Sol-Gel Preparation of Selective Emitters for Thermophotovoltaic Conversion

Selective emitters are materials characterized by a high temperature emissivity significantly changing in different spectral regions. One of the crucial steps for the development of Thermophotovoltaic (TPV) generators is given by an optimal matching of the spectral emissivity of an IR radiation source with the spectral region where is maximum the efficiency of photovoltaic cells. The emitters should retain good structural properties at the working temperature above 1300°C and they can be either an external coating for the a burner or, as a structural material, a burner and emitter at once.In this work, oxide glass and ceramics containing rare earths have been prepared and characterized as selective emitters candidates. Different approaches and materials have been attempted all based on a colloidal route. Rare earths oxides (erbium and holmium) have been incorporated in transparent silica glass and in polycrystalline alumina and zirconia using their hydrated salts as oxide precursors. Rare earth modified silica glass were obtained by sintering silica xerogel containing fumed silica and hydrolysed ortholisicate. Rare earth modified alumina and mixed alumina-zirconia ceramics were obtained from slurries containing alumina colloidal particles and milled ceramic fibres. Functional properties i.e. the high temperature spectral emissivities have been measured by means of a specially designed apparatus where the working conditions of the selective emitters can be reproduced and monitored.     

Growth Orientation of the Mechanosynthesized Fluorapatite-Based Composite Nanopowders: Influence of Subsequent Thermal Treatment

Growth orientation of fluorapatite–zirconia nanopowders was investigated after mechanical activation and thermal annealing process in the range of 600–1,300 °C for 1 h. Results revealed that during heating of the composite nanopowders the transition of the monoclinic zirconia to tetragonal form and its stabilization by calcium fluoride originating from the decomposition of fluorapatite as well as the formation of a solid solution of calcium fluoride in zirconia occurred. The influence of annealing on the growth orientation of fluorapatite–zirconia composite nanopowders indicated that the crystal growth of fluorapatite was preferentially accentuated on the (002) face in the direction of the crystallographic c-axis after heat treatment. Based on FE–SEM observations, the experimental outcome was composed of both agglomerates and fine particles (~33 nm) after 600 °C, while annealing of the sample at 1,300 °C demonstrated the occurrence of abnormal grain growth.     

Thermal Stability of Sol-Gel Derived 6 Mole%CaO-ZrO2 Ceramics

The thermal behavior of the hyperfine interaction at Zr sites on two sol-gel derived 6 mole% CaO-ZrO₂ powders, obtained from the particulate and non-particulate regimes, has been studied by Perturbed Angular Correlations and complementary techniques. The aim was to get experimental support on the thermal stability of the obtained material in order to see the advantages of the different preparation regimes. The results could be interpreted in terms of the different microstructures and nanoscopic configurations exhibited by the resulting powders. After crystallization both powders showed the hyperfine nanoconfigurations of metastable tetragonal zirconia. In the sample obtained following the hydrolysis and the condensation processes via a particulate regime, the undesirable phase transformation towards the monoclinic form of zirconia is inhibited up to higher temperatures.     

Aspects of the pyrometric measurement of graphite furnace temperature

Experimental results are presented to show that the radiation leaving the centre hole of tubular graphite furnace atomisers can deviate significantly from ideal blackbody behaviour. Pyrometric measurements at various wavelengths of the apparent, or brightness, temperatures of two commercial graphite tube atomisers (Varian GTA-95 and CRA-90) showed that the measured brightness temperature decreased appreciably with increasing wavelength, in accordance with the predicted behaviour for a cavity radiator with an emissivity less than unity. Measurement of the sample hole emissivity from the apparent melting temperatures of certain metal and metal carbide samples indicated mean effective hole emissivities of pyrocoated GTA-95 tubes in the range 0.76–0.92, depending on temperature and wavelength. Implications of the results for pyrometric temperature measurement in graphite furnaces are also discussed.     

耐高温高比表面氧化铬/氧化锆体系的制备和表征

采用浸渍法和共沉淀法制备了CrOx/ZrO2样品.制备过程中所得沉淀都经100 ℃碱液回流老化24 h.通过X射线衍射、X射线光电子能谱、氮吸附、差热-热重分析等手段对样品进行了表征.结果证实,碱液回流过程中会有SiO2从所用的玻璃器皿进入样品， SiO2的表面修饰作用提高了载体的热稳定性.氧化铬的引入进一步提高了所得样品的比表面和热稳定性.与浸渍法相比，共沉淀法制备的样品具有更好的性能.其中铬锆摩尔比为0.15时，用NaOH作沉淀剂， pH值为13的条件下制备的样品在1000 ℃焙烧后比表面仍达到121 m2•g－1.     

Synthesis and characterization of TENORM-free nano zirconia from zircon sand

To avoid radiation exposure in the use of nano zirconia in the ceramics and dentistry industries, a Technologically Enhanced Natural Radioactive Materials (TENORM)-free nano zirconia was required. The purpose of this research was to obtain an environmentally friendly TENORM-free nano zirconia prototype. TENORM-free nano zirconia synthesis consists of processing zircon sand into sodium zirconate, leaching of sodium zirconate to form zirconyl chloride solution, separation of impurities (silica, ThO₂, U₃O₈, etc.), crystallization of zirconyl chloride, zirconyl-oxalate sol-gel formation, and calcination. The quality test of nano zirconia products was characterized by XRD, FT-IR, SEM, and Surveymeter, while the composition test was carried out by the XRF method. The results of this research obtained an environmentally friendly TENORM-free nano zirconia prototype, that has the chemical compound of ZrO₂, the crystal size was 15.09 nm, the average particle size was 91.33 nm, free of radiation exposure, and its composition includes ZrO₂: 96.599%, HfO₂: 2.899%, and CaO: 0.303%. This synthesis can process zircon sand containing TENORM (ThO₂: 0.070% and U₃O₈: 0.047%) into TENORM-free nano zirconia and increase the added value by increasing the zirconia content from 40.493% to 96.599%.     

Energy transfer caused by reactions in a graphite tube atomizer

A spectrometer with a charge coupled device detector is employed to measure the temperature inside a graphite furnace using the wavelength distribution of the radiation continuum. For steady-state heating and blank firings, the results are good approximations to those expected from the black body theory. The calculated temperatures from 1900 to 2700 K, can be affected by the emissivity of the tube wall and radiating area by ±60 K. The vaporization of microgram quantities of Mg, Be, Pd and Cu as nitrates is accompanied by transient light scattering and an emission continuum. The effect occurs for Cu in both Ta-lined and pyrocoated tubes, and for Mg, Be and Pd only in the pyrocoated tube. Wavelength distribution of the transient radiation is also characteristic of a black body radiator, but with temperature increase of 400–600 K in comparison with that of the tube wall. The emission originates from the clouds of condensed particles formed almost simultaneously with the vaporization of the sample. The effect is accompanied by increased vaporization rate and appearance of some particularities in the vapor spectra. The concept of isothermal atomization fails to explain both phenomena. Hence, the hypothesis is advanced concerning the evolution of chemical energy during sample interaction with the tube material. Energy transfer and dissipation in the vicinity of the sample control both mass output and kinetic energy of the released atoms. The exothermic process of nucleation and aerosol formation causes release of energy through radiation. It is suggested that such phenomena can occur in the tube furnace during trace element determination in the presence of microgram quantities of matrix and chemical modifiers.     

Thermal expansion of irradiated polyethylene from 10 to 340 K

The coefficient of thermal expansion of γ-irradiated polyethylene has been measured from 10 to 340 K by using the three-terminal capacitance technique. The samples are irradiated to 500 Mrad in steps of 100 Mrad in air at room temperature with γ-rays from a Co⁶⁰ source at a dose rate of 0.3 Mrad/h. The crystallinity of the sample is measured by x-ray diffraction. The crystallinity is found to decrease with radiation dose. The thermal expansion coefficient is found to be constant with radiation doses from 10 to 110 K and decreases with doses from 110 to 340 K. © Wiley & Sons, Inc.     

Investigations of microstructural changes and spectral characteristics of tantala stabilized zirconia refractories

Several samples of zirconia doped tantala have been prepared and well sintered. Measurements of X-ray diffraction, infrared absorption spectra and bulk density were carried out before and after an absorbed energetic gamma radiation dose (5·26 × 10⁶ rd.). Results obtained were consistent and explained on the basis of the interactions of tantala dopant (at high temperature) and energetic gamma radiation with zirconia and stabilized zirconia lattices.     

Generation of WO3-ZrO2 catalysts from solid solutions of tungsten in zirconia

WO₃-ZrO₂ samples were obtained by precipitating zirconium oxynitrate in presence of WO₄ species in solution from ammonium metatungstate at pH=10.0. Samples were characterized by atomic absorption spectroscopy, thermal analysis, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, high-resolution transmission electron microscopy and energy filtered-TEM. The ammonia retained in the dried sample produced a reductive atmosphere to generate W⁵⁺ ions coexisting with W⁶⁺ ions to produce a solid solution of tungsten in the zirconia lattice to stabilize the zirconia tetragonal phase when the sample was annealed at 560 °C. When the sample was annealed at 800 °C, the W atoms near crystallite surface were oxidized to W⁶⁺, producing patches of WO₃ on the zirconia crystallite. The HR-TEM analysis confirmed the existence of the solid solution when the sample was annealed at 560 °C, and two types of crystalline regions were identified: One with nearly spherical morphology, an average diameter of 8 nm and the atomic distribution of tetragonal zirconia. The second one had a non-spherical morphology with well-faceted faces and dimensions larger than 30 nm, and the atom distribution of tetragonal zirconia. When samples were annealed at 800 °C two different zirconia crystallites were formed: Those where only part of the dissolved tungsten atoms segregated to crystallite surface producing patches of nanocrystalline WO₃ on the crystallite surface of tetragonal zirconia stabilized with tungsten. The second type corresponded to monoclinic zirconia crystallites with patches of nanocrystalline WO₃ on their surface. The tungsten segregation gave rise to the WO₃-ZrO₂ catalysts.     

Thermal Behaviour of a TiO2—ZrO2 Microcomposite Prepared by Chemical Coating

A microcomposite powder in the system TiO₂—ZrO₂ as a precursor of zirconium titanate (ZT) materials has been studied by thermal methods (DTA-TG) and X-ray diffraction (XRD). The microcomposite powder has been prepared by chemical processing of crystalline TiO₂ (rutile, 10 mass% anatase),as inner core, coated with in situ precipitated amorphous hydrated zirconia gel, asouter core. The morphology and chemical composition of the resultant powders has been examined by SEM-EDX (Scanning electron microscopy-energy dispersive X-ray spectroscopy). Thermal behaviour of the microcomposite powder was reported, showing the dehydration and dehydroxylation of the zirconia gel, the crystallization into metastable cubic/tetragonal zirconia at temperatures 400—470°C, and the feasibility of preparing ZT powder materials by progressive reaction of TiO₂ and ZrO₂ at higher temperatures (1400°C).This revised version was published online in November 2005 with corrections to the Cover Date.     

Estimation of oxygen ionic conductivity in nickel-zirconia composite by oxygen permeation method

The oxygen transport in the nickel-zirconia composite was investigated using the oxygen permeation method. A disk-shaped sample made of nickel (40 vol%) and yttria-stabilized zirconia (YSZ) was used to construct a permeation cell. By exposing one side of the sample to a CO₂ gas stream and the other side to a CO stream at elevated temperatures, oxide ions were extracted from CO₂ and transported to the other side to oxidize CO. The oxygen permeation flux through the composite was determined by analyzing the effluent from the permeation cell, and the oxygen ionic conductivity of the composite was derived from the permeation data and the oxygen partial pressures. It was shown that the oxygen ionic conductivity of the composite YSZ fraction was about one third of that for the single-phase zirconia ceramic, and the activation energy associated with the transport of oxide ions in the composite is somewhat greater than that of the single-phase zirconia.     

Synthesis of nanostructured titania/zirconia membrane and investigation of its physical separation and photocatalytic properties in treatment of textile industries wastewater

Nanostructured TiO₂/ZrO₂ composite membranes with varying compositions were obtained by sol–gel technique. The influence of 0–30 mol% zirconia doping on microstructure, water permeability, photocatalytic and physical separation properties, removal of methyl violet of textile industries wastewater and thermal and mechanical stability of titania/zirconia composite membranes was described. Firstly, alumina supports were coated with TiO₂ intermediate layers using the colloidal sol–gel route. The TiO₂/ZrO₂ composite sols were prepared via a polymeric sol–gel method and dip-coated on TiO₂ intermediate layer. The samples were characterized by DLS, TG-DTA, XRD, FTIR, BET-BJH, UV–visible, SEM, TEM and AFM. It was shown that zirconia retards the phase transformation of anatase to rutile until at least 700 °C. The minimum pore size and maximum surface area obtained were 1.2 nm and 153 m²/g, respectively, attributed to the sample with 20 mol% zirconia. The mechanical strength of titania membranes was significantly improved by addition of zirconia. The most methyl violet removal efficiency obtained, with and without UV-irradiation, is 80.8 and 72.6%, respectively, attributed to the sample with 20 mol% zirconia.     

Reflective and transparent cellulose-based passive radiative coolers

Radiative cooling passively removes heat from objects via emission of thermal radiation to cold space. Suitable radiative cooling materials absorb infrared light while they avoid solar heating by either reflecting or transmitting solar radiation, depending on the application. Here, we demonstrate a reflective radiative cooler and a transparent radiative cooler solely based on cellulose derivatives manufactured via electrospinning and casting, respectively. By modifying the microstructure of cellulose materials, we control the solar light interaction from highly reflective (>?90%, porous structure) to highly transparent (≈ 90%, homogenous structure). Both cellulose materials show high thermal emissivity and minimal solar absorption, making them suitable for daytime radiative cooling. Used as coatings on silicon samples exposed to sun light at daytime, the reflective and transparent cellulose coolers could passively reduce sample temperatures by up to 15 °C and 5 °C, respectively.

     

Self‐assembly of Carbon Particles as a Heat Sink Coating to Promote Radiative Cooling

Novel composite carbon particles are developed that can self‐assemble as a coating on a substrate without a binder. These carbon particles were used as a coating to enhance thermal dissipation and their thermal conductivity, surface emissivity and cooling performance were measured. Carbon particles with both thiol and epoxy functional groups self‐assembled to form a coating on the surface of a heat sink without a binder, which greatly improved the thermal conductivity of the coating. Coating a heat sink with the carbon particles yielded a higher thermal conductivity and emissivity than could be obtained with the addition of binder in the conventional approach, and significantly enhanced the cooling performance. In addition, the cooling performance of the carbon nanotube outperformed all other particles when coated on a substrate, because it had the highest thermal conductivity and good radiation emissivity. We developed an equation to describe the various parameters affecting the cooling performance of the thermally dissipative coating. This equation was confirmed by the experimental data.     

Thermal design and simulation of space-borne membrane antenna

Thermal deformation of space-borne radar antenna caused by dramatic changes in orbit thermal environment has a serious effect on image qualities. In this paper, the NX TMG module was used to simulate the orbit thermal environment of the antenna, and a thermal control design was proposed. The thermal control structure consists of three layers; the top is a radiator with high emissivity surface, the middle is a multi-layer insulation, and the bottom is a highly reflective layer. The simulation results show that the thermal design could reduce the temperature gradient from 238.1 to 31.4 °C effectively.

     

Thermal Plasma Synthesis of Zirconia Powder and Preparation of Premixed Ca-Doped Zirconia

A novel study about the synthesis of zirconia and calcia-stabilized zirconia powders were carried out by DC thermal plasma starting from cheap precursors as the carbonates. Different operational parameters were investigated to explore the effects of the process conditions, such as the plasma torch power and the gas flow rate on the composition and the morphology of the powders. The products phase changes from a metastable tetragonal to monoclinic/tetragonal mixture. Basically a main tetragonal phase was obtained at low torch power (7 kW) while the amount of monoclinic phase linearly rises with the power, up to 66 wt% at 26 kW of plasma power and high gas flow rate. The gas flow rate also affects the shape and the size of the powder, where high values reduce powder aggregation and enhance the spherical shape. The best results were achieved at 22 kW of plasma power and high gas flow rate, with powders of roundness about 79% and a wide particle size distribution. Adding the calcium carbonate to the zirconium carbonate (corresponding to 8 wt% CaO in the final mixture), the plasma treatment mainly produces a tetragonal phase zirconia, that at 1400 °C in furnace changes in a stable cubic phase. These powders could be made suitable for further industrial applications after proper treatments.

     

Detection of foreign phases in doped a-alumina powders by thermoluminescence

The thermoluminescence (TL) after excitation by UV or X-rays radiation of doped a-alumina powders is investigated. In the case of zirconia, the alumina-zirconia composites present five of the characteristic peaks of zirconia at -170, -145, -90, 0 and 95°C. After a thermal treatment of mixed oxides, a new peak is observed at -35°C in TL. This peak reveals the presence of stabilized tetragonal zirconia in the material. In the case of calcium, the TL curves of a-alumina doped by calcium present a double peak around 110 and 130°C which can be attributed to the presence of the hibonite phase: CaAl₁₂O₁₉. Moreover, in the case of zirconia, by comparing this analysis with those realised by X-rays diffraction (XRD), it can be shown that the TL has one better limit of detection than the XRD. This revised version was published online in July 2006 with corrections to the Cover Date.     

Combustion synthesis and properties of nanocrystalline zirconium oxide

Nanocrystalline tetragonal zirconia powders have been synthesized by aqueous combustion using glycine (Gly) as a fuel and zirconyl nitrate (ZN) as an oxidizer. The effect of the fuel-to-oxidant molar ratio on the structural and morphological properties of nanocrystalline zirconia powders was studied. Thermodynamic modeling of the combustion reaction showed that the increase in the Gly:ZN molar ratio leads to the increase in theoretical combustion temperature, heat of combustion and amount of produced gases. Powder properties were correlated with the nature of combustion and results of thermodynamic modelling. The increase in the Gly:ZN molar ratio produces more agglomerated powders characterized by a lower degree of uniformity, a lower specific surface area and a slightly bigger crystallite size. On the other hand, the presence of hard agglomerates suppresses the volume expansion, stabilizing tetragonal zirconia, as confirmed by Rietveld refinement. The absence of cubic zirconia was confirmed by FTIR and Raman Spectroscopy. The increase in the calcination temperature led to more agglomerated, compact and less uniform powders. The nanocrystalline nature of zirconia is the reason for the formation of bigger crystallites, the increase in the relative amount of monoclinic phase and sample sintering after calcination at high temperature. The highest measured specific surface area of zirconia was 45.8 m²·g⁻¹, obtained using a fuel-lean precursor.     

Thermal Decomposition and Crystallization of Aqueous Sol-Gel Derived Zirconium Acetate Gels: Effects of the Additive Anions

Zirconia powders were prepared by forming gels by desiccation of aqueous precursor solutions of zirconium acetate containing nitric or sulfuric acid at pH 2.4 and 1.4 and pyrolyzing the gels to temperatures up to 825°C. The structure development in the gels and solid pyrolysis products was investigated. The crystalline zirconia structures produced monoclinic (m), metastable cubic (c) and tetragonal (t) polymorphs. The structure transition temperatures were strongly dependent on the pH, the anions and the stoichiometry of the zirconium complex in the precursor solution. The monoclinic polymorph fraction in the zirconia formed by pyrolyzing the gel formed from the precursor solution containing sulfuric acid at pH 2.4 to 750°C approaches zero while this ratio in the zirconia formed by pyrolyzing the gel formed from the precursor solution containing nitric acid at pH 1.4 to 825°C is 0.7.