Thermodynamics of the thermal decomposition of calcium oxalate monohydrate examined theoretically

Geometries and energies of isolated CaC₂O₄·H₂O, CaC₂O₄, CaCO₃, CaO, H₂O, CO and CO₂ were determined at the ab initio level using effective core potential valence basis sets of doublezeta quality, supplemented with polarization functions. The effects of electron correlation were taken into account at the second order Møller-Plesset level of theory. For CaC₂O₄·H₂O, the correlation for the basis set superposition error was also included. Common routines were employed to evaluate entropies, heat capacities, as well as enthalpies and free enthalpies of formation of all entities. The enthalphies and free enthalpies of consecutive dehydration of CaC₂O₄·H₂O, decarbonylation of CaC₂O₄ and decomposition of CaCO₃ towards CaO and CO₂ were determined on the basis of avialable data from the literature or those predicted thoretically. Assuming that upon all the above mentioned processes the system maintains equilibrium, the fractions reacted, enthalpy changes and differential dependencies of thesevs. temperature were derived and compared with experimental thermoanalytical data.     

Synthesis and Catalytic Activity of Magnetic Cryptomelane-Type Manganese Oxide Nanotubes

Magnetic cryptomelane-type manganese oxide (OMS-2) nanotubes were successfully prepared by grafting Fe₃O₄ nanoparticles onto the OMS-2 nanotubes. SEM and HRTEM images show that the prepared magnetic OMS-2 nanotubes exhibited diameters of 100?nm, lengths less than 3.0???m, and the diameters of the Fe₃O₄ nanoparticles are less than 10?nm. The synthesized material exhibits excellent magnetic separation and catalytic properties for the degradation of methylene blue (MB) by a Fenton-like reaction.     

Mineral and microelement compositions of urinary stones

The mineral and microelement compositions of urinary stones from patients in various districts of the Novosibirsk region are analyzed. The mineral composition is determined using X-ray powder diffraction and vibrational spectroscopy. The microelement composition is identified using synchrotron radiation X-ray fluorescence analysis. Calcium oxalates (whewellite CaC₂O₄ · H₂O and weddellite CaC₂O₄ · 2H₂O) are the most frequent components of the urinary stones. Oxalate uroliths contain a variety of microelements in significant amounts. Phosphate uroliths, represented by hydroxylapatite Ca₅(PO₄)₃(OH) and struvite MgNH₄PO₄ · 6H₂O, account for about one-fifth of the collection. Apatite urinary stones contain maximal strontium amounts. The struvite uroliths have higher rubidium levels. Uric acid uroliths (C₅H₄N₄O₃) account for about 11% of the collection. Their strontium concentrations are minimal. The element composition of the urinary stones is a function of their mineral constituents, the environmental surroundings, and the metabolism specifics of the patient.     

Inhibition of the crystal growth and aggregation of calcium oxalate by elemental selenium nanoparticles

Chemical modulation of calcium oxalate (CaC₂O₄) crystals morphologies by elemental selenium nanoparticles (nanoSe⁰) was investigated with scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), Fourier transform infrared spectrometry (FTIR), and X-ray diffraction (XRD) analysis. The coordination between nanoSe⁰ and C₂O₄²⁻ had great effect on the formation of CaC₂O₄ crystals. NanoSe⁰ inhibited the growth of calcium oxalate monohydrate (COM) crystals, prevented the aggregation of COM crystals and induced the formation of the spherical calcium oxalate dihydrate (COD) crystals containing selenium, which are the thermodynamically less stable phase and has a weaker affinity to the cell membranes than COM crystals. The inhibition of the crystal growth and aggregation of CaC₂O₄ crystals by nanoSe⁰ displayed concentration effects.     

水溶液体系中钐离子(III)对草酸钙结晶过程影响效应的研究

进行了水溶液体系中三价稀土离子(Sm^3＋)对草酸钙(CaC₂O₄)结晶过程影响效应的研究. 采用微量热法、X射线衍射(XRD)以及扫描电镜(SEM)法, 研究了Sm^3＋对草酸钙结晶过程动力学的影响效应及对草酸钙晶体晶型、形貌、尺寸的调控作用. 微量热研究结果表明, Sm^3＋对草酸钙结晶过程的影响包括对晶体初期成核以及晶体生长过程的影响, 在适宜的浓度(约2.50×10^－5 mol•L^－1)下达到对晶体成核与生长的最佳抑制效果; XRD研究结果表明, Sm^3＋的加入有利于草酸钙二水合物(COD)的生成; SEM形貌研究表明, Sm^3＋对草酸钙晶体的形态、尺寸产生非常显著的调控作用.     

Synthesis of different polymorphic modifications of calcium oxalate by electrodeposition

Different hydrates of calcium oxalate have been electrodeposited by electrogeneration of acid at the anode from an EDTA-stabilized calcium nitrate bath containing dissolved oxalate ions. The deposition is controlled by varying the bath pH, temperature, and current density. Formation of metastable CaC₂O₄·2H₂O is favored at high current densities at ambient temperature, whereas the thermodynamically stable CaC₂O₄·H₂O is formed at elevated bath temperatures. Both the polymorphs show oriented growth with respect to the substrate normal under different deposition conditions.     

Facile synthesis of multifunctional multiwalled carbon nanotubes/Fe3O4 nanoparticles/polyaniline composite nanotubes

With an average diameter of 100-150 nm, composite nanotubes of polyaniline (PANI)/multiwalled carbon nanotubes (MWNTs) containing Fe₃O₄ nanoparticles (NPs) were synthesized by a two-step method. First, we synthesized monodispersed Fe₃O₄ NPs (d=17.6 nm, σ=1.92 nm) on the surface of MWNTs and then decorated the nanocomposites with a PANI layer via a self-assembly method. SEM and TEM images indicated that the obtained samples had the morphologies of nanotubes. The molecular structure and composition of MWNTs/Fe₃O₄ NPs/PANI nanotubes were characterized by Fourier transform infrared spectra (FTIR), energy dispersive X-ray spectrometry (EDX), X-ray photoelectron spectra (XPS), X-ray diffraction (XRD) and Raman spectra. UV-vis spectra confirmed the existence of PANI and its response to acid and alkali. As a multifunctional material, the conductivity and magnetic properties of MWNTs/Fe₃O₄ NPs/PANI composites nanotubes were also investigated.     

Thermal analysis of kidney stones and their characterization

Thermal decomposition and structural characterization of three human kidney stones (KS1–KS3) extracted from patients of Eastern Bohemia have been carried out using X-ray powder diffraction systems (XRD), scanning electron microscope with energy dispersive X-ray micro analyser (SEM-EDX) and differential thermal analysis (DTA). The samples KS1 and KS2 solely consisted of calcium oxalate monohydrate (a.k.a. whewellite, CaC₂O₄·H₂O). The third sample, KS3, was formed from calcium oxalate dihydrate (weddellite, CaC₂O₄·2H₂O), calcium oxalate monohydrate, and hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂). Thermal measurements were carried out in the range between room temperature and 1,230 °C. XRD analysis was utilized to investigate the change of phases at 800 and 1,230 °C.     

The enthalpies of interactions of Ca2+(aq) and C2O 4 2− (aq) ions in complexon solutions: Competition between complexation and precipitation

The thermal effects of mixing of aqueous calcium chloride with sodium citrate and ethylenedi-aminetetraacetate in the absence and presence of sodium oxalate have been measured at 25°C. The thermal effects of dilution of aqueous calcium chloride solutions were determined. The thermal effects of calcium oxalate precipitation and formation of calcium complexes with citrate and ethylenediaminetetraacetate ions were calculated. The 1% solution of sodium citrate inhibited the formation of CaC₂O₄ (s); in a 1% solution of sodium ethylenediaminetetraacetate with [Ca²⁺][C₂O ₄ ^2? ] > 10^?5, the endothermal formation of the [CaEdta]^2? complex quickly changed to exothermal precipitation. The 3 and 5% solutions of complexons showed a pronounced inhibiting effect on the formation of urinary stones even when the concentration of calcium and oxalate ions in solution exceeded the product of solubility of CaC₂O₄ by four and more orders of magnitude.     

Decoration of MWCNTs with CoFe2O4 Nanoparticles for Methylene Blue Dye Adsorption

In the present work, a simple and viable method for producing multi-walled carbon nanotubes (MWCNTs) decorated with CoFe₂O₄ nanoparticles is presented. Chemical composition and crystal structure of the CoFe₂O₄/MWCNT composite was confirmed by X-ray diffraction measurements, while transmission electron microscopy was used to characterize the morphology and the distribution of nanocrystals in the composite. The obtained particles with relatively small diameter (about 14.9?nm) were found to be dispersed on the carbon nanotubes. The adsorption of methylene blue dye on CoFe₂O₄/MWCNT composites has been investigated. CoFe₂O₄/MWCNT composites show high adsorption capacity for methylene blue dye. Both Langmuir and Freundlich models describe the adsorption isotherms very well and the adsorption thermodynamic parameters (?G ⁰, ?H ⁰ and ?S ⁰) were calculated. The adsorption of methylene blue is generally spontaneous and thermodynamically favorable. The adsorption of methylene blue involves an endothermic process.     

Synthesis of Nanorods of Crystalline Co3O4Using Carbon Nanotubes as Templates

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Large-scale preparation of aluminum borate-coated aluminum oxide nanowires

Single-crystal and uniform aluminum borate (Al₄B₂O₉)-coated aluminum oxide nanowires have been synthesized in high purity and in large yield via a reaction of metal aluminum with boron oxide in the presence of carbon nanotubes (CNTs). The aluminum oxide nanowires exhibit a well-crystallized one-dimensional structure with diameters ranging from 50 to 70 nm, and the Al₄B₂O₉ have a coating thickness of about 1-5 nm. CNTs play a crucial role in the formation of the important ceramic nanowires, by providing a platform to grow the composite structure. The growth mechanism was proposed by the detailed microscopy observations.     

Traitement mecanique des materiaux

Within the limits of a comparative study of solid-state transformations induced by different constraints (thermodynamics, mechanics, electromagnetics, etc.), the authors present the phase-modifications brought about by the grinding of someoxalates (K₂C₂O₄. H₂O; CaC₂O₄. H₂O; BaC₂O₄ ·n H₂O withn=0, 1/2, 1 and 2). The water vapour pressure and temperature during the mechanical treatment were selected and fixed. The specificity of the mechanical constraint is discussed. This study mainly shows that (a) the grinding may or may not bring about dehydration, but it may also bring about rehydration; (b) the evolution of a hydrate during treatment, following a well-defined process, shows all the phases known from the most hydrated to the anhydrous form; (c) the mechanical dehydration may be stopped by a change in the grinding temperature and vapour pressure conditions.     

In situ synthesis and characterization of TiO<Subscript>2</Subscript> nanoarray films

Based on anodic aluminum oxide (AAO) templates prepared in different acidic solutions, highly ordered aligned titania nanotubes array films have been successfully prepared by the liquid phase deposition method. The effect of AAO template type on the microstructure of titania film have been studied. Using the template with a certain volume fraction of Al₂O₃ (less than 0.71), ordered aligned titania nanotubes were obtained, characterized with an outer diameter of 200 nm and an inner diameter of 100 nm, respectively. However, titania existed as ordered aligned nanorods with the diameter of 100 nm when the template with large volume fraction of Al₂O₃ (larger than 0.71) was used. TiO₂ thin films calcined at 400°C for 4 h have an anatase phase and exhibit good photocatalytic activity, i.e., 75% methylene blue could be degraded under ultraviolet irradiation for 2 h.     

卵磷脂-水体系中草酸钙模拟生物矿化的研究

草酸钙通常以三种水化物的形式存在：热力学稳定的一水草酸钙（以下简称COM），亚稳态的二水草酸钙（以下简称COD）和三水草酸钙（以下简称COT）。前人研究已经表明引起草酸钙不同水化物成核、生长以及聚集的因素，不仅仅在于钙离子和草酸根离子浓度的过量，而且与晶体成长所处环境包括离子种类、浓度、环境等有关。有关表面活性剂对草酸钙结晶过程的影响，例如SkriticD．小组做了大量的研究工作犤１～３犦。他们指出草酸钙晶体的成核、生长、组成以及晶体结构同表面活性剂水溶液的状态间存在着复杂的相关性犤１犦。本文选用卵磷脂（P…     

Carbon nanotube assisted synthesis of CeO2 nanotubes

CeO₂ nanotubes have been synthesized facilely using carbon nanotubes (CNTs) as templates by a liquid phase deposition method. The properties of the CeO₂ nanotubes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectrum (XPS) as well as thermogravimetry and differential thermal analysis (TG-DTA). The obtained CeO₂ nanotubes with a polycrystalline face-centered cubic phase have a uniform diameter ranging from 40 to 50 nm. The CeO₂ nanotubes are composed of many tiny interconnected nanocrystallites of about 10 nm in size. The pretreatment of CNTs and calcination temperature were confirmed to be the crucial factors determining the formation of CeO₂ nanotubes. A possible formation mechanism has been suggested to explain the formation of CeO₂ nanotubes.     

(Meta)stabiles CaC2

(Meta)stable CaC₂ One out of four modifications of CaC₂ is the so‐called metastable Calcium Carbide, CaC₂‐III, which was synthesized as pure material. It forms by heating monoclinic CaC₂‐II (C2/c) above 150 °C and remains stable after cooling down to room temperature. The structure was refined from X‐ray powder patterns (C2/m, Z = 4, a = 722.6(1) pm, b = 385.26(7) pm, c = 737.6(1) pm, β = 107.345(2)°). After grinding CaC₂‐III transforms back into CaC₂‐II. Heating CaC₂‐III induces a reversible phase transition into the cubic modification (CaC₂‐IV) at 460 °C. Differences between the three different structures of CaC₂ I–III, being stable at ambient conditions are also shown by ¹³C‐MAS‐NMR measurements, especially the presence of two distinct types of carbon atoms in the structure of the title compound.     

Hierarchical Porous ZnMn2O4 Hollow Nanotubes with Enhanced Lithium Storage toward Lithium‐Ion Batteries

We have purposefully developed a smart template‐engaged methodology to efficiently fabricate well‐defined ternary spinel ZnMn₂O₄ hollow nanotubes (NTs). The procedure involves coating carbon nanotubes (CNTs) with ZnMn₂O₄ nanosheets (NSs), followed by heating at high temperature in air to oxidize the CNT template. Physicochemical characterization demonstrated that the formed ZnMn₂O₄ NTs with a diameter of approximately 100 nm were composed of assembled NSs and/or nanoparticles (NPs) as building blocks and possessed numerous nanopores of several nanometers in the sidewall of the NTs. In favor of the intrinsic structural advantages, the resulting ZnMn₂O₄ NTs exhibited superior electrochemical lithium‐storage performance with a large capacity, good rate behavior, and excellent cyclability when evaluated as promising anodes for lithium‐ion batteries (LIBs). The remarkable electrochemical performance was rationally ascribed to the appealing one‐dimensional (1D) porous hollow tubular architecture with nanoscale subunits and mesopores in the sidewalls, which decreased the diffusion length for the Li⁺ ions, improved the kinetic process, and enhanced the structural integrity with sufficient void space to tolerate the volume variation during Li⁺‐ion insertion/extraction. These results highlight the promising application of 1D ZnMn₂O₄ NTs as anodes for high‐performance LIBs.     

Excess capacity on compound phases of Li2FeTiO4 composite cathode materials synthesized by hydrothermal reaction using optional titanium sources to boost battery performance

Li₂FeTiO₄ composites have been produced using commercial LiAC, FeCl₂ and different titanium sources by hydrothermal synthesis (HS) at 175 °C and subsequent annealing at 700 °C. Impure phase TiO₂, Fe₂O₃ and FeTiO₄ were detected out among the Li₂FeTiO₄ composites with different titanium sources. Micron and nano-sized particles of Li₂FeTiO₄ were prepared from various titanium raw materials, with nano-sized particles predominating when titanium raw materials were layered hydrogen titanate nanowire (H₂Ti₃O₇NW, HTO-NW) and titanium oxide nanotubes (TiO₂NB). The Li₂FeTiO₄ composites synthesized by HTO-NW shows a primary particle size of 50−200 nm of high crystallinity staggered with undissolved nanowire with a diameter size of about 100 nm. The samples using one-dimensional nanometer titanium oxide (TiO₂ NB) as the raw material can get a super high initial discharge capacity of 367.8 mAh/g at the rate of C/10 and excellent cycling stability. The selection of raw materials and adopting multi-phase modification can be considered as an effective strategy to improve the electro-chemical properties of Li₂FeTiO₄ composite cathode materials for the lithium secondary battery.     

Differential Non-Linear Isoconversional Procedure for Evaluating the Activation Energy of Non-Isothermal Reactions

A differential isoconversional non-linear procedure for evaluating activation energy from non-isothermal data is suggested. This procedure was applied to model reactions (simulations) and to the dehydration of CaC₂O₄⋅H₂O. The results were compared with those obtained by other isoconversional methods. This revised version was published online in August 2006 with corrections to the Cover Date.