Electrical properties of crystalline borates

Anisotropy of electrical and dielectric properties of α- and β-BaB₂O₄, Ba₂Na₃(B₃O₆)₂F, LiB₃O₅, and CsLi(B₃O₅)₂ single crystals is reported and discussed. In these crystals, alkali ions are dominant charge carriers; pre-heating to 300°C eliminates the humidity, preheating to 500 or 600°C, stabilizes the structure and electrical properties of crystals. Then, both ionic conductivity and dielectric response are determined by movement of alkali ions, and temperature dependences of the ionic conductivity and static permittivity are well reproducible.     

Electrical conductivity studies in sulphate glasses and the mixed alkali effect

Electrical conductivities of alkali sulphate-zinc sulphate glasses have been measured. The variation of conductivity with compositon confirms the presence of the mixed alkali effect. The origin of mixed alkali effect has been explained on the basis of structural considerations reported earlier by us. Communication No. 160 from the Solid State and Structural Chemistry Unit.     

Impact of anionic substitutions on apatite structure and properties

A review of the results of the authors on single and coupled substitutions of F for OH, and of CO₃ and SO₄ for PO₄ in synthetic and natural apatites, their influence on apatite structure and properties, studied by peak fitting FTIR, XRD, TG/DTA and TG/EGA methods, is presented. Calcination of carbonate and sulphate substituted apatites leads to the formation of stable stoichiometric apatite.     

A simple and general route for the preparation of pure and high crystalline nanosized lanthanide silicates with the structure of apatite at low temperature

Rare earth silicates with the structure of apatite are attracting considerable interest since they show oxygen ion conductivities higher than that of yttria-stabilized zirconia (YSZ) at moderate temperature. Based on the hydrothermal synthesis we presented a simple one step process for the direct preparation of the pure and the high crystalline nanosized rare earth silicates with the structure of apatite under a mild condition (230 °C). Since the preparation of the high crystalline silicon based rare earth apatites is performed at high temperature previously and accompanied by subsequent process of grinding, results of this work provide a promising alternative of the existing methodology. Furthermore, due to the relatively low temperature of the preparation of these materials, high doping of monovalent cation can be done, which was not achieved before.     

Defect and transport properties of nanocrystalline ceramics and thin films

This paper presents an overview of recent research on the defect and transport properties of nanocrystalline ionic and mixed conducting ceramics and thin films. In the first part, some basic concepts and properties of boundaries are reviewed, including diffusion, segregation, and space charge regions. Experimental data on nanoceramics and thin films made from pure and doped CeO₂, TiO₂, ZrO₂, and CaF₂ are presented and discussed in the second part; opportunities for future work on this topic are outlined. Electronic Publication     

Lattice effects in cubic La2Mo2O9: Effect of vacuum and correlation with transport properties

This study aims to investigate correlations between lattice effects and transport properties in cubic La₂Mo₂O₉. High temperature neutron diffraction data, recorded in air and under vacuum, are used to follow the evolution with temperature of selected structural parameters, i.e. bond lengths and angles. Results suggest a possible correlation with the experimentally observed decrease of the activation energy for oxygen migration at high temperature. The effect on the structural properties of the low oxygen partial pressure used during the measurements in vacuum is negligible and this represents a valuable information in view of possible applications of the material in solid state devices.     

^35Cl的核磁共振法研究高氯酸钙的离子缔合和离子溶剂化

本文研究了在10种溶剂中0.5mol/L的Ca(ClO4)2中^35Cl的峰宽和6种溶剂中^35Cl峰宽随盐浓度的变化，讨论了离子缔合与溶剂性质及离子性质的关系；以乙晴或乙醇作溶剂，在Ca(ClO4)2浓度固定时，观察^35Cl峰宽随第2溶剂组分B（此处B为H2O或DMF）的加入量（以[B]/[Ca^2 ]表示）的变化，讨论了变化规律、原因及钙离子被水或DMF的溶剂化数；还结合电导数据，讨论了Ca^2 离子与ClO4^-离子的相互作用和缔合形式。     

Polyurethane anionomers synthesised with aromatic, aliphatic or cycloaliphatic diisocyanates, polyoxyethylene glycol and 2,2-bis-(hydroxymethyl)propionic acid. Part 3. Electrical properties of polyurethane coatings

The following electrical properties were found for polymer coatings obtained from polyurethane anionomers synthesised with the use of various diisocyanates: volume resistivity, permittivity and dielectric dissipation factor. The effects were discussed from the molecular structures and phase structures of those anionomers on the value of their ionic conductivity and polarizability. The anionomer prepared from the aliphatic diisocyanate was found to offer ionic conductivity; hence, that material can be considered to be a solid electrolyte, which exhibits a considerable susceptibility to structural modifications in the alternating electric field.     

Study on the fluoride adsorption of various apatite materials in aqueous solution

The aim of this study was to evaluate the defluoridation efficiencies of various sorbents in aqueous solution. These sorbents include synthetic nano-hydroxyapatite (n-HAp), biogenic apatite (bone meal), treated biogenic apatite (bone meal prepared by H₂O₂ oxidation) and geogenic apatite (rock phosphate), which were characterized by XRD, FTIR, TEM and SEM. It has been observed that the defluoridation capacities follow the order: n-HAp > BH₂O₂ > B > rock phosphate. The controlling factors, sorbent dose, initial fluoride concentration, pH, contact time and temperature were investigated. The defluoridation capacities increased with the increase in the initial fluoride concentration and contact time, decreased with the increase in the sorbent dose. The optimum pH range for removal of fluoride on various apatite sorbents was considered to be 5.0-6.0. The fluoride adsorption can be explained by Langmuir, Freundlich isotherms, and the adsorption kinetic data follow the pseudo-second-order model. Thermodynamic parameters such as ΔH⁰, ΔS⁰ and ΔG⁰ indicated that the adsorption on various apatite sorbents was spontaneous and endothermic. These results showed that bone meal is a promising material for fluoride adsorption.     

Investigation of the stability of Co-doped apatite ionic conductors in NH3

Hydrogen powered solid oxide fuel cells (SOFCs) are of enormous interest as devices for the efficient and clean production of electrical energy. However, a number of problems linked to hydrogen production, storage and transportation are slowing down the larger scale use of SOFCs. Identifying alternative fuel sources to act as intermediate during the transition to the full use of hydrogen is, therefore, of importance. One excellent alternative is ammonia, which is produced on a large scale, is relatively cheap and has the infrastructure for storage and transportation already in place. However, considering that SOFCs operate at temperatures higher than 500 °C, a potential problem is the interaction of gaseous ammonia with the materials in the cathode, anode and solid electrolyte. In this paper, we extend earlier work on high temperature reactions of apatite electrolytes with NH₃ to the transition metal (Co) doped systems, La_9.67Si₅CoO₂₆ and La₁₀(Si/Ge)₅CoO_26.5. A combination of PXRD, TGA and XAFS spectroscopy data showed a better structural stability for the silicate systems. Apatite silicates and germanates not containing transition metals tend to substitute nitride anions for their interstitial oxide anions, when reacted with NH₃ at high temperature and, consequentially, lower the interstitial oxide content. In La_9.67Si₅CoO₂₆ and La₁₀(Si/Ge)₅CoO_26.5 reduction of Co occurs as a competing process, favouring lower levels of nitride-oxide substitution.     

Study of the ionic conductivity of Ca6La4(PO4)2(SiO4)4F2 and Ca4La6(SiO4)6F2

In order to enhance our knowledge about the Ca_10−xLa_x(PO₄)_6−x(SiO₄)_xF₂ (0 ≤ x ≤ 6) series, whose chemical stability decreases as the substitution degree increases, Ca₆La₄(PO₄)₂(SiO₄)₄F₂ and Ca₄La₆(SiO₄)₆F₂ compounds were prepared through a solid-state reaction. Their ionic conductivity was measured by impedance spectroscopy. The results indicate that the conductivity increases with substitution, and fits the Arrhenius equation over the investigated temperature range. At high temperatures, a change in the activation energy has been observed, which has been related to the nature of the Ca/La–F bond, i.e. to the polarizability of lanthanum.     

Real-time monitoring of the mechanism of poorly crystalline apatite cement conversion in the presence of chitosan, simulated body fluid and human blood

In this study, the real-time monitoring of structural changes, occurring upon poorly crystalline apatite bone cement hardening in the presence of chitosan, simulated body fluid and human blood, was performed. Strong experimental evidence of octacalcium phosphate intermediate phase is provided. The energy dispersive X-ray diffraction was applied in situ to monitor the structural changes upon the transformation process, while the Fourier transform infrared spectroscopy and the scanning electron microscopy supplied information on the vibrational and morphological properties of the system. The cooperative action of chitosan and simulated body fluid induces the formation of a preferentially oriented hydroxyapatite phase, this process being similar to the oriented self-assembling process in collagen-apatite matrix in human plasma, occurring upon in vivo biomineralization. Conversely, the presence of blood does not induce any significant change in hardening kinetics and the final structure of the investigated cement.     

Characterization of the conduction properties of a solid electrolyte by short-circuiting a potentiometric galvanic cell

By short-circuiting a solid electrolyte galvanic cell, the ionic conductivity of the electrolyte employed in the cell can be determined. There is no other potential involved in this technique with regard to the characterization of the conduction properties of the electrolyte. In particular, the method does not offer any information about the electronic conductivity.     

NaCl对离子液体中电解精炼铝的影响

研究了添加NaCl对BMIC-AlCl3离子液体电导率及电解精炼铝的影响,分析了阴极电流效率、电流密度的变化,并通过扫描电镜和能谱分析研究了沉积层的形貌及成分。结果表明,添加NaCl可以提高电解液的电导率,阴极电流效率也可提高至82%～96%,但电流密度则有所降低;添加NaCl还可以改善电解精炼铝的沉积质量,使晶粒尺寸...     

An experimental investigation of ionic transport properties in CuI-Ag2WO4 and CuI-Ag2CrO4 mixed systems

The phenomenon of ionic transport in the case of two different mixed systems (CuI)_(1−x)-(Ag₂WO₄)_x(0.15?x?0.6) and (CuI)_(1−y)-(Ag₂CrO₄)_y(0.15?y?0.5) has been investigated. Powder X-ray diffraction (XRD) analysis coupled with differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR), FT-Raman and electrical transport studies involving ionic transport number and temperature-dependent electrical conductivity measurements have been carried out in order to identify the various phases responsible for the conduction process. The occurrence of typical ionic conductivity values of 4.5×10⁻³ Scm⁻¹ for the composition (CuI)_0.45-(Ag₂WO₄)_0.55 and 1.1×10⁻⁴ Scm⁻¹ in the case of (CuI)_0.55-(Ag₂CrO₄)_0.45 at room temperature has been discussed in terms of the observed characteristics.     

两种疏水型膦类离子液体的密度、动力粘度及电导率

Two air and water stable hydrophobic phosphonium ionic liquids (ILs), tributyl-hexylphosphonium tetrafluoroborate ([P4446][BF4]) and tributyl-hexylphosphonium bis (trifluoromethylsulfonyl) imide ([P4446][NTf2]), were prepared by the traditional method. Their basic physico-chemical properties of density, dynamic viscosity, and electrical conductivity were measured in the temperature range of 283.15-353.15 K. The effect of the temperature and structure of the anion on the thermodynamic properties were discussed. The properties are compared with the cation structures changing of the phosphonium type ILs. The most important thermodynamic properties for their practical application, such as molecular volume, standard molar entropy, and lattice energy, were calculated from their density using empirical equations. The calculated values were compared with those of imdazolium and pyridinium type ILs. Molar electrical conductivity was determined from density and electrical conductivity. The applicability of the Vogel-Fulcher-Tamman (VFT) and Arrhenius equations to the fitting of the dynamic viscosity and electrical conductivity was validated. The activation of the electrical conductivity and dynamic viscosity were obtained from the final VFT equation. According to the Walden rule, the density, dynamic viscosity, and electrical conductivity were described by the Walden equation. The results are very important for academic studies as well as industrial applications of these ILs.     

The confinement and anion type effect on the physicochemical properties of ionic liquid/halloysite nanoclay ionogels

This work is the first attempt to study the physicochemical properties of ionogels - quasi-solid hybrid materials formed by ionic liquids (ILs) − 1-butyl-3-methylimidazolium (BMIm⁺) salts with dicyanamide- (DCA⁻), bis(trifluoromethylsulfonyl)imide- (TFSI⁻), and trifluoromethanesulfonate- (Otf⁻) anions - and halloysite, a powdered clay filler with nanotube particles (at the IL:Hal molar ratio of 2:1) in order to find possible new applications of ionic liquids and industrial minerals. The electron microscopy, TG, and DSC analysis, FTIR spectroscopy, X-ray diffraction analysis, conductometry and cyclic voltammetry methods are used to investigate the anion effect on the IL interaction with halloysite. It has, for the first time, been found that the distinguishing feature of halloysite interaction with an IL determining the structural changes in the clay mineral and electrochemical characteristics of the ionogels is partial dehydration of the clay and absorption of the released water by the ionic liquid. It is shown that the halloysite dehydration effect depends on the IL hydrophilicity determined by the anion type, corresponds to the series: BMImDCA > BMImOtf > BMImTFSI. The electrochemical and thermal behaviour of ILs confined within a halloysite matrix differs from that of bulk ILs and is controlled by the anion type. Temperature dependences of the structural resistance of the halloysite filler are radically different for the ILs with high and low hydrophilicity. The effects resulting from the formation of halloysite-based ionogels can be of interest to those who develop quasi-solid ionic conductors that can work within a wide temperature range.     

Transport properties of protic ionic liquids,pure and in aqueous solutions: Effects of the anion and cation structure

Ionic conductivities of twelve protic ionic liquids (PILs) and their mixtures with water over the whole composition range are reported at 298.15 K and atmospheric pressure. The selected PILs are the pyrrolidinium-based PILs containing nitrate, acetate or formate anions; the formate-based PILs containing diisopropylethylammonium, amilaminium, quinolinium, lutidinium or collidinium cations; and the pyrrolidinium alkylcarboxylates, [Pyrr][C_nH_2n+1COO] with n = 5–8. This study was performed in order to investigate the influence of molecular structures of the ions on the ionic conductivities in aqueous solutions. The ionic conductivities of the aqueous solutions are 2–30 times higher than the conductivities of pure PILs. The maximum in conductivity varies from ww=0.41 ??to ??0.74$w_w=0.41\text{\hspace{0.17em}??}\text{to}\text{\hspace{0.17em}??}0.74$ and is related to the nature of cations and anions. The molar conductance and the molar conductance at infinite dilution for (PIL + water) solutions are then determined. Self-diffusion coefficients of the twelve protic ionic liquids in water at infinite dilution and at 298.15 K are calculated by using the Nernst–Haskell, the original and the modified Wilke–Chang equations. These calculations show that similar values are obtained using the modified Wilke–Chang and the Nernst–Haskell equations. Finally, the effective hydrodynamic (or Stokes) radius of the PILs was determined by using the Stokes–Einstein equation. A linear relationship was established in order to predict this radius as a function of the anion alkyl chain length in the case of the pyrrolidinium alkylcarboxylates PILs.     

Electrical and mechanical properties of the zone-drawn polypyrrole films

The zone-drawing method (ZD) was applied to electrochemically synthesized polypyrrole films containing tosylate (PPy/TsO) and the mechanical and electrical properties of the resulting films were investigated. It was found that the electrical conductivity of the zone-drawn film reached 365 S cm⁻¹ in the drawing direction, which was 4.7 times that of the original film. The tensile properties of the zone-drawn film were improved and Young's modulus and strength at break increased to 4.32 GPa and 90.1 MPa from 0.53 GPa and 40.4 MPa of the as-synthesized film, respectively. The dynamic storage modulus (E) increased by the zone-drawing over a whole experimental temperature range and attained 7.0 GPa at room temperature and 4.0 GPa even at 200°C. © 1996 John Wiley & Sons, Inc.     

Formate incorporation in the structure of Ca-deficient apatite: Rietveld structure refinement

Two sets of non-stoichiometric apatites (Ca-deficient apatites) were prepared from calcium phosphate solutions by homogeneous precipitation through the hydrolysis of formamide at 95°C. One set of products contained monetite (CaHPO₄) and apatite, whilst the second, with more formamide, contained only apatite. Rietveld whole pattern fitting structure refinements were undertaken on all samples, and chemical analyses, IR and NMR spectroscopy, on the second set of samples. The Ca/P mol ratio was 1.596. Rietveld analysis gave lattice parameters a=9.4729(20) and c=6.8855(9) Å and showed that Ca²⁺ ions were lost exclusively from Ca2 sites, and that the PO₄ tetrahedron volume and P-O bonds were 4.4% and 1.4% smaller, respectively, than in hydroxyapatite (OHAp). Formate, HCO₂⁻, was clearly visible in the IR and NMR spectra, but the diffraction studies showed it was not present as a separate crystalline phase. Chemical analysis gave 5.8 wt % formate. We propose that the enlarged a-axis compared with OHAp (a=9.4243(55) Å) and reduced PO₄ dimensions and P occupancy are, respectively, caused by the partial replacement of OH⁻ and PO₄³⁻ ions in the structure by HCO₂⁻ ions. These substitutions would parallel the similar known substitutions of CO₃²⁻ ions in precipitated carbonate apatites.