Hydration characteristics of monocalcium aluminate at a low water/solid ratio

The hydration characteristics of calcium monoaluminate were studied using an effective water/aluminate ratio of 0.15 at 20° or 80°C, from a few minutes of two months. The material hydrated at 80°C shows a large shrinkage while at the lower temperature a continuous expansion occurs. The product at 80°C shows a much higher strength than that hydrated at 20°C. The main initial hydration products are 2Ca0, Aℓ₂0₃, 8H₂0 and alumina gel. Microcracks are developed in the products hydrated at 20°C while at the higher temperature a very compact mass results. The data indicate that it is possible to obtain a durable high alumina cement by using a low water/cement ratio and hydrating at higher temperatures, and under these conditions C₃AH₃---C₃AH₆ bond is favoured.     

Effect of γ-alumina crystallinity on the state of rhodium during high-temperature treatments in oxygen and hydrogen

Rhodium catalysts, supported on six γ-Al₂O₃ supports with different crystallinities, were exposed to sequential treatments in hydrogen at 500°C, in oxygen at 760°C, in hydrogen at 500°C and at 760°C, respectively. Samples were characterized by X-ray diffraction and hydrogen chemisorption at various stages in the sequential treatment. Based on the characterization results, it is concluded that the formation of crystalline Rh₂O₃ is a function of γ-Al₂O₃ crystallinity; formation of crystalline Rh₂O₃ increased with increasing crystallinity of γ-Al₂O₃ during treatment in oxygen at 760°C. The crystalline Rh₂O₃ formed during treatment in oxygen at 760°C was reduced to Rh metal by hydrogen at 500°C, but most of the Rh did not adsorb hydrogen at room temperature. Subsequent treatment in hydrogen at 760°C increased the hydrogen adsorption capacity by as much as a factor of three. X-ray line broadening measurements showed that oxygen treatment of reduced Rh/γ-Al₂O₃ at 760°C followed by hydrogen reduction at 500°C resulted in significant increases in Rh crystal size; further treatment in hydrogen at 760°C resulted in additional sintering of Rh.     

Raman spectroscopic studies on the sulfation of cerium oxide

In the present study, we have examined sulfation of cerium oxide via impregnation of (NH₄)₂SO₄, followed by heating in the temperature range of 220–720°C, using Raman Spectroscopy. Based on the SO and SO stretching frequencies in the range of 900–1400 cm⁻¹, a wide range of surface oxysulfur species and bulk cerium-oxy-sulfur species are identified. At 220°C, a mixture of (NH₄)₂SO₄ crystals, SO²⁻_4(aq) and HSO¹⁻_r(aq) is found to have formed on ceria's surface, whereas complete conversion of (NH₄)₂SO₄ to SO²⁻_4(aq) and HSO¹⁻_4(aq) occurs at 280°C. At 350°C, formation of a mixture of surface pyrosulfate S₂O²⁻_7(surf.0, consisting of two SO oscillators and a bulk type compound identified as Ce(IV)(SO₄)_x(SO₃)_2−x (0 < x < 2) have been observed. Upon introduction of moisture, the former transforms to HSO¹⁻_4(surf.), whereas the latter remains unchanged. At 400°C, only the bulk type compound can be observed. At 450°C, only Ce₂(SO₄)₃ is generated and remains stable until 650°C. Further increase in the temperature to 720°C results in the formation of CeOSO₄. The present study not only provides a more thorough understanding of the sulfation of cerium oxide at a molecular level, but also demonstrates that Raman spectroscopy is a highly effective technique to characterize sulfation of metal oxides.     

The storage of nitrogen oxides on alumina-supported barium oxide

The storage and release of NO₂ on alumina-supported barium oxide has been studied with particular attention to the stoichiometry of the two processes. At 400 °C the storage process is characterised by a short period of complete uptake, possibly as nitrito or nitro species, followed by a slower partial uptake in which approximately one NO is released for every three NO₂ lost. The latter reaction appears to supply the oxygen necessary to store NO₂ as nitrate ions. Molecular O₂ has little direct involvement even if in large excess. The second storage reaction also occurs, but to a much lesser extent, with Al₂O₃ alone. During temperature programmed desorption, release of NO_x from Al₂O₃ peaks at 430 °C with evolution of NO₂ and some O₂. Release from BaO/Al₂O₃ exhibits an additional peak near 520 °C corresponding to formation of NO and a higher O₂ concentration. The NO may arise from NO₂ since BaO/Al₂O₃ has activity for NO₂ decomposition by 500 °C. Although CO₂ at low concentration is rapidly taken up by BaO/Al₂O₃ at 400 °C it is displaced by NO₂ and does not interfere with storage. Thermodynamic calculations show that the formation of Ba(NO₃)₂ by the reaction of NO₂ with bulk BaCO₃ under the conditions used here is more favourable above 380 °C if NO is evolved than if O₂ is consumed.     

Al18B4O33 aluminium borate: A new efficient support for palladium in the high temperature catalytic combustion of methane

Well crystallised aluminium borate Al₁₈B₄O₃₃ has been synthesised from alumina and boric acid with a BET area of 18 m²/g after calcination at 1100 °C. Afterwards, 2 wt.% Pd/Al₁₈B₄O₃₃ was prepared by conventional impregnation of Pd(NO₃)₂ aqueous solution and calcination in air at 500 °C. The catalytic activity of Pd/Al₁₈B₄O₃₃ in the complete oxidation of methane was measured between 300 and 900 °C and compared with that of Pd/Al₂O₃. Pd/Al₁₈B₄O₃₃ exhibited a much lower activity than Pd/Al₂O₃ when treated in hydrogen at 500 °C or aged in O₂/H₂O (90:10) at 800 °C prior to catalytic testing. Surprisingly, a catalytic reaction run up to 900 °C in the reaction mixture induced a steep increase of the catalytic activity of Pd/Al₁₈B₄O₃₃ which became as active as Pd/Al₂O₃. Moreover, the decrease of the catalytic activity observed around 750 °C for Pd/Al₂O₃ and attributed to PdO decomposition into metallic Pd was significantly shifted to higher temperatures (820 °C) in the case of Pd/Al₁₈B₄O₃₃. The existence of two distinct types of PdO species formed on Al₁₈B₄O₃₃ and being, respectively, responsible for the improvement of the activity at low and high temperature was proposed on the basis of diffuse reflectance spectroscopy and temperature-programmed desorption of O₂.     

Phase diagram of the system: Al2O3–ZrO2

The system Al₂O₃–ZrO₂ was studied by differential thermal analysis in inert atmosphere and in vacuum. The eutectic was located at 1866°C and 40% mass of ZrO₂. Zirconia solid solution at the eutectic temperature is up to 1.1±0.3% mass of Al₂O₃. Enthalpy of melting of this eutectic is 1080±90 J/g. Pure ZrO₂ transforms from monoclinic to tetragonal at 1162±7°C, but the saturated solid solution of ZrO₂, with 0.7±0.2% mass Al₂O₃ at this temperature, transforms at 1085±5°C. Inverse transitions occur with hysteresis correspondingly at 1055±5 and 995±5°C. Enthalpy of transformation of pure ZrO₂ from monoclinic to tetragonal phase is 42±5 J/g (5.2±0.6 J/mol) but only 30±5 J/g for a ZrO₂ saturated solid solution.     

Effect of sintering and poling conditions on the properties of 0·125Pb (Mg1/3Nb2/3)O3−0.875Pb(Zr0·5Ti0·5)O3 ceramics doped with 4PbO. B2O3

The influence of sintering and poling conditions on dielectric properties and microstructures of the system 0·125Pb(Mg_1/3Nb_2/3)O₃−0·875Pb (Zr_0·5Ti_0·5)O₃ was investigated. Specimens were prepared by the conventional mixed-oxide technique. On account of eliminating the pyrochlore phase and lowering the sintering temperature, the calcined 0·125PZT−0·875PMN ceramic was doped with 4PbO.B₂O₃ glass powder. The 4PbO.B₂O₃ glass frit not only has a low flow temperature, but also a high polarizability. Additions of 4PbO.B₂O₃ to the perovskite 0·125PMN–0·875PZT solid solution will form a liquid phase, which served as a densification aid for the ceramics. With additions of 0·2 wt% glass frit, densities in excess of 98% of theoretical were obtained after sintering at 115°C. By variation of the fabrication processes, the influence of sintering and poling conditions on the properties of the ceramics was studied.     

Low-temperature sintering of PZT ceramics

The required sintering temperature of Pb(Zr_0·52Ti_0·48)O₃ ceramics (abbreviated as PZT 52/48) can be lowered to about 1000°C by incorporating Li₂CO₃, Na₂CO₃ or Bi₂O₃. A dielectric constant of about 1000 and a planar coupling factor of between 45% and 65% are obtained in PZT 52/48 ceramics sintered at 1025°C, with added Li₂CO₃ and Bi₂O₃. The optimal amount of the additives, which can be deduced from the densification, the dielectric and piezoelectric properties of the sintered PZT 52/48 ceramics, is 0·375 wt% of Li₂CO₃ together with an equal mole fraction of Bi₂O₃. A planar coupling factor of 65% is obtained. This is explained, with the aid of X-ray diffraction (XRD) analysis, by a maximum c/a ratio and consequently by a large spontaneous polarization. The PZT 52/48 ceramics sintered with Li₂CO₃ and Bi₂O₃ under the optimal conditions can have ε₃₃^T of about 1000, k_p higher than 60%, Q_m around 100 and tan δ less than 2·0%.     

Plasma-Sprayed Aluminum and Titanium Adherends: II. Durability Studies for Wedge Specimens Bonded with Polyimide Adhesive

The durability of plasma-sprayed metals bonded with a polyimide adhesive has been studied. Metal adherend surfaces were prepared for adhesive bonding by plasma-spraying inorganic powders on aluminum and titanium. The plasma-sprayed materials included Al₂O₃, AlPO₄. MgO, and SiO₂ on aluminum, and TiO₂, TiSi₂, MgO, and SiO₂ on titanium. The coatings were sprayed at two different thicknesses. Durability studies of samples prepared in a wedge-type geometry were carried out. Bonded specimens were maintained in an environmental cycle that included exposure to the conditions; low temperature, - 20°C; relative humidity at elevated temperature, 70% RH at 66°C; elevated temperature (160°C) in air, high temperature (160°C) in vacuum (130 torr, 0.2 atm.), and room temperature. Crack growth rate and mode of failure were determined. The results of the durability tests indicate that thin coatings (25 μm) of plasma-sprayed materials perform better than thicker (150 μm) coatings. The crack growth rate for thin coatings (25 μm) of Al₂O₃, AlPO₄, SiO₂, and MgO plasma-sprayed on aluminum was equivalent to that for phosphoric acid anodized aluminum. Similarly, the durability performance for titanium samples prepared with a 25 μm-thick TiO₂, TiSi₂, and SiO₂ plasma-sprayed coatings was equivalent to that for a Turco®-prepared titanium surface. Although the evaluation of durability as a function of surface chemistry was an objective of the study, it was not possible to evaluate the effect, since most failures occurred within the adhesive (cohesive failure) during the environmental tests. That failure occurred in the adhesive indicates that the coating-adherend and the coating-adhesive interactions are sufficiently robust to prevent interfacial failure under the experimental conditions investigated.     

Physicochemical investigation of the decomposition products of ammonium metal carboxylates: ammonium ferric citrate hydrate

The thermal decomposition up to 400 °C of ammonium ferric citrate hydrate, of unknown structure and formula weight, was studied by thermogravimetry, differential thermal analysis, infrared (IR) spectroscopy and X-ray diffractometry. The possible identities of the formula weight and the intermediate products of calcination are discussed. The results revealed that the parent material is amorphous and contains two moles of water and two moles of ammonia. Decomposition takes place via six weight-loss processes, three endothermic (90–230 °C) and three exothermic (240–298 °C), leading eventually to the formation of Fe₂O₃. The intermediate solid products are mainly unstable amorphous oxycarbonates, as indicated by X-ray and IR spectroscopies. The gas-phase decomposition products identified by IR spectroscopy are NH₃, CO₂, CO, CH₃COCH₃, CH₄ and NH₄OH. Surface area measurement and scanning electron microscopy showed that Fe₂O₃, the final product at 400 °C, hada surface area of 40 m²/g and good crystalline and porous character.     

NO reduction by CH4 in the presence of O2 over La2O3 supported on Al2O3

Dispersing La₂O₃ on δ- or γ-Al₂O₃ significantly enhances the rate of NO reduction by CH₄ in 1% O₂, compared to unsupported La₂O₃. Typically, no bend-over in activity occurs between 500° and 700°C, and the rate at 700°C is 60% higher than that with a Co/ZSM-5 catalyst. The final activity was dependent upon the La₂O₃ precursor used, the pretreatment, and the La₂O₃ loading. The most active family of catalysts consisted of La₂O₃ on γ-Al₂O₃ prepared with lanthanum acetate and calcined at 750°C for 10 h. A maximum in rate (mol/s/g) and specific activity (mol/s/m²) occurred between the addition of one and two theoretical monolayers of La₂O₃ on the γ-Al₂O₃ surface. The best catalyst, 40% La₂O₃/γ-Al₂O₃, had a turnover frequency at 700°C of 0.05 s⁻¹, based on NO chemisorption at 25°C, which was 15 times higher than that for Co/ZSM-5. These La₂O₃/Al₂O₃ catalysts exhibited stable activity under high conversion conditions as well as high CH₄ selectivity (CH₄ + NO vs. CH₄ + O₂). The addition of Sr to a 20% La₂O₃/γ-Al₂O₃ sample increased activity, and a maximum rate enhancement of 45% was obtained at a SrO loading of 5%. In contrast, addition of SO⁼₄ to the latter Sr-promoted La₂O₃/Al₂O₃ catalyst decreased activity although sulfate increased the activity of Sr-promoted La₂O₃. Dispersing La₂O₃ on SiO₂ produced catalysts with extremely low specific activities, and rates were even lower than with pure La₂O₃. This is presumably due to water sensitivity and silicate formation. The La₂O₃/Al₂O₃ catalysts are anticipated to show sufficient hydrothermal stability to allow their use in certain high-temperature applications.     

Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.     

Catalytic performance of Co3O4/CeO2 and Co3O4/CeO2–ZrO2 composite oxides for methane combustion: Influence of catalyst pretreatment temperature and oxygen concentration in the reaction mixture

The influence of catalyst pre-treatment temperature (650 and 750 °C) and oxygen concentration (λ = 8 and 1) on the light-off temperature of methane combustion has been investigated over two composite oxides, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ containing 30 wt.% of Co₃O₄. The catalytic materials prepared by the co-precipitation method were calcined at 650 °C for 5 h (fresh samples); a portion of them was further treated at 750 °C for 7 h, in a furnace in static air (aged samples).

Tests of methane combustion were carried out on fresh and aged catalysts at two different WHSV values (12 000 and 60 000 mL g⁻¹ h⁻¹). The catalytic performance of Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ were compared with those of two pure Co₃O₄ oxides, a sample obtained by the precipitation method and a commercial reference. Characterization studies by X-ray diffraction (XRD), BET and temperature-programmed reduction (TPR) show that the catalytic activity is related to the dispersion of crystalline phases, Co₃O₄/CeO₂ and Co₃O₄/CeO₂–ZrO₂ as well as to their reducibility. Particular attention was paid to the thermal stability of the Co₃O₄ phase in the temperature range of 750–800 °C, in both static (in a furnace) and dynamic conditions (continuous flow). The results indicate that the thermal stability of the phase Co₃O₄ heated up to 800 °C depends on the size of the cobalt oxide crystallites (fresh or aged samples) and on the oxygen content (excess λ = 8, stoichiometric λ = 1) in the reaction mixture. A stabilizing effect due to the presence of ceria or ceria–zirconia against Co₃O₄ decomposition into CoO was observed.

Moreover, the role of ceria and ceria–zirconia is to maintain a good combustion activity of the cobalt composite oxides by dispersing the active phase Co₃O₄ and by promoting the reduction at low temperature.     

Ferroelectric Pb5-xBix (Ge.Si)3-xBxO11 single crystals as a material for IR radiation detectors

The coupled substitution of Bi³⁺ for Pb₂₊ and B³⁺ for Ge⁴⁺ was successfully achieved in ferroelectric Pb₅Ge₃O₁₁. Large single crystals of optical quality were grown from the melt. Deterioration of the crystal quality could not be observed within a period of two years under ambient conditions. The dielectric permittivity ε_r, electric conductivity p and pyroelectric coefficient γ are investigated as a function of temperature. The room temperature data (εr = 43, γ = 2.4·10^-4Cm^-2 K^-1, p = 7·10⁷ Ω, volume specific heat s = 2·10⁶ Jm^-3K^-1) show the usefulness of Pb_5-xBi_xGe_3-xB_xO₁₁ around x = 0.1 as a material for pyroelectric thermal detectors operating at room temperature. Also the difficulty of producing lead germanate silicate mixed crystals in the size and quality needed for vidicon applications is overcome by additional replacement of some Pb and Ge by Bi and B.     

Synthesis, densification and electrical properties of strontium cerate ceramics

Powders of pure and 5% ytterbium substituted strontium cerate (SrCeO₃/SrCe_0.95Yb_0.05O_3−δ) were prepared by spray pyrolysis of nitrate salt solutions. The powders were single phase after calcination in nitrogen atmosphere at 1100 °C (SrCeO₃) and 1200 °C (SrCe_0.95Yb_0.05O_3−δ). Dense SrCeO₃ and SrCe_0.95Yb_0.05O_3−δ materials were obtained by sintering at 1350–1400 °C in air. Heat treatment at 850 and 1000 °C, respectively, was necessary prior to sintering to obtain high density. The dense materials had homogenous microstructures with grain size in the range 6–10 μm for SrCeO₃ and 1–2 μm for SrCe_0.95Yb_0.05O_3−δ. The electrical conductivity of SrCe_0.95Yb_0.05O_3−δ was in good agreement with reported data, showing mixed ionic–electronic conduction. The ionic contribution was dominated by protons below 1000 °C and the proton conductivity reached a maximum of 0.005 S/cm above 900 °C. In oxidizing atmosphere the p-type electronic conduction was dominating above 700 °C, while the contribution from n-type electronic conduction only was significant above 1000 °C in reducing atmosphere.     

The hydration of calcium dialuminate and its mixtures containing slag

In a paste CA₂ hydrates very slowly at 20°C but the reaction is more rapid at 40°C. At both temperatures the products of hydration comprise C₂AH₈, gibbsite and alumina gel after 7 days. For mixtures of CA₂ + CA the initial hydration at 20°C is dominated by CA. In the presence of ground granulated blastfurnace slag CA₂ or a mixture of CA₂ + CA will form strätlingite on hydration at 40°C within 3 days. Slag addition reduces the amount of heat evolved during the first 24 hours of hydration at both 20° and 40°C.     

PRECIPITATION IN THE Mg+2-Na+-SO3-2-SO4-2 AQUEOUS SYSTEM

Spontaneous precipitation in the aqueous system Mg₊₂-Na₊-SO₃^-2-SO₄^-2 affected by mixing solutions of MgSO₄ and Na₂SO₃, together was studied for temperature varying from 40 to 80°C and for pH from 5,5 to 9. The initial composition of a precipitating system was 0·67 and 1·17 mol of MgSO₃ and Na₂SO₄ per liter and 0·82 mol of MgSO₃ and Na₂SO₄ together with 0·83 mol of MgSO₄ per liter, respectively. Depending on the prevailing reaction conditions, solid phase consisting of MgSO₃ 6H₂O, MgSO₃ 3H₂O, Mg₂NaOH(SO₃)₂ H₂O or their mixture is formed. Each solid phase forms crystals of typical size and shape. The precipitation diagrams drawn in the temperature and pH coordinates for three different initial composition of the studied system are presented.     

Nucleation and growth of Pd clusters in mordenite

The nucleation and growth of Pd clusters in mordenite were investigated using in situ extended X-ray absorption fine structure (EXAFS) spectroscopy and Fourier transform infrared (FTIR) spectroscopy of absorbed CO. Calcination of [Pd(NH₃)₄]²⁺-exchanged mordenite at 350°C in O₂ results in decomposition of the amine complex and formation of square-planar Pd²⁺ oxo species within the mordenite pores. Reduction of these species at 150°C in H₂ yields Pd clusters with an average nuclearity of 3. On an average two 2.22 Å Pd-O bonds are associated with each Pd₃ cluster; we infer that this interaction serves to anchor the clusters within the pores. After reduction at 150°C, the FTIR spectrum of irreversibly adsorbed CO is indicative of a mixture of Pd⁺, Pd^δ+, and Pd⁰ carbonyl species. Reduction at 350°C produces larger intrazeolitic Pd clusters (average nuclearity of 6) that exhibit only a weak interaction with the mordenite, as evidenced by their facile aggregation in the presence of CO at 30°C. Reduction at 450°C yields large 20 Å Pd clusters that we infer are located on external mordenite surfaces or locally disrupt the intracrystalline structure.     

Removal of Fe(III) ion from aqueous solution by adsorption on raw and treated clinoptilolite samples

Iron (III) adsorption from aqueous solutions onto raw and pretreated clinoptilolite was investigated here. Various parameters for iron removal; initial solution pH, contact time and metal ion concentration were optimized. The equilibrium data were modeled by both the Langmuir and Freundlich adsorption isotherms at optimal conditions. Adsorption capacities of raw samples and those pretreated with Na₂S₂O₈ at 20 °C , 70 °C and with HNO₃ at 20 °C were all similar but samples pretreated with HNO₃ at 70 °C were significantly different; iron (III) removal from samples pretreated with HNO₃ decreased with increasing pretreatment temperature. Tests with Fe⁺³ solutions containing phenol, CsCl or KCl, indicated the continued presence of these ions in zeolite which either promoted or retarded the adsorption of iron. The Fe⁺³ adsorption capacity of clinoptilolite pretreated with HNO₃ at 70 °C was about two times greater with, than without, CsCl and KCl. The kinetics of iron adsorption from aqueous solution were also investigated using the first-order Lagergren equation and a pseudo-second-order model.     

Optical and electro-optical properties of (CH3)4NHgBrI2 crystals

(CH₃)NH_gBrI₂ is an electro-optic material which shows a structural phase transition with a symmetry change from orthorhombic to monoclinic at T = 108°C upon heating. In this contribution we report first experimental data on the optical properties (refractive indices, absorption coefficients), on the elastic and electro-optical properties. It is shown, that the dispersion of the refractive indices is adequately described by a single term Sellmeier oscillator model. Measurements of the temperature dependence of the birefringence and of the elastic constants show pronounced changes at the structural phase transition. The biaxial crystal with the three main indices n_a = 1.761±0.001, n_b = 1.802±0.001 and n_c = 1.755±0.001 at room temperature and a wavelength λ=633nm becomes optically uniaxial at T = (50±0.5)°C with n_a=n_c=1.750, due to different temperature dependences n_a(T) and n_b(T). Room temperature electro-optic coefficients and the corresponding half-wave voltages have been determined, and indicate that the electro-optic activity of (CH₃)₄NH_gBrI₂ is about two orders of magnitude smaller than in KH₂PO₄.