Improvement in hydration resistance of CaO granules by addition of Zr(OH)4 and Al(OH)3

Improving the hydration resistance of CaO aggregates is the key to successful application of lime-based refractories in metallurgical industry. Additive Zr(OH)₄ and Al(OH)₃ were introduced in the preparation of CaO granules using granulation equipment and calcination method in this study. The results showed that the hydration resistance of CaO granules was improved significantly, especially for granules with 0.6 wt.% Zr(OH)₄ and 0.9 wt.% Al(OH)₃, respectively. The shell of CaO granules was relatively dense after calcination and the volume of open pores of CaO granules decreased from 3.56 × 10⁻² to 1.80 × 10⁻² cm³/g when additive was introduced. Zr(OH)₄ and Al(OH)₃ have the opposite effect on the closed porosity of CaO granules, the closed porosity of CaO granules was decreased with Zr(OH)₄ addition, but increased with Al(OH)₃ addition.     

Improving hydration resistance of MgO–CaO ceramics by in situ synthesized CaZrO3 coatings prepared using a non-hydrolytic sol

As refractories, MgO–CaO materials exhibit excellent properties such as high refractoriness and good thermal shock resistance; however, their poor hydration resistance limits their practical applications. In this study, calcium zirconate (CaZrO₃) coatings were deposited on CaO and MgO–CaO ceramics by dipping the ceramics in a non-hydrolytic sol. The optimised coating on the MgO–CaO ceramics was prepared by dipping the ceramics once in a 0.6 mol/L zirconia sol. The CaZrO₃ coating was in situ synthesized after calcination. The multiphase ceramics with different CaO contents were characterised using scanning electron microscopy to determine the grain sizes of MgO and CaO and to analyse the distribution of CaO in the MgO matrix and the surface porosity of the samples. The microstructure and phase analysis results showed that most of the CaO on the surface transformed into CaZrO₃ and was located at the grain boundaries. The MgO–CaO ceramics with the CaZrO₃ coatings, especially the ceramics with 20 wt% CaO, showed significantly improved hydration resistance as compared to the untreated ceramics.     

The impact of Al2O3 amount on the synthesis of CASH samples and their influence on the early stage hydration of calcium aluminate cement

In this work the impact of Al₂O₃ amount on the synthesis (200?°C; 4–8?h) of calcium aluminium silicate hydrates (CSAH) samples and their influence on the early stage hydration of calcium aluminate cement (CAC) was examined. It was found that the amount of Al₂O₃ plays an important role in the formation of calcium aluminate hydrates (CAH) because in the mixtures with 2.7% Al₂O₃ only calcium silicate hydrates (CSH) intercalated with Al³⁺ ions were formed. While in the mixtures with a higher amount of Al₂O₃ (5.3–15.4%), calcium aluminate hydrate – C₃AH₆, is formed under all experimental conditions. It is worth noting that the largest quantity of mentioned compound was obtained after 4?h of hydrothermal treatment, in the mixtures with 15.4% of Al₂O₃. It was proved that synthesized C₃AH₆ remain stable up to 300?°C and at higher temperature (945?°C) recrystallized to mayenite (Ca₁₂Al₁₄O₃₃), which reacted with the rest part of CaO and amorphous structure compound, resulting in the formation of gehlenite (Ca₂Al₂SiO₇). Moreover, the synthesized C₃AH₆ addition induced the early stage of CAC hydration. Besides, in the samples with an addition, the induction period was effectively shortened: in a case of pure CAC (G70) paste, hydration takes about 6–6.5?h, while with addition – only 2–2.5?h. The synthesized and calcinated compounds was characterized by using XRD and STA analysis.     

Densification and properties of ZrO2 nanoparticles added magnesia–doloma refractories

In this work the effect of nano- and microZrO₂ addition on the densification and hydration resistance of MgO–CaO refractories was investigated. 0, 2, 4, 6 and 8 wt% ZrO₂ was added to MgO–CaO refractories that contain 35 wt% CaO. The crystalline phases and microstructure characteristics of specimens sintered at 1650 °C for 5 h in an electric furnace were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The physical properties are reported in terms of bulk density, apparent porosity and hydration resistance. Results show that with addition of ZrO₂ the bulk density and hydration resistance of the samples increased while apparent porosity decreased. Also the hydration resistance of the samples was appreciably improved by the addition of ZrO₂ due to its effect on decreasing the amount of free CaO in the refractories, promotion of densification as well as modification of the microstructure. Also it revealed that the nanoZrO₂ addition was more effective than microZrO₂ due to its higher activity.     

Corrosion behaviors of porous reaction-bonded silicon carbide ceramics incorporated with CaO

Reaction-bonded SiC (RBSC) porous ceramics were fabricated at 1450?°C in air by incorporating CaO using ZrO₂ as sintering aids, activated carbon as pore-forming agent, and mullite fibers as reinforcing agent. The effects of CaO content on the properties of the porous RBSC ceramics were studied. Corrosion behaviors of the prepared RBSC porous ceramics in different environments were also investigated. The optimal open porosity, bending strength, average pore size and gas permeability of the ceramics with 0.5% CaO were 40%, 22.5?MPa, 42.9?µm, and 2100?m³/m² h?kPa, respectively. A well-developed neck reaction-bonded by calcium zirconium silicate (Ca₃ZrSi₂O₉) was identified. The porous RBSC ceramics exhibited excellent corrosion resistance in acid and basic solutions. The anti-oxidation temperature of the porous RBSC ceramics could reach 1200?°C in air. The RBSC ceramics maintained the bending strength of 17.5?MPa after 60 cold-hot cycles in air (0–800?°C). The porous RBSC ceramics also exhibited relatively good corrosion resistance in molten salts (NaCl, Na₂SO₄ and CaCl₂). Melten NaOH can aggravate the reaction by breaking the SiO₂ layers on the SiC surface. Overall, these findings offer significant insights into expanding the applications porous RBSC ceramics incorporated with CaO.     

Microstructural and hydration resistance study of CaO with powder surface modification by Al coupling agents: Alkoxy type and phosphate type

The surface of Ca(OH)₂ powders were pre-treated with alkoxy type aluminium coupling agent (ALC) and phosphate type aluminium phosphorus coupling agent (ALPC), respectively in this work. The shaped specimens were calcinated at 1600 °C for 3 h and then the phase compositions and microstructures of CaO specimens were investigated. The results revealed that both ALC and ALPC could conspicuously enhance the hydration resistance of CaO specimens by modifying surface microstructures in different ways. The boundaries of CaO grains in the specimens were covered with C₃A glass phase after introducing of ALC, which was replaced by calcium phosphate when the ALC was replaced by ALPC. The hexagonal barrier layer, which was the hydration product of C₃A, played a protective role in CaO grains. The obtained results in our work indicated that ALC was more effective in improving hydration resistance of CaO materials.     

On the Modification of Hydration Resistance of CaO with ZrO2 Additive

Various ZrO₂/CaO samples were fabricated by cold isostatic pressing and sintered at 1750°C for 4 h. It was observed that the sample with 12% ZrO₂ additive possessed the good hydration resistance and had the lowest apparent porosity of about 0.75%; its weight additive stored after 56 days was less than 0.6 wt%, and it contributed to the occurrence of CaZrO₃ on the surface of CaO. The CaO crucible with 12 mol% ZrO₂ additive did not react with titanium melt during melting TiNi alloy. This provides a support for searching a new refractory with the good hydration resistance for induction melting titanium alloys.     

Influence of tricalcium aluminate on the microstructure evolution of CaO specimen during hydration

C₃A-containing CaO specimen was prepared and the evolution of its microstructure during hydration process was investigated to clarify the protective mechanism of tricalcium aluminate (C₃A) on hydration resistance of CaO specimen. The slit-shaped micropores were formed on the grain boundary of CaO due to the stacking of lamellar C₄AH₁₃ formed by the hydration of C₃A. The contact area of residual C₃A with the moisture was reduced by the porous C₄AH₁₃ layer at the original site, which resulted in a slower dissolution rate of C₃A grain through the porous layer. In addition, the crack propagation and the formation of macropores were inhibited by the pinning effect of C₄AH₁₃, which was beneficial to the improvement of hydration resistance.     

Improved hydration resistance of CaO granules via sol-processed metal oxide protective layers

Well-sintered CaO granules with hydration resistance are very important for the manufacturing and application of CaO-containing refractories. CaO granules with sol-processed metal oxide protective layers were prepared by granulation and surface treatment. The obtained results indicated that the usage of nano sol greatly improved the hydration resistance of CaO granules, especially when the CaO granules were treated by alumina sol. The promoting effect of nano sols in the sintering processes improved the density of CaO granules. Nanoparticles reacted with lime at lower temperature and a new phase was formed uniformly in the treated layer, which promoted densification of the treated layer. The grain size of CaO granules in the treated layer was increased obviously with the promotion of sintering. Moreover, nanoparticles were favorable for the formation of direct bonding between CaO grains by decreasing the dihedral angle.     

Role of ZrO2 in sintering and mechanical properties of CaO containing magnesia from cryptocrystalline magnesite

As main components of magnesia-based refractories, magnesia exhibits excellent properties such as high refractoriness and good basic slag corrosion resistance. However, magnesia produced from CaO containing cryptocrystalline magnesite has limited application owing to the low hydration resistance and poor thermal shock resistance (TSR). This work aimed to investigate the reinforcing effects of microscale monoclinic ZrO₂ on free CaO containing magnesia for optimizing mechanical properties, TSR and hydration resistance. The results showed that adding ZrO₂ could promote the removal of the open pores, strengthen the interface bonding between various grains and produce crack deflection, which improved flexural strength and fracture toughness. As a result, the TSR of the specimens was enhanced effectively due to increased strength and toughness and reduction in the thermal expansion coefficient. Besides, as the ZrO₂ was introduced, hydration resistance of the specimens improved significantly, mainly attributing to the decrease in apparent porosity and elimination of the free CaO by forming CaZrO₃ and cubic ZrO₂ phases.     

Effect of CaO content on hydration rates of Ca-based sorbents at high temperature

The CaO hydration behavior of four Ca-based sorbents (Deyang, Yangguan, Dawa, and Kuzuu) with different CaO contents was examined. A high-pressure thermogravimetric apparatus was used to measure the hydration rates at high temperatures (773–923 K) and high steam pressures (1.3–2.3 MPa). CaO hydration occurred at high temperatures up to 923 K at high steam pressure. The hydration rates and the final CaO conversion values varied substantially among the different sorbents. Hydration rate and CaO conversion decreased with increasing CaO content. The order of CaO hydration rate with respect to the difference between the reactant steam pressure and the equilibrium steam pressure (P_H2O − P^?_H2O) varied with CaO content. The apparent activation energy for rate constant k also varied with CaO content.     

3D printing of CaO-based ceramic core using nanozirconia suspension as a binder

The 3D printing of a ceramic core with nanoceramic suspension as a binder was performed to investigate a novel method for the fabrication of a complex-shaped ceramic core. Green bodies were printed using CaO powder as a precursor material and nanozirconia-absolute ethyl alcohol solution suspension as a binder. The green bodies were sintered at 1300–1500 °C for 2 h. The effects of binder saturation level on the properties of the sintered bodies were investigated. Increasing the binder saturation level caused decreases in the linear shrinkage of the sintered bodies, but increases in hydration resistance and bending strength. The nanozirconia particles were deposited on the surfaces of the CaO particles and filled the pores of green bodies, and then formed a high melting temperature CaZrO₃ layer with the CaO at the surfaces of the CaO grains, which improved the hydration resistance of the CaO-based ceramic core parts.     

Effect of porosity on carbonation and hydration resistance of CaO materials

CaO pellets with different porosity were carbonated at 700 °C in CO₂ atmosphere. The carbonation rate was controlled by the diffusion of CO₂, regardless of the difference in porosities. For the low-porosity pellet, carbonation reaction only occurred on the surface, with a dense CaCO₃ film thus formed, which combined well with the substrate material; while for the pellet of high-porosity, the carbonation reaction occurred simultaneously both on surface and inside pores, and each CaO grain was surrounded by CaCO₃ film that contained microfissures. Hydration test results showed that carbonation treatment could effectively improve the hydration resistance of CaO materials regardless of porosity, but the carbonated high-porosity pellet was prone to breakage due to poor combination between the carbonated CaO grains. Therefore, for the purpose to improve the hydration resistance by carbonation treatment, it is recommended that the CaO materials should be either with less appreciable apparent porosity or with a limited carbonation ratio for the high-porosity CaO material.     

Density,viscosity and surface tension of high-silicate CaO–SiO2 and CaO–SiO2–Fe2O3 slags derived by aerodynamic levitation. The behavior of Fe3+ in high-silicate melts

Thermophysical data for liquid slag are required for the optimization and control of metallurgical processes. The density, surface tension and viscosity were measured by employing aerodynamic levitation under contactless conditions. The high-silicate slag (44 and 63 mass-% of SiO₂) of the CaO–SiO₂ and CaO–SiO₂–Fe₂O₃ systems (with 5 and 10 mass-% Fe₂O₃) was investigated under (80% Ar + 20% O₂) gas atmosphere. The temperature ranges were between 800 °C and 2000 °C for the density and 1500 °C–2000 °C for surface tension and viscosity measurements. The influence of the CaO/SiO₂ ratio on the investigated properties and the behavior of Fe³⁺ ions in high-silicate melts were examined. The density of the CaO–SiO₂ melt was lower than that of the CaO–SiO₂–Fe₂O₃ systems. The surface tension of all compositions tested decreased with temperature and showed compositional dependence. The viscosity measured was higher in the Fe₂O₃-containing slag. The Raman spectroscopy analyses confirmed the increase in the degree of polymerization with the addition of Fe₂O₃ for the silicate-rich slag. The formation of a complex anion of a ferric ion and contribution to the silicate network were assumed. The trends observed were related to the structural properties and different interionic bonding. Urbain's viscosity model and FactSage? 7.3 were applied for the assessment of the experimental data.     

Densification and Properties of Fe2O3 Nanoparticles added CaO Refractories

Up to 8 wt. % of Nano-iron oxide was added to CaO refractory matrix. The crystalline phases and microstructure characteristics of specimens sintered at 1650 °C for 5 h in an electric furnace were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. The physical properties are reported in terms of bulk density, apparent porosity and hydration resistance. The mechanical behavior was studied by a cold crushing strength (CCS) and flexural strength at 1200 °C test. As a result, it was found that the presence of Nano-iron oxide in the CaO refractory matrix induced 2CaO.Fe₂O₃ (C₂F), CaO.Fe₂O₃ (CF) and 3CaO.Al₂O₃ (C₃A) phase’s formation, which improved the sintering process. Nano-iron oxide also influenced the bonding structure through a direct bonding enhancement. On the Other hand, the presence of Nano-iron oxide resulting in improvement properties of CaO refractory matrix refractories such as bulk density, hydration resistance and cold crushing strength. The maximum flexural strength at 1200 °C is achieved by the samples containing 4 wt. % nano-Fe₂O₃.     

Reactivation of partially-sulphated limestone particles from a cfb combustor by hydration

Spent limestone samples from the bed and baghouse of a 22 MWe circulating fluidized bed (CFB) boiler were hydrated and then sulphated in a thermogravimetric analyzer under conditions similar to those found in CFB combustors (850°C, 0.3% SO₂, 9% O₂, 9% CO₂ and 81.7% N₂). Hydration using water gave faster rates and higher levels of conversion of the residual CaO to Ca (OH)₂ than immersion in pure steam at 150 and 200°C. The particles expanded during hydration and their internal volume increased from 0.1 cm³/g Ca before hydration to nearly 0.6 cm³/g Ca after dehydration. Hydration rejuvenated the reactivity of the bed material but not that of the baghouse particles. The conversion of Ca to CaSO₄, in the treated bed particles increased from 32% to over 80% during re-sulphation.     

Effect of MgAl2O4 nanoparticles addition on the densification and properties of MgO-CaO refractories

MgAl₂O₄nanoparticles were added to MgO–CaO refractory ceramic composites in the range of 0–8 wt%. Refractory specimens were obtained by sintering at 1650 °C for 3 h in an electric furnace. Refractory specimens were characterized by measurements of bulk density, apparent porosity, hydration resistance, cold crushing strength, crystalline phase formation, and microstructural analysis. Results show that with additions of MgAl₂O₄ nanoparticles the bulk density of the samples increased. But the apparent porosity and cold crushing strength decreased and increased, respectively with addition MgAl₂O₄ nanoparticles up to 6 wt% and for further MgAl₂O₄ nanoparticles, due to the thermal expansion mismatch, the results is reversed. Also, the hydration resistance of the samples was appreciably improved by the addition of MgAl₂O₄ nanoparticles due to its effect on decreasing the amount of free CaO in the refractory composite and promotion of densification by creating a dense microstructure.     

Hydration of calcium sulphate hemihydrate in the presence of phosphoric acid and calcium oxide: ii. physical properties

The physical properties of plaster slurries and cast gypsum made from calcium sulphate hemihydrate containing small quantities of orthophosphoric acid, calcium oxide, added singly and together with varying CaO/P₂O₅ weight ratios from 0 to 5, were studied. Small quantities of 0.1–0.4% P₂O₅ severely retarded the setting times of plaster slurries, while CaO accelerated them slightly. However, when the CaO and P₂O₅ were added together, the physical properties exhibited some unusual behaviour due to the formation of secondary calcium orthophosphate, CaHPO₄.2H₂O, in situ. At the CaO/P₂O₅ weight ratio range of about 1–2, the initial setting times became excessively long, the compressive strengths and combined water contents decreased, and due to incomplete hydration the casts contained large amounts of unhydrated hemihydrate which increased with increasing concentrations of P₂O₅. Above the CaO/P₂O₅ weight ratio of about 2, the setting time decreased, the compressive strength increased, the hydration was completed and the physical properties returned to the usual values reported for commercial casting plaster. The practical implications of these findings on the industrial use of phosphogypsum are discussed.     

Effect of electromagnetic field on slag corrosion resistance of low carbon MgO–C refractories

Using MgO–C refractories containing 6% carbon and the slag with a basicity (CaO/SiO₂) of around 0.8, the melting slag resistance experiments of low carbon MgO–C refractories were carried out in induction furnace and resistance furnace, respectively. The microstructure of low carbon MgO–C refractories corroded by slag under the different conditions was analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectrometer (EDAX). The results show that in induction furnace having electromagnetic field (EMF), there are MgFe₂O₄ spinel with a little of Mn ions generated in the interfacial layer. Part of the solid solution is monticellite [CaMgSiO₄] containing a little MnO and FeO. While under the condition of EMF free, there is not MgFe₂O₄ spinel in the interfacial layer and the solid solution is monticellite (CaMgSiO₄). At a high temperature, EMF increases the diffusion coefficient of Fe^2+/3+ ions, which displaces Mg²⁺ and forms MgFe₂O₄ with a little of Mn ions. There are MgAl₂O₄ spinel in the penetration layers under the conditions of both EMF and EMF free. EMF speeds up corrosion of low carbon MgO–C refractories.     

Contribution to the hydration of expansive cement on the basis of metakaolinite

The study of hydration of expansive cement prepared from 64% portland cement clinker, 23% metakaolinite and 13% CaSO₄.2H₂O is described. It was found that in the course of a 10-day hydration period, all the gypsum entered the reaction with the formation of ettringite. In 7–10 days, after the termination of the expansion processes, typical stalk-like crystals were transformed into leaf-shaped or other formations. Ettringite was identified even after 4 months of hydration. Monosulphate (3CaO.Al₂O₃.CaSO₄.12H₂O) was found in none of the investigated high-expansion cement paste samples.