential scanning calorimetry (DSC). In the general analysis of the non-isothermal crystallization curves, it was found that the Si₃N₄ nanoparticles could effectively accelerate the nucleation of PET, but the crystal growth rate was slowed down when the Si₃N₄ content was more than 1 wt%. This might be attributed to the interaction between the PET chains and the surface-treated Si₃N₄ nanoparticles. Results obtained from Avrami and Mo treatments agreed well with the general analysis. Application of the Kissinger method and isoconversional method of Flynn-Wall-Ozawa also showed that Si₃N₄ nanoparticles had a good nucleation effect on the crystallization of PET, and the crystal growth was hindered by Si₃N₄ when the particle loading is higher than 1 wt%.     

Luminescence enhancement of Eu, Ce co-doped Ba3Si5O13−δNδ phosphors

Host lattice Ba₃Si₅O_13−δN_δ oxonitridosilicates have been synthesized by the traditional solid state reaction method. The lattice structure is based on layers of vertex-linked SiO₄ tetrahedrons and Ba²⁺ ions, where each Ba²⁺ ion is coordinated by eight oxygen atoms forming distorted square antiprisms. Under an excitation wavelength of 365 nm, Ba₃Si₅O_13−δN_δ:Eu²⁺ and Ba₃Si₅O_13−δN_δ:Eu²⁺,Ce³⁺ show broad emission bands from about 400-620 nm, with maxima at about 480 nm and half-peak width of around 130 nm. The emission intensity is strongly enhanced by co-doping Ce³⁺ ions into the Ba₃Si₅O_13−δN_δ:Eu²⁺ phosphor, which could be explained by energy transfer. The excitation band from the near UV to the blue light region confirms the possibility that Ba₃Si₅O_13−δN_δ:Eu²⁺, Ce³⁺ could be used as a phosphor for white LEDs.     

Solid solubility of Yb2Si2O7 in β-, γ- and δ-Y2Si2O7

This paper examines the structural changes with temperature and composition in the Yb₂Si₂O₇-Y₂Si₂O₇ system; members of this system are expected to form in the intergranular region of Si₃N₄ and SiC structural ceramics when sintered with the aid of Yb₂O₃ and Y₂O₃ mixtures. A set of different compositions have been synthesised using the sol-gel method to obtain a xerogel, which has been calcined at temperatures between 1300 and 1650 °C during different times. Isotherms at 1300 and 1600 °C have been analysed in detail to evaluate the solid solubility of Yb₂Si₂O₇ in β-Y₂Si₂O₇ and γ-Y₂Si₂O₇. Although Yb₂Si₂O₇ shows a unique stable polymorph (β), Yb³⁺ is able to replace Y³⁺ in γ-Y₂Si₂O₇ and δ-Y₂Si₂O₇ at high temperatures and low Yb contents. IR results confirm the total solid solubility in the system and suggest a constant SiOSi angle of 180° in the Si₂O₇ unit across the system. The temperature-composition diagram of the system, obtained from powder XRD data, is dominated by the β-RE₂Si₂O₇ polymorph, with γ-RE₂Si₂O₇ and δ-RE₂Si₂O₇ showing reduced stability fields. The diagram is in accordance with Felsche's diagram if average ionic radii are assumed for the members of the solid solution at any temperature, as long as the β-γ phase boundary is slightly shifted towards higher radii.     

Thermal Plasma Chemical Vapor Deposition of Si-Based Ceramic Coatings from Liquid Precursors

In this paper a process based on the use of rf inductively coupled plasma is applied for the synthesis and deposition of Si-base ceramic materials (i.e., SiC, Si₃N₄, SiO₂). The starting materials are low-cost liquid disilanes. The atomization process is first investigated and the structure of the resulting coatings is characterized by means of X-ray diffraction, scanning electron microscopy as well as with transmission electron microscopy. Results of the influence of some processing parameters (i.e., chamber pressure, spray distance, substrate cooling, plasma gas nature and composition, precursor composition and atomization parameters) on the phase and microstructure of the coating is reported. Control of the microstructure (or nanostructure) as well as the phase content, namely the / ratio of the phases for SiC and Si3N4, can be achieved with such a synthesis and deposition technique.     

Study of Surface Modification of Nanosize Si3N4 with Macromolecular Coupling Agent LMPB-g-GMA in Different Solvents

A new macromolecular coupling agent, low-molecular-weight polybutadiene liquid rubber (LMPB)-glycidyl methacrylate (GMA), was synthesized using solution polymerization initiated by benzoyl peroxide (BPO). The molecular structure was confirmed by FTIR and NMR. This macromolecular LMPB-GMA was used for surface modification of silicon nitride (Si₃N₄) nanopowder in n-heptane, chloroform, ethyl acetate, and DMF, respectively. LMPB-GMA and modified nano-Si₃N₄ were systematically investigated by FTIR, NMR, TGA, and TEM. The results showed that LMPB-GMA bonded and formed an organic coating layer onto the surface of nanosized Si₃N₄ particles. The polarity of the solvents plays an important role in this process. Strong or weak polar both affect the results. The dosage loading of LMPB-GMA is 12 wt% of nanosized Si₃N₄. Nanosized Si₃N₄ modified in ethyl acetate has better dispersibility and stability than that modified in n-heptane or DMF. TEM pictures also reveal that modified nano-Si₃N₄ possesses good dispersibility.     

Comparative surface and bulk analysis of oxygen in Si3N4 powders

Summary Five commercially available -Si₃N₄ powders and one in the modification were subjected to Auger electron spectroscopy (AES) and carrier-gas-heat extraction (CGHE) analysis.AES depth profiles of the oxygen/nitrogen ratio could be obtained, from which total oxygen contents were calculated and compared to CGHE data. It is demonstrated that by the latter method also dissolved oxygen in -Si₃N₄ is detected, whereas by AES only chemically bound oxygen can semiquantitatively be analyzed. Evidence is found for the existence of water, adsorbed or present as hydroxyl groups, near the surface.

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Vergleichende Oberflächen- und Bulkanalyse von Sauerstoff in Si₃N₄-Pulvern

List of Symbols A Surface area of an idealized Si₃N₄ grain - c _o ^AES Bulk concn. (by wt.) of oxygen in Si₃N₄ as estimated from AES depth profiles - C _O ^GHE Bulk concn. (by wt.) of oxygen in Si₃N₄ as obtained using CGHE in the fixed temperature mode - C _pr Bulk concn. (by wt.) of oxygen in Si₃N₄ as obtained using CGHE in the temperature programme mode - C_surf Bulk concn. (by wt.) of oxygen in Si₃N₄, tentatively assigned to superficial oxygen on Si₃N₄ particles, as obtained using CGHE in the temperature programme mode - C _U c _o ^AES as recalculated from X_U - d Diameter of an idealized Si₃N₄ grain (1 m) - M_index Formula mass of the species named in the index (O, 2 SiO₂, Si₃N₄) - m _o Mass of oxygen in the Si₃N₄ material - M_x Estimated formula mass of a (SiO₂)_2XSi₃N₄ compound as detected by AES via X - r Radius of an idealized Si₃N₄ grain (0.5 m) - V Volume of an idealized Si₃N₄ grain - X atomic oxygen-to-nitrogen ratio (AES) - X_a X values obtained in the scanning beam (area) mode - X_dec X values obtained in the fixed beam (point) mode after about 30 min measuring time (i.e., in some cases, severe decomposition) - X_p X values obtained in the fixed beam (point) mode within about 2 min measuring time (before severe decomposition) - X_U Background value for X in the AES depth profiles - xxps Atomic oxygen-to-nitrogen ratio as obtained from XPS data - Z Sputter depth - Z _E End value for the integration below the depth profile curves - _O Oxygen mass per unit area - _O Oxygen mass per unit volume (recalculated bulk concentration) - _U Oxygen mass per unit volume as recalculated from X_U.     

g-C_3N_4/CaTi_2O_5复合材料制备及其光催化性能

利用类石墨氮化碳(g-C_3N_4)和亚稳相钙钛氧化物(CaTi_2O_5)固相法制备C_3N_4/CaTi_2O_5复合材料。利用X射线衍射(XRD)、金相显微镜、扫描电子显微镜(SEM)及附带能谱分析仪(EDS)和N2吸附-脱附对样品的显微结构和比表面积进行检测分析,并用紫外-可见吸收光度计(UV-Vis)测试了样品的光吸收性能,研究C_3N_4与CaTi_2O_5物质的量之比(nC_3N_4/nCaTi_2O_5)对C_3N_4/CaTi_2O_5复合样品的物相结构和微观形貌的影响,同时考察C_3N_4/CaTi_2O_5复合样品在可见光照射下光催化降解罗丹明染料效果。实验结果表明:相比纯C_3N_4和CaTi_2O_5样品,C_3N_4/CaTi_2O_5复合样品在可见光下具有较高的光催化性能,随着nC_3N_4/nCaTi_2O_5增加,样品的光催化降解率随之增加而后降低,当nC_3N_4/nCaTi_2O_5=1∶1时,样品的光催化降解率达到最大值99.5%,并且循环重复利用5次后,样品的光催化剂降解率仍几乎保持不变。复合样品光催化性能提高主要归因于复合能级结构有效地抑制了电子和空穴复合所致。     

Crystal structures and magnetic properties of CeAu4Si2 and CeAu2Si2

Single crystals of CeAu₄Si₂ and CeAu₂Si₂ have been grown out of ternary fluxes rich in Au, and the former, also by sintering the stoichiometric composition at 750 °C. The single-crystal X-ray refinement result for CeAu₄Si₂ is orthorhombic, Cmmm (No. 65, Z=2), different from a tetragonal result found from an X-ray powder diffraction refinement [H. Nakashima, et al., J. Alloys Compds. 424 (2006) 7]. For CeAu₂Si₂, this is the first report of the stoichiometric crystalline phase, in the known tetragonal I4/mmm structure. The anisotropic field- and temperature-dependent magnetizations, as well as specific heat and resistivity data are compared. Although both compounds have related structural packing, they present unique magnetic features. CeAu₂Si₂ is a typical antiferromagnet with T_N=8.8(1) K and CeAu₄Si₂ features a ferromagnetic component below T_c=3.3(1) K. Both phases have effective moments close in value to that of free Ce³⁺.     

Formation of perovskite phase mixed metal oxides via thermal decomposition of metal-organic complexes with bifunctional ligands

Single-source metal precursors designed to form crystalline perovskite phase mixed metal oxides at low temperatures have been synthesized using -hydroxycarboxylates and alkoxides as ligands. Divalent salts of Ba, Sr, Ca and Pb, [A(O₂CCR₂OH)₂], R = H, Me, were formed from the reaction between ACO₃ and HO₂CCR₂OH in which the hydroxyl group is free to react with metal alkoxide compounds B(OR)₄ where B=Ti, Zr, Sn. These compounds react to eliminate two equivalents of alcohol producing precursors with fixed stoichiometry as shown by the equation: A(O₂CCR₂OH)₂+B(OR)₄ A(O₂CCR₂O)₂B(OR)₂+2HOR. The reaction product is only slightly soluble in pyridine, however upon hydrolysis these compounds form clear solutions from which yellow powders can be isolated by removal of the solvent. Thermolysis of these powders in the temperature range 300–350°C yields perovskite ABO₃. Aqueous solutions of these powders can also be used to form sub-micron sized particles of ABO₃ materials via aerosol processing techniques. In control experiments it was shown that Pb(O₂CCH₂OPh)₂ does not react with metal alkoxide compounds. As a result perovskite PbTiO₃ is not formed below 550°C. Solutions for spin coating thin films can be formed by dissolution of the powder in ethanol, but the crystallization behavior is quite different compared to the bulk powders.     

Effect of sodium oxide doping on solid-solid interactions between V2O5 AND Al2O3

A V₂O₅/Al₂O₃ mixed solids sample was prepared with a molar ratio of 0.41 Na₂O (4 and 10 mol%) was added in the form of sodium nitrate prior to calcination in air in the temperature range 500–1000C. Solid-solid interactions between V₂O₅ and Al₂O₃ were studied using DTA and TG curves and their derivatives together with XRD techniques.The results obtained showed that Na₂O interacted with V₂O₅ at temperatures starting from 500C to yield a sodium/vanadium compound, Na_0.3V₂O₅ which remained stable and decomposed in part by heating at 1000C. V₂O₅ exists in orthorhombic and monoclinic forms in the case of pure mixed solids and those containing 4 mol% of Na₂O and preheated at 500C, and in monoclinic form in the case of the mixed solid doped with 10 mol% of Na₂O.Heating of pure and doped mixed oxide solids at 650C resulted in the conversion of most of the V₂O₅ into AlVO₄. Doping with sodium oxide enhanced the solid-solid interaction between V₂O₅ and Al₂O₃ at 650C to produce AlVO₄. The produced AlVO₄ decomposed completely on heating at 700C to form -Al₂O₃ and V₂O₅, (orthorhombic and monoclinic forms).The presence of Na₂O was found to decrease the relative intensity of the diffraction lines of -Al₂O₃ (corundum) produced at 750C which indicated some kind of hindrance of the crystallization process.Heating of pure and doped mixed solids at 1000C resulted in a further crystallization of acorundum together with V₂O₅ and sodium vanadate, Na_0.3V₂O₅. However, the intensities of diffraction lines relative to those of the sodium vanadium compound were found to decrease markedly by heating at 1000C, indicating partial thermal decomposition into vanadium and aluminium oxides.     

Structural and compositional investigations of Zr4Pt2O: A filled-cubic Ti2Ni-type phase

Syntheses, structural and compositional analyses of the filled cubic Ti₂Ni-type phase in Zr-Pt-O system have been studied, largely for the platinum-richer compositions. Diffraction quality crystals were grown by annealing an arc-melted composition Zr₄Pt₂O_0.66 at 1600 °C under Ar. The refined composition Zr_4.0Pt_1.95(1)O_0.93(6) (a=12.5063(6) Å, , Z=16) is close to the idealized composition Zr₄Pt₂O known in several other Zr-T-O systems (T=late 4d or 5d transition element). (This composition has been erroneously reported by ICDD for years as Zr₆Pt₃O (No. 00-017-0557) and referred to as ε-Zr₆Pt₃O.) The product is only marginally poor in platinum and oxygen, in contrast to the 1960 reports of metallographic studies (∼Zr₄Pt_1.62O_0.44). Under arc-melting conditions, high yields of the cubic phase are obtained from samples with lower platinum concentrations (Zr₄Pt_1.74O_1.04), whereas samples near the refined cubic composition contain hexagonal Zr₅Pt₃O_x as well (Mn₅Si₃-type). The hexagonal structure of binary Zr₅Pt₃ was also refined (Mn₅Si₃ type, P6₃/mcm, a=8.210(1) Å, c=5.385(2) Å) and shown to be non-stoichiometric to at least Zr₅Pt_2.5.     

Crystal structure of Li2Cu3(SeO3)2(SeO4)2

Summary Single crystal X-ray data of the hydrothermally grown new phase Li₂Cu₃(SeO₃)₂(SeO₄)₂ were measured with a four-circle diffractometer up to sin /=0.81 Å^–1 [I2/a,Z=4,V=1175.5 ų,a=16.293(6),b=5.007(2),c=14.448(6) Å, = 94.21(1)°]. The structure was determined by direct and Fourier methods and refined toR=0.034,R _w =0.027 for 2 086 independent reflections.Cu(1)^[4+1]O₅ forms a tetragonal pyramid, Cu(2)^{[4 + 2]}O₆ is a strongly elongated octahedron. The Li atom is surrounded by four O atoms forming a distorted tetrahedron. Se(IV)O₃ and Se(VI)O₄ groups are in accordance to literature, mean Se-O bond lengths are 1.714 and 1.644 Å.

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Die Kristallstruktur von Li₂Cu₃(SeO₃)₂(SeO₄)₂

Zusammenfassung Einkristall-Röntgendaten der hydrothermal gezüchteten neuen Phase Li₂Cu₃(SeO₃)₂(SeO₄)₂ wurden mit einem Vierkreisdiffraktometer im Bereich bis zu sin /=0.81 Å^–1 gemessen [I2/a,Z=4,V=1175.5 ų,a=16.293(6),b=5.007(2),c=14.448(6) Å, =94.21(1)°]. Die Kristallstruktur wurde mittels direkter und Fourier-Methoden bestimmt und für 2 086 unabhängige Reflexe zuR=0.034,R _w =0.027 verfeinert.Cu(1)^[4+1]O₅ bildet eine tetragonale Pyramide, Cu(2)^[4+2]O₆ ist ein stark verlängertes Oktaeder. Das Li-Atom ist von vier O-Atomen in Gestalt eines verzerrten Tetraeders umgeben. Die Se(IV)O₃-und Se(VI)O₄-Gruppen entsprechen der Literatur, die mittleren Se-O-Abstände betragen 1.714 und 1.644 Å.

     

Thermal decomposition of cobalt nitrato compounds: Preparation of anhydrous cobalt(II)nitrate and its characterisation by Infrared and Raman spectra

The thermal decomposition of Co(NO₃)₂·6H₂O (1) as well as that one of NO[Co(NO₃)₃] (Co(NO₃)₂·N₂O₄) (2) was followed by thermogravimetric (TG) measurements, X-ray recording and Raman and IR spectra. The stepwise decomposition reactions of 1 and 2 leading to anhydrous cobalt(II)nitrate (3) were established. In N₂ atmosphere, cobalt oxides are finally formed whereas in H₂/N₂ (10% H₂) cobalt metal is produced. Rapid heating of cobalt(II)nitrate hexahydrate causes melting (formation of a hydrate melt) and therefore side reactions in the hydrate melt by incoupled reactions and evolution/evaporation of different species as, e.g., HNO₃, NO₂, etc. In case of larger amounts in dense packing in the sample container, the formation of oxo(hydoxo)nitrates is possible at higher temperature. For 2, its thermal decomposition to 3 was followed and its decomposition mechanism is proposed.     

Factor analysis of AES depth profiles on Si3N4 ceramic powders

Summary Factor analysis of AES depth profiles is performed on combined spectral regions, thus employing a maximum amount of information. Applied to untreated and oxidized, sub-gm ceramic Si₃N₄ powders as well as to Si₂N₂O, this method reveals significant differences with regard to number and stoichiometry of main components. In case of hydrolyzed Si₃N₄, no significant difference compared with the untreated powder was observed, probably because of irradiation effects.

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Faktorenanalyse von AES-Tiefenprofilen an keramischen Si₃N₄-Pulvern

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Dedicated to Prof. Dr. G. Tölg on the occasion of his 60th birthday     

Vibrational frequencies and force constants of N2O4 in complexes with molecules of different solvents determined by Raman spectra andAb initio calculation

The Raman spectra of N₂O₄ solutions in organic solvents have been recorded. The frequencies ofv ₁,v ₂, andv ₃ bands of N₂O₄ increase with increasing solvent electron-donor properties. Especially large changes ofv ₃ N-N stretching band have been observed (254.5 cm^–1 in n-hexane, 276.5 cm^–1 in 1,4-dioxane). The ab initio calculations have shown that the interaction between N₂O₄ and electron-donor molecules causes an increase of N-N and N-O stretching and O-N-O bending force constants of N₂O₄ in agreement with the results of Raman study.     

g-C3N4/CaTi2O5复合材料制备及其光催化性能

利用类石墨氮化碳（g-C₃N₄）和亚稳相钙钛氧化物（CaTi₂O₅）固相法制备C₃N₄/CaTi₂O₅复合材料。利用X射线衍射（XRD）、金相显微镜、扫描电子显微镜（SEM）及附带能谱分析仪（EDS）和N₂吸附-脱附对样品的显微结构和比表面积进行检测分析,并用紫外-可见吸收光度计（UV-Vis）测试了样品的光吸收性能,研究C₃N₄与CaTi₂O₅物质的量之比（n_C3N4/nCaTi₂O₅）对C₃N₄/CaTi₂O₅复合样品的物相结构和微观形貌的影响,同时考察C₃N₄/CaTi₂O₅复合样品在可见光照射下光催化降解罗丹明染料效果。实验结果表明：相比纯C₃N₄和CaTi₂O₅样品,C₃N₄/CaTi₂O₅复合样品在可见光下具有较高的光催化性能,随着n_C3N4/nCaTi₂O₅增加,样品的光催化降解率随之增加而后降低,当n_C3N4/nCaTi₂O₅=1：1时,样品的光催化降解率达到最大值99.5%,并且循环重复利用5次后,样品的光催化剂降解率仍几乎保持不变。复合样品光催化性能提高主要归因于复合能级结构有效地抑制了电子和空穴复合所致。     

Research on Molecular Structure and Electronic Properties of Ln3+ (Ce3+, Tb3+, Pr3+)/Li+ and Eu2+ Co-Doped Sr2Si5N8 via DFT Calculation

We use density functional theory (DFT) to study the molecular structure and electronic band structure of Sr₂Si₅N₈:Eu²⁺ doped with trivalent lanthanides (Ln³⁺ = Ce³⁺, Tb³⁺, Pr³⁺). Li⁺ was used as a charge compensator for the charge imbalance caused by the partial replacement of Sr²⁺ by Ln³⁺. The doping of Ln lanthanide atom causes the structure of Sr₂Si₅N₈ lattice to shrink due to the smaller atomic radius of Ln³⁺ and Li⁺ compared to Sr²⁺. The doped structure’s formation energy indicates that the formation energy of Li⁺, which is used to compensate for the charge imbalance, is the lowest when the Sr2 site is doped. Thus, a suitable Li⁺ doping site for double-doped lanthanide ions can be provided. In Sr₂Si₅N₈:Eu²⁺, the doped Ce³⁺ can occupy partly the site of Sr₁²⁺ ([SrN₈]), while Eu²⁺ accounts for Sr₁²⁺ and Sr₂²⁺ ([SrN₁₀]). When the Pr³⁺ ion is selected as the dopant in Sr₂Si₅N₈:Eu²⁺, Pr³⁺ and Eu²⁺ would replace Sr₂²⁺ simultaneously. In this theoretical model, the replacement of Sr²⁺ by Tb³⁺ cannot exist reasonably. For the electronic structure, the energy level of Sr₂Si₅N₈:Eu²⁺/Li⁺ doped with Ce³⁺ and Pr³⁺ appears at the bottom of the conduction band or in the forbidden band, which reduces the energy bandgap of Sr₂Si₅N₈. We use DFT+U to adjust the lanthanide ion 4f energy level. The adjusted 4f-CBM of Ce_Sr1Li_Sr1-Sr₂Si₅N₈ is from 2.42 to 2.85 eV. The energy range of 4f-CBM in Pr_Sr1Li_Sr1-Sr₂Si₅N₈ is 2.75–2.99 eV and its peak is 2.90 eV; the addition of Ce³⁺ in Eu_Sr1Ce_Sr1Li_Sr1 made the 4f energy level of Eu²⁺ blue shift. The addition of Pr³⁺ in Eu_Sr2Pr_Sr2Li_Sr1 makes part of the Eu²⁺ 4f energy level blue shift. Eu²⁺ 4f energy level in Eu_Sr2Ce_Sr1Li_Sr1 is not in the forbidden band, so Eu²⁺ is not used as the emission center.     

Vibrational spectra of the peroxotantalates (NH4)3[Ta(O2)4], K3[Ta(O2)4], Rb3[Ta(O2)4] and Cs3[Ta(O2)4] and the crystal structure of Rb3[Ta(O2)4]

The compounds (NH₄)₃[Ta(O₂)₄], K₃[Ta(O₂)₄], Rb₃[Ta(O₂)₄] and Cs₃[Ta(O₂)₄] have been prepared and investigated by X-ray powder methods as well as Raman- and IR-spectroscopy. In the case of Rb₃[Ta(O₂)₄] the structure has been solved from single crystal data. It is shown that all these compounds are isotypic and crystallize in the K₃[Cr(O₂)₄] type (SG , No. 121). The infrared- and Raman spectra (recorded on powdered samples) are discussed with respect to the internal vibrations of the peroxo-group and the dodecahedral [Ta(O₂)₄]³⁻ ion. Symmetry coordinates for the [Ta(O₂)₄]³⁻ ion are given from which the vibrational modes of the O-O stretching vibrations of the O₂²⁻ groups, the Ta-O stretching vibrations and the Ta-O bending vibrations are deduced.     

PbCu3(OH)(NO3)(SeO3)3·1/2H2O und Pb2Cu3O2(NO3)2(SeO3)2: Synthese und Kristallstrukturuntersuchung

Crystals of PbCu₃(OH)(NO₃)(SeO₃)₃·1/2H₂O [a=7.761(3)Å,b=9.478(4)Å,c=9.514(4)Å, =66.94(2)°, =69.83(2)°, =81.83(2)°, space group P ,Z=2] and Pb₂Cu₃O₂(NO₃)₂(SeO₃)₂ [a=5.884(2)Å,b=12.186(3)Å,c=19.371(4)Å, space group Cmc2₁,Z=4] were synthesized under hydrothermal conditions. Their crystal structures were refined with three-dimensional X-ray data toR _w=0.033 resp. 0.055. In PbCu₃(OH)(NO₃)(SeO₃)₃·1/2H₂O the Cu atoms are [4+1] and [4+2] coordinated and via SeO₃ groups a three-dimensional atomic arrangement is built up. In Pb₂Cu₃O₂(NO₃)₂(SeO₃)₂ there are sheets, which are connected only via Pb-O bonds ranging from 2.98 Å to 3.16 Å.