The Superstructure of Lead Tetragonal Tungsten Bronze

Electron-optical studies of the superstructure of lead tetragonal tungsten bronze (lead-TTB) are presented. Samples were synthesized for a range of lead compositions and synthesis conditions. For lead-TTB synthesized for very short reaction times, compositional analysis combined with electron diffraction revealed these specimens to also contain significant levels of an intergrowth tungsten bronze (ITB) phase. It was proposed that ITB was formed during the reaction as an intermediate between the tungsten oxide reagent and lead-TTB. Electron-diffraction investigations of lead-TTB over a range of specimen compositions determined that the large majority of crystallites examined exhibited a well-ordered 2√2a_TTB×√2b_TTB×2c_TTB supercell periodicity, although evidence of a larger a-axis repeat was also observed. No evidence for a variation in the supercell with lead composition was observed. A model for the supercell was generated from consideration of stacking sequences of correlated ordered arrays of lead and tilted octahedra and it was demonstrated that larger superstructures could be generated using alternative stacking sequences.     

Design of experiment for evaluation of uncertainty from sampling in the framework of the fitness for purpose concept: a case study

The design of an experiment for the evaluation of sampling uncertainty in the framework of the fitness for purpose concept is described in terms of probabilities (risks of the user) of type 1 and type 2 errors in decisions concerning the significance of effects influencing the sampling uncertainty and the measurement results. As a case study, an experiment based on the duplicate method for quantification of the sampling uncertainty and inhomogeneity (heterogeneity) of a melt of tin-free bronze produced in a 10-ton reflective oven is analyzed. The melt is defined as the sampling target. It is shown that the number of such targets (melts), the number of samples under analysis and the number of replicate analyses can be minimized, i.e., the size and cost of the experiment can be reduced, if the user knows which risks are acceptable. When inhomogeneity of the sampling target has a systematic character, like the decrease of the mass fraction of aluminum from the beginning to the end of the melt pouring in the case study, the inhomogeneity effect can be separated from the sampling uncertainty and evaluated according to the user’s needs.     

Mutual indirect probing of platinized platinum/tungstate nanostructural features

The comparative study of isopolytungstates immobilized on smooth Pt and platinized Pt (Pt/Pt) provides a possibility to separate several specific effects on H- and O-upd at an external platinum surface and inside the pores of Pt/Pt. In the former case, a solid rechargeable product is formed (nonstoichiometric tungsten bronze), which an inherent porous structure allows solution penetration and does not prevent charging of the Pt/solution interface. Electrochemical responses of smooth Pt give more precise information on the film behaviour, when adsorption phenomena are clarified on the basis of data for Pt/Pt. Electrocatalytic tests (nitrate reduction) confirm unambiguously that the major part of the internal Pt/Pt surface area is modified by adsorbed polytungstate. This result gives, in its turn, new understanding of the size of Pt/Pt pores on the nanometre scale.

Effects of Pressure and Temperature on the Formation of Tungsten-Bronze-Related Phases, RExWO3+y, with RE=La and Nd

The influence of pressure (P) and temperature (T) on the formation of tungsten-bronze-related phases containing lanthanum and neodymium was investigated. A large number of samples with bulk compositions RE_xWO₃, prepared by solid-state reaction in the pressure and temperature regions P= 10-80 kbar and T= 1170-1620 K were examined by X-ray powder diffraction and electron microscopy, and a (P-T) diagram showing the phase relations was drawn. Three tungsten-bronze-related phases with perovskite (PTB)-, hexagonal (HTB)- and intergrowth (ITB)-type structures were identified. The PTB bronze RE_xWO₃ with x≈ 0.10 was formed at p≤50 kbar. The HTB-related phase with x≈ 0.10 was observed in samples prepared at P≥20 kbar, whereas phases of (n)-ITB-type were observed only in the 25-50 kbar region. In the latter pressure region, the PTB and ITB phases were only seen in samples prepared at T > 1520 K, while the HTB-related phase was found in almost all samples. The HTB- and ITB-related compounds are metastable, probably fully oxidized, high-pressure phases of composition RE_xWO_3+3x/2 with x≤0.13. They transform to a cubic PTB bronze during annealing in inert atmosphere under ambient pressure conditions. According to microanalysis studies of individual crystals, less than 40% of the hexagonal tunnel sites in the HTB and ITB structures are occupied by RE³⁺ ions. A superstructure of HTB-type with ≈60% occupancy of the hexagonal tunnel sites (x≈0.20) was observed in a few crystals from the samples prepared at P= 80 kbar. Ordered, defect and intergrowth structures are presented.     

Synthetic beta‐K0.33V2O5 Nanorods: A Metal–Insulator Transition in Vanadium Oxide Bronze

We found a linear relationship between the metal–insulator transition (MIT) temperature and the A⁺ ionic radius of the beta‐A_0.33V₂O₅ bronze family, leading our attention to beta‐K_0.33V₂O₅ which has been neglected for a long time. We have introduced a facile hydrothermal method to obtain the single‐crystalline beta‐K_0.33V₂O₅ nanorods. As expected, both the temperature‐dependence of the resistivity and magnetization demonstrated MITs at about 72 K for beta‐K_0.33V₂O₅, thus matching well with the linear relationship described above. The beta‐K_0.33V₂O₅ was assigned as a new member of the beta‐A_0.33V₂O₅ bronze family for their similar crystal and electronic structures and their MIT property; this addition enriches the beta‐A_0.33V₂O₅ bronze family.     

载电条件下铬青铜／纯铜摩擦副摩擦磨损性能研究

考察了纯铜销试样和铬青铜QCr0．5盘试样摩擦副在载电条件下的滑动摩擦磨损性能，并初步探讨了摩擦磨损机制．结果表明，电流对铬青铜／纯铜摩擦副的滑动干摩擦行为具有显著影响，随着电流增加，销试样的磨损率增加，摩擦系数增大，摩擦表面塑性流动和粘着加剧．     

Investigation of patinas formed on Chinese bronzes using modern multianalytical techniques

This paper presents an integrated study on nine natural Chinese bronze patinas without causing any damage to the bronze substrates, employing five modern analytical techniques including X‐ray diffraction (XRD), Fourier transform infrared (FT‐IR) and Raman spectroscopy, inductively coupled plasma atomic emission spectroscopy (ICP‐AES), and inductively coupled plasma mass spectrometry (ICP‐MS). Two artificial Chinese bronze patinas were also investigated by the same techniques for comparative purposes. As a result, XRD determined the chemical compositions of all selected samples and showed that the primary compound was malachite in natural soil environment under the general situation. Meanwhile, some interesting corrosion products such as gerhardtite and free copper were also observed. Three groups were classified according to the XRD results in order to provide a deeper insight into their spectroscopic characterization. Spectroscopic data of these patinas from FT‐IR and Raman spectroscopy are shown and interpreted in detail. ICP‐AES and ICP‐MS analyses provided valuable quantitative information, and made the study of the patinas more profound. Furthermore, all analytical results indicated that bronze patinas are extremely complex by virtue of the storage environment and their substrate alloys. The natural samples were rather heterogeneous and the artificial samples, especially the sample formed in the laboratory, were rather homogeneous of which the chemical constituents could be well defined. Copyright © 2007 John Wiley & Sons, Ltd.     

Electrochemical properties of systems with rubidium-tungsten-oxide bronze

Single-phase rubidium-tungsten-oxide bronze of the composition Rb_0.3WO₃ with hexagonal syngony (a = 0.7387 ± 0.0004 nm, c = 0.7547 ± 0.0004 nm) is synthesized. The ionic constituent of the bronze conductivity, determined for the first time ever, is nearly three orders of magnitude as small as the electronic constituent and varies from 1.1 × 10^?2 to 2.7 × 10^?2 S cm^?1 at 30–84°C. The reversibility of the Rb_0.3WO₃/Rb₆La₂Si₆O₁₈ interface increases with the environment humidity. The exchange current is equal to 6.4 × 10^?4 A cm^?2 at a temperature of 30°C and a relative humidity of 58%. It is shown that the synthesized bronze may, in principle, be utilized in the role of a reference electrode in solid-state potentiometric sensors for carbon dioxide and hydrogen sulfide that would be capable of operating in natural conditions.     

Chemical Processing of Potassium Substituted (Pb0.6Ba0.4)Nb2O6 Powders and Thin Films Through Metallo-Organics

Highly oriented tungsten bronze K_0.4(Pb_0.6Ba_0.4)_0.8Nb₂O₆ ferroelectric thin films have been prepared from metal alkoxides and metal acetate by chemical process. The formation of solid solution with potassium was found to be very effective to form the tungsten bronze phase at lower temperatures compared with (Pb_0.6Ba_0.4)Nb₂O₆. The amount of potassium in the composition of K_x(Pb_0.6Ba_0.4)_{1 – x/2}Nb₂O₆ [0 x 0.4] is also important to crystallize in the tungsten bronze phase. K_0.4(Pb_0.6Ba_0.4)_0.8Nb₂O₆ films with c-axis preferred orientation were successfully synthesized on MgO(1 0 0) and Pt(1 0 0)/MgO(1 0 0) substrates above 700°C. KPBN60 thin film on Pt(1 0 0)/MgO(1 0 0) showed a remnant polarization of 20 C/cm² and a coercive field of 140 kV/cm at –150°C.