Low-temperature synthesis of cements from rice hull ash

Rice hull is an agricultural by-product containing about 20% of silica. Usually, this material is burned at the rice fields generating small silica particles, which may cause respiratory and environmental damage. This work describes the use of rice hull ash as a raw material to prepare Ca₂SiO₄-related cements, which is a component of commercial Portland cement. Rice hull was heated at 600 °C rendering silica with a surface area of 21 m² g⁻¹. This material was mixed with CaO and BaCl₂·2H₂O in several proportions, added stoichiometricaly in order to keep a ratio (Ca+Ba)/Si=2. The solids were mixed with water 1:20 (w/w) and sonicated for 60 min. The suspensions were dried and heated at several temperatures (from 500 to 1100 °C). The resulting solids were analyzed by FT-IR spectroscopy and X-ray diffraction. Cements with structure similar to that of β-Ca₂SiO₄ were obtained at temperatures as low as 700 °C, according to the composition.     

Room temperature transesterification of soybean oil to biodiesel catalyzed by rod-like CaxSiOx + 2 solid base

Rod-like Ca_xSiO_x + 2 catalysts were synthesized by using one-pot hydrothermal method. Catalysts calcined at 550 °C were used in the transesterification reaction of soybean oil with methanol. Under methanol reflux condition, FAME yields of 82% and 95% were achieved on Ca₄SiO₆ in a reaction time of 1 and 2 h, separately. Also, the FAME yields on different Ca_xSiO_x + 2 catalysts were correlated with their basic properties. Besides, a FAME yield of ca. 80% can be achieved under room temperature over Ca₄SiO₆ catalyst.     

Structural investigation relating to the cementitious activity of bauxite residue — Red mud

The cementitious behavior of red mud derived from Bauxite-Calcination method was investigated in this research. Red mud were calcined in the interval 400–900 °C to enhance their pozzolanic activity and then characterized in depth through XRD, FTIR and ²⁹Si MAS-NMR techniques with the aim to correlate phase transitions and structural features with the cementitious activity. The cementitious activity of calcined red mud was evaluated through testing the compressive strength of blended cement mortars. The results indicate that red mud calcined at 600 °C has good cementitious activity due to the formation of poorly-crystallized Ca₂SiO₄. The poorly-crystallized Ca₂SiO₄ is a metastable phase which will transform into highly-crystallized Ca₂SiO₄ with the increase of calcination temperature from 700 °C moving to 900 °C. It is the metastable phase that mainly contributes to the good cementitious activity of red mud. This paper points out another promising direction for the proper utilization of red mud.     

Cationic substitution in tricalcium aluminate

Cubic and orthorhombic crystals of tricalcium aluminate doped with Na₂O, Fe₂O₃ and SiO₂ were prepared and examined using an electron probe microanalyzer. The cationic ratios based on six oxygen atoms were derived from the oxide compositions. These data, together with those in previous studies for clinker aluminates containing Mg²⁺ and K⁺, provided excellent correlations between Al+Fe and Si (Al+Fe=2.001−1.03Si) and Ca+Mg and Na+K+Si [Ca+Mg=3.006−0.51(Na+K+Si)]. The chemical variation that is constrained by these equations is well accounted for by the general formula (Na,K)_2x(Ca,Mg)_3−x−y[(Al,Fe)_1−ySi_y]₂O₆, where x is the amount of Ca substituted by Na and K (0≤x<0.158), and y is the amount of Al substituted by Si (0≤y<0.136). The crystal system changed from cubic to orthorhombic with increasing x value. The substitution of Si and Fe for Al extended the solid solution range of the orthorhombic phase to lower values of x, while its effect on the solid solution range of the cubic phase was reversed.     

The effect of SiO2 additions on barium aluminate cement formation and properties

Barium aluminate cements have been synthesized by barium carbonate, alumina, kaolin and colloidal silica as starting materials. The effects of the source of SiO₂ and of firing temperature on phase formation and physical properties of the fired cements have been studied. Cement samples were characterized using XRD, SEM, EDX. The setting time and heat of hydration of cements were also evaluated. The barium aluminate cements were mixed in castables. Cold crushing strengths evaluated, and values compared to those obtained using calcium aluminate cement (Secar 71). Mixtures of BaCO₃ and Al₂O₃ were targeted to produce BaAl₂O₄; which had fast set time, expansive behavior and lower strength compared to samples with SiO₂ additions. SiO₂ additions, regardless of source, resulted in BaAl₂Si₂O₈ (celsian) formation. The prepared samples had short setting times and higher mechanical properties in comparison with standard calcium aluminate cement.     

Influence of SiO2 modification on hydrogarnets formation during hydrothermal synthesis

Formation and stability of hydrogarnet and Al-substituted tobermorite were examined at 175 °C temperature in saturated steam environment processing CaO-quartz and CaO-amorphous SiO₂ suspensions. A large quantity of Al₂O₃ was added to the starting mixtures [molar ratio A/(S+A)=0.10, duration of hydrothermal synthesis—from 0 to 24 h]. It was determined that hydrogarnets always tend to form more rapidly than 1.13 nm tobermorite. However, later, with extension of synthesis duration, they start to fracture and their quantity reduces almost in half during 24 h. CaO is present in the further reaction with SiO₂ forming hydrated calcium silicates, and released Al³⁺ ions are inserted into Al-substituted tobermorite crystal lattice. Using amorphous SiO₂·nH₂O as SiO₂ component, starting raw materials react considerably quicker—the total Ca(OH)₂ is joined already while increasing the temperature up to 175 °C. Meanwhile, in the mixtures with quartz when their composition is described by the molar ratio C/(S+A)=1.0, traces of Ca(OH)₂ are found even after 24-h isothermal treatment at 175 °C temperature. Moreover, it depends on SiO₂ modification the hydrogarnets of what type are to be formed. Si-free hydrogrossular forms in the mixtures with quartz and katoite in the mixtures with SiO₂·nH₂O. Si⁴⁺ ions are inserted into the crystal lattice of the latter compound while the first one remains undisturbed. This is presumably related to the lower solubility of the quartz. It was also noticed that an isomorphic Si⁴⁺ ions substitution with Al³⁺ ions in the hydrated calcium silicate lattice is considerably quicker when an amorphous SiO₂ is used as SiO₂ component instead of quartz.     

Synthesis and characterization of manganese oxide-doped dicalcium silicates obtained from rice hull ash

This work describes the synthesis and hydration behavior of dicalcium silicates doped with manganese. The syntheses were performed using silica obtained from rice hull ash. The solids (SiO₂, CaO and MnO) were weighed in stoichiometric proportions to prepare silicates having a ratio (Ca + Mn)/Si = 2. Insertion of manganese varied from 1 to 10% (mol). Solids were grounded and water was added rendering aqueous suspensions. The suspensions were sonicated for 60 min in an ultrasonic bath. After drying, the resulting solids were grounded and burned at 800 °C. The preparation of calcium silicates containing up to 10% of manganese oxide was observed.Hydration degree of a dicalcium silicate and calcium silicate containing 5% of manganese was determined by thermal analysis. Both materials present similar behavior. Hydration degree reaches approximately 70% after 60 days.     

Effect of the Ratio of Precipitated SiO2 to Binder SiO2 on Iron-based Catalysts for Fischer–Tropsch Synthesis

The effects of the ratio of precipitated SiO₂ to binder SiO₂ (Si(P)/Si(B)) on the reduction, carburization and catalytic behavior of precipitated Fe–Cu–K–SiO₂ catalysts for Fischer–Tropsch synthesis (FTS) were investigated by N₂ physisorption, temperature-programmed reduction/desorption (TPR/TPD) and Mössbauer effect spectroscopy (MES). FTS performances of the catalysts were tested in a continuous stirred tank reactor (CSTR). It is found that the increase of Si(P)/Si(B) ratio (Si(P)/Si(B) = 0/25 ～ 15/10) decreases the crystallite size of the catalysts, improves the surface basicity, enhances the reduction and carburization of the catalysts, and increases the activity of the catalyst. However, when Si(P)/Si(B) ratio is further increased (Si(P)/Si(B) = 25/0), the catalyst exhibits a restrained reduction and carburization behavior, which may be attributed to the stronger metal–support interaction. Based on the present work, a catalyst with a suitable ratio of Si(P)/Si(B), for example Si(15)/Si(10) displays an optimal FTS performances.     

Microwave dielectric properties of SnO2-doped CaSiO3 ceramics

SnO₂-doped CaSiO₃ ceramics were successfully synthesized by a solid-state method. Effects of different SnO₂ additions on the sintering behavior, microstructure and dielectric properties of Ca(Sn_1−xSi_x)O₃ (x=0.5–1.0) ceramics have been investigated. SnO₂ improved the densification process and expanded the sintering temperature range effectively. Moreover, Sn⁴⁺ substituting for Si⁴⁺ sites leads to the emergence of Ca₃SnSi₂O₉ phase, which has a positive effect on the dielectric properties of CaO–SiO₂–SnO₂ materials, especially the Qf value. The Ca(Sn_0.1Si_0.9)O₃ ceramics sintered at 1375 °C possessed good microwave dielectric properties: ε_r =7.92, Qf =58,000 GHz and τ_f=−42 ppm/°C. The Ca(Sn_0.4Si_0.6)O₃ ceramics sintered at 1450 °C also exhibited good microwave dielectric properties of ε_r=9.27, Qf=63,000 GHz, and τ_f=−52 ppm/°C. Thus, they are promising candidate materials for millimeter-wave devices.     

Thermal treatment of C-S-H gel at 1 bar H2O pressure up to 200 °C

Homogeneous CaO-SiO₂-H₂O gels were prepared at Ca/Si molar ratios 0.83, 1.01, 1.21, 1.50, 1.83 and 2.02. These were aged for 12-24 months at 25 °C and subsequently treated in steam, 1 bar total pressure, at 130 or 200 °C; also in water at 55 and 85 °C. Gels with low Ca/Si ratios partially crystallised at 85 °C. At 130 °C in steam, crystalline products included 11 and 14 Å tobermorite, xonotlite, afwillite, portlandite and another incompletely characterised phase. At 200 °C, the gels retained much water but remained amorphous to X-ray powder diffraction (XRD). However, electron microscopy, coupled with diffraction and analysis, disclosed that the “amorphous” product obtained at 85-200 °C had undergone crystallisation with domains typically 10-1000 nm. At higher bulk Ca/Si ratios, 1.83 and 2.02, much nanoscale precipitation of Ca(OH)₂ occurs, probably by exsolution, such that the residual C-S-H product has a Ca/Si ratio in the range 1.4-1.5. The complex thermal history of the products is reflected in their pH conditioning ability, measured at 25 °C. The results are applied to predict the evolution of pH in a cement-conditioned nuclear waste repository which experiences a prolonged thermal excursion.     

Influence of A-site Ba substitution on microwave dielectric properties of (BaxMg1−x)(A0.05Ti0.95)O3 (A=Zr,Sn) ceramics

The microwave dielectric properties of (Ba_xMg_1−x)(A_0.05Ti_0.95)TiO₃ (A=Zr, Sn) ceramics were investigated with regard to substitution of Ba for Mg of A-site. The microwave dielectric properties were correlated with the Ba content. With an increase in Ba content from 0.01 to 0.1, the dielectric constant and the τ_f value increased, but the Q×f value decreased. The sintered (Ba_xMg_1−x)(Zr_0.05Ti_0.95)TiO₃ (called B_xMZT) ceramics had a permittivity in the range of 19.1−20.6, quality factor from 180,000 to 25,000 GHz, and variation in temperature coefficient of resonant frequency from −35 to −39 ppm/°C with increasing composition x. For sintered (Ba_xMg_1−x)(Sn_0.05Ti_0.95)TiO₃ (called B_xMST) ceramics, the dielectric constant increased from 19 to 20.5, Q×f value increased from 120,000 to 37,000 (GHz), and the τ_f value increased from −50 to −3.3 ppm/°C as the x increased from 0.01 to 0.1. When A=Sn and x=0.1, (Ba_0.1Mg_0.9)(Sn_0.05Ti_0.95)TiO₃ ceramics exhibited dielectric constant of 20.5, Q×f value of 37,000 (GHz), and a near-zero τ_f value of −3.3 ppm/°C sintered at 1210 °C for 4 h.     

Experimental determination of phase equilibria in the CaO-BaO-SiO2-12 mol pct. Al2O3-13 mol pct. MgO system at 1573 K and 1623 K

Phase equilibria of the CaO-BaO-SiO₂-12mol pct. Al₂O₃-13mol pct. MgO system with a wide substitution range of CaO with BaO have been experimentally determined at 1623 K (1350°C) and 1573 K (1300°C) using high-temperature equilibration followed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron probe microanalysis (EPMA) analysis. The (Ca,Ba)₃MgSi₂O₈, BaAl₂O₄, BaAl₂Si₂O₈ and Ca₂(Al_0.46Mg_0.54)(Al_0.46Si_1.54)O₇ phases have been designated within the phase diagram. The liquidus temperature initially decreased and then increased for the samples substituting CaO with BaO at a constant (C + B)/S ratio between 1.50 and 1.86. For samples with a constant BaO/CaO ratio, the liquidus temperature showed similar trends with a lower (C + B)/S ratio from 1.22 to 0.67. The volume fraction of crystal phases of the samples as-quenched from 1573 K (1300°C) correlated well with the variation of liquidus and the primary phases. In addition, the change in the Gibbs free energy of the reactions and the bond parameter (X_p × Z/R_k) of the cations were analyzed, where the maximum change in the Gibbs free energy was found for the formation of Ca₃MgSi₂O₈; furthermore, the stronger basic tendency of Ba²⁺ than Ca²⁺ facilitates Ba²⁺ substitution for Ca²⁺ and bonding with acidic tendency cations to form Ba-containing phases.     

Structural and hydration properties of amorphous tricalcium silicate

Mechanical milling was carried out to synthesize amorphous tricalcium silicate (Ca₃SiO₅) sample, where Ca₃SiO₅ is the most principal component of Portland cement. The partial phase transformation from the crystalline to the amorphous state was observed by X-ray and neutron diffractions. Moreover, it was found that the structural distortion on the Ca-O correlation exists in the milled Ca₃SiO₅. The hydration of the milled Ca₃SiO₅ with D₂O proceeds as follows: the formation of hydration products such as Ca(OD)₂ rapidly occurs in the early hydration stage, and then proceeds slowly after about 15 h. The induction time for the hydration of the milled Ca₃SiO₅ is approximately one half shorter than that for the hydration of the unmilled one. This result means that the mechanical milling brings about the chemical activity of Ca₃SiO₅ for hydration, and may be particularly useful for increasing the reactivity in the early hydration stage.     

Heavy metals in cement phases: on the solubility of Mg, Cd, Pb and Ba in Ca3Al2O6

The compounds formed when the divalent cations Mg²⁺, Cd²⁺, Ba²⁺ and Pb²⁺ are present during the preparation of Ca₃Al₂O₆ have been studied using X-ray microanalysis and diffraction methods. The smaller Mg cations are found to partially substitute for Ca²⁺, and structural refinements show that Mg preferentially occupies the smaller six-coordinate sites in Ca_3−xMg_xAl₂O₆. When Ba is present, it preferentially occupies the larger eight- and nine-coordinate sites. X-ray microanalysis suggests that Pb and Cd are lost from the samples during the preparation process. The diffraction patterns show a small decrease in the lattice parameters, suggesting that a defect structure of the type Ca_3−x(vac)_xAl₂O₆ is formed. The distribution of products formed on hydration of the doped Ca_3−xM_xAl₂O₆ is found to be very different than that observed for the undoped material.     

Hydration of dibarium silicate I. Stoicheiometry of hydration

Dibarium silicate, Ba₂SiO₄, was hydrated in two ways: in paste form at 25° using a water/solid weight ratio of 0.7:1, and in a polyethylene bottle rotated on a wheel at 5°, 25° and 50°, using a water/solid weight ratio of 9.0:1. When Ba₂SiO₄ is hydrated in paste form, the stoicheiometry of the reaction at 25° is the same as in bottle-hydration at 50°: 2BaO.SiO₂+2.2H₂O = 1.2BaO.SiO₂.1.4H₂O+0.8Ba(OH)₂. The stoicheiometry of bottle-hydration at 5° and 25° is represented by the equation: 2BaO.SiO₂+2.2H₂O = BaO.SiO.1.2H₂O+Ba(OH)₂. Barium silicate hydrate, 1.2BaO.SiO₂.1.4H₂O, is well crystallised and has a specific surface area of ? 3m²/g. The crystals are plate-like and have a tendency to form clusters. The low-baria hydrate, BaO.SiO₂.1.2H₂O, is poorly crystallised and consists of thin platelets. It has a specific surface area of ? 35m²/g. The thermal dehydration of fully hydrated barium silicate and of the barium silicate hydrates was investigated by thermogravimetric and differential thermal analysis techniques. The similarities and differences between the barium silicate hydrates obtained in the hydration of barium silicate and the calcium silicate hydrates obtained in the hydration of β-dicalcium silicate and Ca₃SiO₅ are discussed. A mechanism of hydration of barium silicate is proposed which involves solution, precipitation and crystallisation steps.     

Suppression of 3D mobility of carrier and superconductivity by Y substitution in Cu0.5Tl0.5Ba2(Ca2−xYx)Cu3O10−δ samples

Bulk Cu_0.5Tl_0.5Ba₂(Ca_2−xY_x)Cu₃O_10−δ superconductor ceramic samples were synthesized by the conventional solid-state method and characterized by X-ray diffraction, dc-resistivity, ac-susceptibility and Fourier Transform Infrared spectroscopy. The main purpose of this study was to investigate the role of charge carriers and the effect of Y substitution at Ca sites in between the CuO₂ planes on superconductivity. The superconducting properties are suppressed by Y substitution at Ca sites in between the CuO₂ planes of Cu_0.5Tl_0.5Ba₂(Ca_2−xY_x)Cu₃O_10−δ samples. It is most likely that Y³⁺ may create correlated domains in between the CuO₂ planes and localizes the carriers, which lowers the diamagnetic screening and suppresses the superconductivity. Therefore, cationic substitution reduces the three dimensional (3D) mobility of carriers, resulting in the reduction of the Fermi vector and velocity of the carriers, which in turn suppresses the superconducting properties of the material.     

Synthesis and electrical properties of nanostructured Ba2SnYO5.5 proton conductor

Ba₂SnYO_5.5 nanopowders were synthesized by a gel polymerization method. In this process, a gel containing Ba, Sn and Y cations has been obtained by the polymerization of acrylic acid using N,N′-methylene bis-acrylamide as a cross-linking reagent and hydrogen peroxide as an igniting reagent. The gel was calcined at 1200 °C, giving rise to the Ba₂SnYO_5.5 single-phase nanopowders with the grain size ranging from 50 nm to 70 nm. Nanopowders were sintered at 1150 °C by spark plasma sintering (SPS) to obtain dense nanostructure materials (> 95%) containing grains whose size ranges between 70 nm and 100 nm. Nanostructured Ba₂SnYO_5.5 shows a good chemical stability in wet atmosphere. However, its protonic conductivity decreases compared with that of microcrystallin Ba₂SnYO_5.5 ceramics.     

Partial oxidation of CH4 at low pressure over SiO2 prepared from Si

The oxidation of CH₄ with O₂ at low pressure was carried out over SiO₂ prepared from metal Si. The Si showed only total oxidation activity while the Si partly oxidized to SiO₂ showed high selectivities to CH₃OH and HCHO. The results on SiO₂ prepared from Si were compared with those over commercial silicas. The role of SiO₂ in the CH₄ oxidation was discussed.     

SiO2‐supported bimetallic Rh–Co catalysts derived from [Rh(CO)2Cl]2 and cobalt carbonyls

According to the results of IR characterization and catalytic study in ethylene hydroformylation, bimetallic Rh–Co catalysts can be efficiently prepared from [Rh(CO)₂Cl]₂ and cobalt carbonyls by co‐impregnation on SiO₂. The reaction of Co₂(CO)₈ with [Rh(CO)₂Cl]₂ (Rh : Co = 1 : 3 atomic ratio) gives rapidly RhCo₃(CO)₁₂ on the surface of SiO₂. Although Co₄(CO)₁₂ is not reactive with [Rh(CO)₂Cl]₂ on SiO₂ to form directly RhCo₃(CO)₁₂, an equivalent bimetallic catalyst can be easily obtained from ([Rh(CO)₂Cl]₂ + Co₄(CO)₁₂)/SiO₂ or its derivative (Rh⁺ + Co²⁺)/SiO₂ (Rh : Co = 1 : 3 atomic ratio) under reducing conditions. This revised version was published online in July 2006 with corrections to the Cover Date.