Hydration of a low‐grade magnesium oxide. Lab‐scale study

BACKGROUND: Low grade magnesium oxide (LG‐MgO) is a by‐product from the calcination of natural magnesite that is currently hydrated to magnesium hydroxide by storing it in the open for up to 6 months. It is eight to ten times cheaper than pure magnesium oxide and therefore the revalorization of this by‐product is very attractive for those applications requiring great quantities of magnesium hydroxide for which high purity is not required. Here the hydration of LG‐MgO is studied as a function of two parameters: hydrating agent and temperature. RESULTS: Addition of acetic acid during the hydration of LG‐MgO improved the effectiveness of treatment. At 50 °C, the maximum percentage hydration was 40% in pure water and increased to 65% and 70% using aqueous solutions of 0.5 and 1.0 mol L^?1 acetic acid. Increase of temperature also had a positive effect on the final degree of hydration. When the treatment was carried out with 0.5 mol L^?1 acetic acid, the hydration increased from 50 to 65 and 80% at 25, 50 and 90 °C respectively. Accordingly under the optimum conditions of 90 °C and 0.5 mol L^?1 acetic acid 80% hydration was achieved within 8 h. CONCLUSIONS: The results showed that much shorter hydration times are possible and therefore an industrial alternative to the spontaneous process could satisfy an increasing demand for magnesium hydroxide. Moreover, agitation is not needed as the reaction is chemically controlled. Copyright © 2012 Society of Chemical Industry     

The influence of hydrating agents on the hydration of industrial magnesium oxide

BACKGROUND: The influence of different hydrating agents on the pH of the hydrating solutions, rate of hydration of MgO to Mg(OH)₂ and product surface area was studied as a function of temperature of hydration. Hydrating agents used were aqueous solutions of ammonium chloride, magnesium acetate, magnesium nitrate, nitric acid, acetic acid, magnesium chloride, sodium acetate and hydrochloric acid and distilled water as control. These were chosen to determine either the effect of addition of a common ion, the effect of changing the solution pH or due to the presence of an acetate ion, found earlier to have a beneficial effect on the hydration of MgO. RESULTS: There was no significant difference in the hydration behaviour of the hydrating agents up to 50 °C, where less than 10% of magnesium hydroxide was formed. The amount of hydroxide increased at temperatures above 60 °C. When compared with the hydration in water, all the hydrating agents, with the exception of sodium acetate, showed a significant increase in the degree of hydration. Sodium acetate formed the lowest amount of magnesium hydroxide, ranging between 1.2 and 12.2% magnesium hydroxide. The largest percentage (56.7%) of magnesium hydroxide was formed from hydration in magnesium acetate. CONCLUSION: It seems that MgO hydration is a dissolution‐precipitation process controlled by the dissolution of MgO. The increased degree of hydration in magnesium acetate is possibly due to the presence of acetate and Mg²⁺ ions. Copyright © 2010 Society of Chemical Industry     

Phase stability and microstructure evolution of MgO-ZrO2 and MgO-6YSZ ceramic fibers

In this work, MgO-ZrO₂ and MgO-6YSZ ceramic fibers were prepared with sol-gel method via electrospinning. Polymorph stability and microstructure evolution of zirconia fibers were fully characterized by X-ray diffraction, Raman spectra, X-ray photoelectron spectroscopy, and Scanning electron microscope. The results indicated that tetragonal zirconia for MgO-ZrO₂ was obtained and cubic zirconia could be fully stabilized for MgO-6YSZ with MgO molar fractions varying from 0.1 to 0.5 at 800°C. Monoclinic phase appeared with MgO molar fractions even up to 0.5 for MgO-ZrO₂ system and partially or fully stabilized zirconia could be achieved for MgO-6YSZ at 1000°C and 1200°C. Grain size was gradually decreased with increasing of MgO content at 800°C both for MgO-ZrO₂ and MgO-6YSZ ceramic fibers. The grain size of both systems increased with MgO molar fractions varying from 0.1 to 0.2 and then decreased at higher contents at 1000°C and 1200°C. A discussion on relationship among MgO state and the phase stability and grain size was presented. This work shows surface excess and solid solution of MgO predominantly controlled the phase stability and microstructure evolution of zirconia fibers.     

MgO calcination for easy direct coagulation casting of aqueous alumina slurries

The reactivity of MgO with ammonium poly(acrylate) and diammonium hydrogen citrate dispersants was decreased by high-temperature calcination which enabled easy preparation of direct coagulation casting slurries without cooling. The decrease in reactivity of MgO with an increase of calcination temperature (30–1200?°C) was due to the decrease of surface area (52.7–0.7?m²/g) as a result of an increase of average particle size (285–2075?nm) as well as a change of particle morphology from flaky to near spherical. The MgO calcined at a temperature of 1000?°C and above provided sufficient time for mixing with aqueous alumina slurries by ball milling at room temperature (~30?°C) without producing an adverse increase in viscosity before casting. The setting time of 55?vol% alumina slurries was in the ranges of 260–1070 and 10–50?min at room temperature and at 70?°C, respectively, at MgO concentrations in the range of 0.1123–1.2?wt%. The faster setting at 70?°C was due to a combination of faster dispersant-MgO reaction, faster hydration of MgO and high valance counter ion effect.     

Early hydration properties and microstructure evolutions of MgO-activated slag materials at different curing temperatures

This study reports on the early hydration properties and microstructure evolutions of MgO-activated slag at five curing temperatures (20 °C, 40 °C, 50 °C, 60 °C, and 80 °C) and three MgO types (S-MgO, M ? MgO, and R-MgO). The results indicated that high-temperature curing substantially increased the compressive strength of the specimens. Particularly, the highest strength was obtained at 40 °C and 60 °C for the S-MgO and M-MgO-activated slag specimens, respectively, and the high curing temperature for the R-MgO-activated slag specimen was 40 °C. We focused on the relationship between the mechanical properties, pore structure characteristics, and hydration products. The combination of calcium-silicate-hydrate (C-S-H) gel and Al increased under high-temperature curing conditions. XRD, FT-IR, TG-DTG, and ²⁷Al MAS-NMR results showed a high Al content in the formation of calcium silicate hydrate with Al in its structure (C-A-S-H gel) for the R-MgO-activated slag pastes under high-temperature curing; however, the microstructure was loose owing to the formation of excessive brucite. For the S-MgO-activated slag specimen, the Ca/Si ratio was high, with more Mg²⁺ penetrating the C-S-H gel interlayer, forming more hydrotalcite-like phases and increasing the chain length of the C-S-H gel. The microstructure showed good compatibility of the hydration products interweaving to form dense microstructures.     

Tape casting and characterizations of MgO ceramics

We report a high density MgO ceramic substrate produced by the tape casting technology. The tape casting formulation and process produced a uniform tape free of cracking. Y₂O₃ and SiO₂ were used as the sintering aid for the pressureless sintering of the green tape. X-ray diffraction phase identification indicates that MgO is the main phase, while both Y₂O₃ and SiO₂ sintering aids react with MgO to form MgY₄Si₃O₁₃ as the second phase. Liquid phase sintering occurs in the temperature range from 1030°C to ~1500°C, which is confirmed by the simultaneous Thermal Gravitation Analysis/Differential Scanning Calorimeter (TGA/DSC) and the percent linear shrinkage and densification. A 96.5% theoretical density was achieved by presureless sintering at 1650°C for 2 hours, which was further increased to a fully dense structure using hot-isostatic-pressing(HIP) at 1650°C and 207 MPa in argon. Scanning electron microscopy (SEM) and energy dispersive(EDS) spectroscopic analysis on the HIP’ed sample show that MgY₄Si₃O₁₃is located at the MgO grain boundary and the sample has a fully dense structure. The refractive indices and extinction coefficient were measured on the HIP’ed sample along with thermal properties and dielectric properties. Thermal diffusivity and heat capacity were measured to calculate the thermal conductivity.     

活性MgO含量对碱式硫酸镁水泥强度及水化产物的影响

为了研究活性MgO含量对碱式硫酸镁水泥强度及水化产物的影响,采用不同活性MgO含量的轻烧氧化镁制备水泥试样,进行抗压强度和抗折强度试验,并对水泥水化产物进行X射线衍射分析.结果表明,当改性剂掺量为活性MgO质量的1％时,活性MgO含量为60％的轻烧氧化镁制备的水泥试样在室温条件下养护28 d的抗压强度最高,水化产物的主要物相为5·1·7相和少量Mg(OH)2相;活性MgO含量为70％的轻烧氧化镁配制的水泥试样在同等条件下的抗压强度仅为活性MgO含量为60％时的60％,水化产物的主要物相为Mg(OH)2相和少量5·1·7相;活性MgO含量为43.2％的轻烧氧化镁制备的水泥试样强度最低,水化产物中以Mg(OH)2相为主,5·1·7相含量较少,以及剩余MgO相和未分解的MgCO3相.采用活性MgO含量为70％的轻烧氧化镁制备水泥试样时,增加改性剂掺量为活性MgO质量的2％时,试样各龄期强度有较大提高.     

Effect of Additives on the Hydration Resistance of Materials Synthesized from the Magnesia–Calcia System

The effect of a variety of doping additives on the hydration resistance of calcined materials in the MgO–CaO system was investigated. Samples were prepared from lightly calcined flotation magnesite that was mixed with dolomite, as well as from analytically pure CaO and MgO; then, the samples were doped with additives that contained cations with various valences (monvalent to tetravalent). Both the hydration rate and the powdering rate were measured. The important role of the higher-valence cations in improving the hydration resistance of the MgO–CaO materials was revealed. This behavior is believed to be due to the formation of vacancies in solid solutions of CaO or MgO with higher-valence cations. The Ti⁴⁺ cation forms a solid solution with CaO, which reduces the Ca²⁺ concentration and leads to the improved hydration resistance of calcined materials from the MgO–CaO system.     

The effect of magnesium compounds (MgO and MgAl2O4) on the synthesis of Lanthanum magnesium hexaaluminate (LaMgAl11O19) by solid-state reaction method

In the present study, the lanthanum magnesium hexaaluminate (LaMgAl₁₁O₁₉)(LaMA) powder was synthesized by the solid–state reaction method using two types of magnesium compounds, including magnesium oxide (MgO) and magnesium aluminate (MgAl₂O₄) spinel (MAS). The effect of substitution of magnesium oxide with MAS on the synthesis temperature, intermediate compounds and morphology of synthesized powders were investigated. The microstructural results showed that the intermediate compounds of lanthanum aluminate (LaAlO₃), aluminum oxide and MAS were formed in the presence of magnesium oxide, whereas in the latter case, the LaAlO₃ intermediate phase was not observed and La₄Al₂MgO₁₀ was formed at about 810 °C. Also in both cases, a single LaMA phase with the platelet-like morphology was formed. The thickness of the LaMA platelets decreased from 300 nm to 125 nm and the synthesis temperature increased from 1330 °C to 1355 °C, by replacing MgO with MAS.     

The Diffusion of Moisture in Paddy During Hydration and Dehydration Processes

Hydration and dehydration behavior and the effective diffusivity of paddy during the process of parboiling were studied. Hydration of three different paddy samples (Sherpa low and high head rice yield and Reiziq) were performed below (60°C) and above (90°C) the gelatinization temperature. The hydration period ranged from 5 to 300 minutes at 60°C and 5 to 90 minutes at 90°C. All of the paddy samples showed different hydration behavior below and above the gelatinization temperature, discerned with two different stages at 60°C and three stages at 90°C. Dehydration was carried out at 40°C just after hydration (without tempering the kernel), which mostly took place at the falling rate period. The hydration and dehydration pattern was not different between the high HRY and low HRY paddy, indicating a limited contribution of microfissures to the diffusion rate in the paddy. Five commonly used semi-empirical models were used to predict the hydration and dehydration behavior of paddy and, among them, the Page model was found to be the most suitable. The effective diffusivity during hydration was dependent on the temperature of hydration, which was 1.83 × 10^?11 to 2.11 × 10^?11 m²/s at 60°C and 6.68 × 10^?11 to 7.94 × 10^?11 m²/s at 90°C. The effective diffusivity during dehydration depended on the soaking temperature and period of soaking; it was lower for high-temperature-hydrated samples than low-temperature-hydrated samples. The study concluded that the mass water diffusivity was not affected by the microfissures within the paddy kernel, and the hydration pattern was strongly dependent on whether the temperature was above or below the gelatinization temperature.     

Preparation and properties of porous Al2O3-based ceramics by gel casting using MgO as a gelling and consolidating agent

Low-cost and environment-friendly MgO was used as a new gelling and consolidating agent to fabricate porous Al₂O₃-based ceramics via a gel casting routine. Effects of 800°C calcined additions of MgO (.5, 1.0, 1.5, and 2.0 wt%, respectively) on open porosity (OP), pore size distribution, gas flux, and microstructure of the porous ceramics were investigated deliberately. The experimental results showed that 800°C calcined MgO exhibits excellent gelling and consolidating performance at 80°C, mainly owing to the hydration reaction between MgO and H₂O and thus results in high-quality porous Al₂O₃-based ceramics without deformation and cracking. The Al₂O₃–water suspensions with different MgO additions have good flowability at room temperature. Moreover, water absorption, open porosity, and gas flux of the as-prepared porous ceramics increase remarkably with rising of MgO addition. Furthermore, MgO addition significantly suppresses the abnormal growth of Al₂O₃ grains, and thus the microstructure of the porous Al₂O₃-based ceramics becomes more uniform. This technique of gel casting using MgO as a new gelling and consolidating agent offers an alternative routine for a large-scale production of porous ceramics.     

Oxidation mechanism of MgO–C in air at various temperatures

Abstract

Oxidation of MgO–C refractories containing 20 wt-%graphite was conducted by measuring the weight loss at regular intervals at various temperatures from 800 to 1600°C in air. The rate of decarburisation increased with rise in temperature from 800 to 1400°C and then remained more or less constant from 1400 to 1600°C. The oxidation kinetics were analysed in detail and reaction rate models derived for the temperature range 800–1400°C. The reaction rate was found to be controlled by diffusion of oxygen through the decarburised layer. At higher temperatures (>1400°C), oxidation of graphite also takes place indirectly by the reaction MgO(s) + C(s) → Mg(g) + CO(g). The magnesium vapour thus produced is reoxidised at the outer surface and redeposited as MgO. This leads to a reduction in porosity in the decarburised outer shell and, consequently, a reduction in the rate of oxidation.     

Regeneration and reuse of magnesium oxide (MgO) nanocrystallites

The study focuses on regeneration and reuse of in-house synthesized MgO nanocrystallites used as an adsorbent for the removal of Acid Orange 7 dye from wastewater. The dye-adsorbed MgO were regenerated by two major steps: drying and combustion. The used MgO were dried at room temperature of 35°C ± 5°C, at an optimized time of 8–10 h time and the dried MgO were combusted at an optimized temperature of 500°C in muffle furnace for 25 min. The regeneration and reuse of MgO could be effectively carried out for five adsorption-combustion cycles. In every cycle of regeneration, 8–10% by weight of MgO was lost. The X-ray diffraction analysis showed the phase purity and the calculated crystallite size of synthesized, first, second, third, fourth and fifth regenerated MgO were noted as 21.67, 21.67, 21.67, 24.74, 24.74 and 24.74 nm, respectively. The scanning electron microscopy analysis showed that agglomeration of regenerated MgO particles increased with the increase in number of adsorption-combustion cycles.     

Hydrogenation of phenol to cyclohexanone over Pd/MgO

Hydrogenation of phenol to cyclohexanone has been investigated in the temperature range 160–250°C on a series of Pd/MgO catalysts. At 160°C the orders of reaction were found on all catalysts to be about ?1 with respect to phenol and about + 1 with respect to hydrogen. On the basis of the kinetic results it is suggested that the rate determining step is the surface reaction between phenol and hydrogen adsorbed on the catalyst. An increase in the reaction temperature decreases the rate of reaction. This has been explained through a change of the orders of reaction which increase with temperature. Palladium dispersion does not influence the reaction mechanism. The specific activity was found to be independent of palladium particle size.     

THE SYSTEM MAGNESIUM OXIDE-BORIC OXIDE*

Equilibrium In the system has been investigated for compositions from 0.6 to 75 weight per cent MgO. Three intermediate compounds are present. MgO⋅B₂O₃ melts incongruently at 988°C. to form 2MgO⋅B₂O₃ and a liquid containing more than 99% B₂O₃. The other two compounds melt congruently: 2MgO⋅B₂O₃ at 1340°C. and 3MgO⋅-B₂O₃ at 1366°C. At 1142°C., a region of liquid immiscibility extends from 0.6 to 36.0% MgO. Temperatures are accurate within =5°C. Conflicts between these results and those of Toropov and Konovalov (see footnote 8) are discussed.     

MgO fumes as a potential binder for in situ spinel containing refractory castables

MgO is pointed out as an alternative binder for refractory materials, mainly for systems where the presence of CaO might not be desired. Selecting the most suitable magnesia source is an important step as its purity and reactivity should influence the hydration reaction, leading to binding effect or cracks. This work investigated the design of vibratable high-alumina compositions bonded with MgO fumes [which is a very fine powdered oxide (d < 3?µm) resulting from the production process of electrofused magnesia] and/or dead-burnt magnesia (d < 212?µm). Acetic and formic acids were added to the castables during their processing steps in order to adjust the density of active sites for Mg(OH)₂ formation and control the crystal growth of this phase. The green mechanical strength and thermomechanical performance (cold and hot mechanical strength, thermal shock, refractoriness under load, corrosion, etc.) of designed MgO-bonded compositions were analyzed. Improved green mechanical strength and crack-free samples were obtained when adding up to 6?wt% of MgO fumes to the refractories and processing them with aqueous solutions with 3?wt% of formic acid. The compositions with 6?wt% of magnesia fumes resulted in samples with flexural strength in the range of 12.0?MPa after curing at 50?°C/24?h and similar green mechanical strength (12.9?MPa) as the ones bonded with 4.0?wt% of calcium aluminate cement after drying at 110?°C for 24?h, which highlights the great potential of this MgO source. Despite the enhanced green mechanical strength, alumina-based castables containing 6?wt% of MgO (fumes, dead-burnt or their blend) showed low mechanical strength at intermediate temperatures and high linear expansion, as a consequence of the in situ spinel phase formation above 1200?°C. Thus, better densification, improved HMOR, thermal shock resistance and corrosion behavior were obtained for the castables prepared with less MgO fume contents.     

Heterocoagulation moulding of alumina powder suspensions prepared using citrate dispersant

Coagulation characteristics of aqueous alumina suspensions prepared using di-ammonium hydrogen citrate (DHC) dispersant has been studied using MgO coagulating agent for direct coagulation casting (DCC). Mg–citrate complexes formed by the reaction between the DHC and MgO act as dispersant for alumina at pH near its iso-electric point. Setting of the alumina suspensions takes place, at MgO concentrations higher than the equivalent amount required to react with the DHC, by heterocoagulation of the alumina and MgO particles due to their opposite surface charges. The yield strength and Young's modulus of the wet-coagulated alumina bodies increased with aging time due to the hydration of the excess MgO. The minimum time required for mould removal decreases and yield strength and Young's modulus of the wet-coagulated bodies increases with MgO concentration. Alumina green bodies prepared at MgO concentrations in the range of 0.2–0.5 wt% sintered to ～97% theoretical density at 1550 °C and the sintered ceramics showed more or less similar microstructures irrespective of MgO concentrations.     

MgO assisted densification of highly transparent YAG ceramics and their microstructural evolution

In current study, various amounts of MgO single dopant was adopted to fabricated high quality transparent YAG ceramics, by utilizing a simple one-step solid state reaction sintering method in vacuum. At a MgO doping amount of only 0.03 wt.%, YAG transparent ceramics with a transmittance of 84.5% at 1064 nm could be obtained, after sintering at 1820 °C for 8 h. The microstructure evolution and optical property of as-fabricated YAG ceramics as a function of MgO doping concentration were systematically investigated. MgO dopant could effectively promote densification of YAG ceramics when the sintering temperature was lower than 1660 °C, and dramatically accelerate its grain growth between 1540 °C and 1660 °C. Further increase the doping amount of MgO would not benefit to the optical quality of YAG ceramics, and the intragranular pores as well as the Mg-riched secondary phase were observed from the MgO heavily doped ceramics.     

PHYSICAL PROPERTIES OF SOME HIGH-TEMPERATURE REFRACTORY COMPOSITIONS*

In the course of an investigation that involved a study of pyrochemical reactions, it was necessary to develop a refractory that could be used satisfactorily at temperatures in the range of 1800° to 2200°C. It was found that calcined magnesia (96%, MgO) or electrically fused magnesia (98% MgO) could be bonded adequately by mixing sized aggregates with 2.5%, by weight of calcined sea-water magnesia and wetting with a 24° Bé. solution of magnesium chloride Large shapes of these compositions fired at 1450°C. were satisfactory for use in the required temperature range. A small-scale study OF the properties of various refractory bodies showed that compositions containing relatively pure limestone or dolomite readily hydrated in water even after firing to 2100°C. and were unsuitable for refractory use. The addition of silica, alumina, zirconia, chromic oxide, or combinations of these oxides to dolomite or limestone resulted in a refractory stable against hydration. The inversion of zirconia was reduced appreciably by the addition of 5% magnesia. Bodies containing BaO·ZrO₂ and CaO·ZrO₂ were found to be stable after firing to 2100°C. with no inversion up to 1200°C. and with a coefficient of expansion less than that of electrically fused magnesia. Small- and large-scale tests of an MgO·Cr₂O₃ spinel composition showed this material to be highly refractory with a low coefficient of expansion; the compound, however, dissociates and loses Cr₂O₃ above 1700°C. While the small-scale tests disclosed a number of compositions which show promise as high-temperature refractories, their full evaluation for use on a large scale was not made.     

Pyrolysis mechanism of magnesium citrate nonahydrate and microstructural evolution during the process

The key characteristics of the porous carbon materials and ceramic composites derived from citrates are directly affected by the pyrolysis mechanism of parent citrates and the microstructural revolution during the process. The pyrolysis mechanism of magnesium citrate nonahydrate (MCN) and the microstructural evolution during its pyrolysis were investigated by analysing the C/MgO nanocomposite powders from MCN pyrolyzed in carbon embedded condition and flowing argon atmosphere. The pyrolysis process of MCN was composed of the following stages: (1) MCN dehydrated to magnesium citrate at about 150 °C; (2) magnesium citrate decomposed into itaconic acid magnesium and MgO at about 300 °C; (3) itaconic acid magnesium decomposed into carbon, MgO and CH₄ at around 500 °C; (4) CH₄ was pyrolyzed and graphene was deposited on MgO. The carbon produced in stage (3) was turbostratic while that derived from the pyrolysis-deposition of CH₄ was few-layered-graphene. The MgO nano grains produced in stage (2) precipitated and agglomerated while those derived from itaconic acid magnesium were much smaller in size. In carbon embedded condition, the few-layered-graphene not only deposited on the MgO aggregates surface but also inserted into the MgO nano grain boundaries, which suppressed the growth and sintering of MgO nano grains.