Optimized microstructure with nano-alumina and its effects on properties of corundum spinel castables

The mechanical properties, thermal shock resistance, and microstructure evolution of corundum spinel castables with different nano-alumina contents were investigated. The results show that the addition of nano-alumina has advantages on the microstructure evolution and properties of castables. An optimum nano-alumina amount is 2 wt%. When nano-alumina addition changes from 0 to 2 wt%, the cold modulus of rupture (CMOR) and cold compressive strength (CCS) improved by 69.7% and 78.1% after firing at 1100°C, respectively. The CMOR and CCS increased by 42.5% and 35.2% after firing at 1500°C, respectively. Meanwhile, the hot modulus of rupture (HMOR) was enhanced by 21.5% to 13.4 MPa. The retained Young's modulus values of castables were improved from 49.6% to 59.6% after eight thermal shock cycles. Furthermore, the HMOR and the retained Young's modulus values of castables slightly reduced when nano-alumina content up to 3 wt%. XRD, DSC, SEM, and EDS analyses revealed that the addition of nano-alumina leads to the formation of calcium dialuminate (CaO·2Al₂O₃) at 1100°C and it is beneficial to the formation of more platelet hibonite (CaO·6Al₂O₃) at 1500°C. As a result of using nano-alumina with large surface area, the solid phase sintering of the nanoscale particles can occur at lower temperatures. Moreover, the mechanical properties and thermal shock resistance of the castables were improved remarkably.     

Mullite-based refractory castable engineering for the petrochemical industry

Refractory castables used in fluid catalytic converter (FCC) risers should present suitable particle erosion and thermal shock resistances at temperatures below 900 °C. Considering that calcium aluminate cement (CAC)-bonded refractories usually start their densification above 1200 °C, the use of sintering additives to induce faster densification is a promising technological alternative. Therefore, this work addresses the evaluation of mullite-based castables containing a boron-based sintering additive and CAC and/or hydratable alumina as the binder sources. Hot elastic modulus, cyclical thermal shock, hot modulus of rupture and cold erosion resistance measurements were carried out to evaluate the compositions. According to the attained results, adding 1.5 wt% of the evaluated sintering additive to the designed castables led to a remarkable increase of the hot modulus of rupture (maximum of 40.4 MPa at 800 °C for the CAC-containing refractory) and high erosion resistance (1.5–2.9 cm³) after pre-firing at 800 °C for 5 h. Moreover, the combination of CAC and hydratable alumina gave rise to an improved refractory (M–2CAC–2HA–S) showing a transient liquid formation at an increased temperature, high thermal shock resistance (no E decay after 8 thermal cycles, ΔT=800 °C) and high mechanical strength at 800 °C and 1000 °C.     

Low Temperature Synthesis of High Alumina Cements by Novel Co‐Melt Precursors and Their Implementation as Castables with Some Micro Fine Additives

In the present investigations nano size high alumina cements (HAC) were prepared by very effective co‐melt precursor sintering technique from their metal nitrate precursors. The prime cementing phases observed were CA, CA₂, and C₁₂A₇. The addition of nano structured cements in refractory castables has improved the thermo‐chemical‐mechanical properties to a significant extent. Each batch of low cement castables (LCC) was prepared from calcined Chinese bauxite, HAC, and superfine additives. The effect of HAC in bauxite castable with the additives similar to Silicon Carbide, reactive alumina, and micro‐fine silica on the sinterability and properties of these castables was investigated. Physical properties such as apparent porosity and bulk density, mechanical properties such as hot modulus of rupture (HMOR), cold and hot modulus of rupture (CMOR), and cold crushing strength (CCS) of hydrated and sintered castables were studied. The sintered castables were also characterized for their solid phase compositions and microstructure using X‐ray diffraction (XRD) and FE‐SEM, respectively. In the castables new phases such as mullite, α‐alumina were formed at the expense of bauxite and silica. Solid solution of mullite formed at high temperature acts as a bonding phase and is accounted for high HMOR, CMOR, and CCS values. These excellent properties of such castables may enable their uses in various applications such as refractory lining for fabrication of steel, aluminium, copper, glass, cement, chemicals, and ceramics.     

Effect of spinel content on hot strength of alumina-spinel castables in the temperature range 1000–1500°C

Hot modulus of rupture of Al₂O₃-spinel castables containing 5–15 wt% alumina-rich magnesia alumina spinel and 1·7 wt% CaO generally increases with increase in spinel content and temperature from 1000 to 1500°C. The magnitudes of hot modulus of rupture of castables containing 15 wt% spinel and 1·7 wt% CaO are 14·3 MPa at 1400°C and 15·6 MPa at 1500°C, while those of castables containing 20 wt% spinel and 1·7 wt% CaO are 12·5 MPa at 1400°C and 14·7 MPa at 1500°C. The former castables contained 15 wt% spinel of −75 μm size, while the latter contained 10 wt% spinel of +75 μm size and another 10 wt% spinel of −75 μm size. The bond linkage between the CA₆ and spinel grains in the matrix is believed to cause both the spinel content and temperature dependence of hot strength of Al₂O₃-spinel castables, as well as fine grain spinel even in amount less than coarser grain spinel to be more effective for enhancing hot strength. The trend of the magnitude of thermal expansion under load (0·2 MPa) above 1500°C of the castables is not necessarily indicative of the magnitude of hot modulus of rupture at 1400 or 1500°C. ©     

Monoaluminum phosphate-bonded refractory castables for petrochemical application

Phosphate-bonded refractories may be applied as repairing materials due to their short setting time and good thermo-mechanical properties in the 30–1000 °C temperature range. This works addresses the development of vibratable high-alumina castables containing commercial monoaluminum phosphate (MAP) solutions (Fosbind 151 and Fosbind 50) and dead-burnt magnesia (d<212 µm, setting agent) as the binder systems. Flowability, setting time, X-ray diffraction, cold erosion, thermal shock resistance, cold and hot modulus of rupture, thermogravimetric measurements and hot elastic modulus tests were carried out in order to understand the phase evolution and thermo-mechanical behavior of the refractories. Furthermore, the effect of adding a boron source (sintering additive) to the phosphate-bonded compositions was also investigated. According to the attained results, the reaction of MAP with MgO and the reactive aluminas of the compositions resulted in setting times of the mixtures around 90–120 min at 30 °C, which was associated with the in situ generation of magnesium and aluminum phosphates [MgHPO₄·3H₂O, Mg(H₂PO₄)₂(H₂O)₂ and AlPO₄.2H₂O]. The boron-containing castables presented Al₁₈B₄O₃₃ around 650–800 °C and this phase favored the increase of the samples' stiffness, mechanical strength, erosion and thermal shock resistance. The refractoriness under load measurements indicated that the maximum working temperature for the evaluated refractories was in the range of 1400–1500 °C.     

Effect of in-situ formation of columnar mullite and pore structure refinement on high temperature properties of corundum casatbles

The effects of in-situ synthesis columnar mullite and pore structure on the hot modulus of rupture (HMOR), thermal shock resistance and corrosion resistance of corundum castables have been investigated in this paper. When 2% nano silica was added, the pore diameters of castables could be decreased to 15 nm (at 110 °C), 1 μm (1100 °C) and 6 μm (1500 °C), respectively. The corresponding reducing magnitude of pore size is 98.5%, 83.3% and 33.3%. The HMOR of castables fired at 1500 °C increased by 110% to 3.64 MPa. Furthermore, after three thermal shock cycles, the residual strength ratio of castables increased from 5.2% to 15.3%. A large amount of cross-distributed columnar mullite was formed between nano silica and α-Al₂O₃ by the two-dimensional nucleation mechanism, which remarkably enhanced the high temperature properties. The penetration index reduced from 30.86% to 19.88%, suggesting that smaller pore size and higher viscosity had a great influence to the penetration process.     

Hot bending strength and creep behaviour at 1000–1400 °C of high alumina refractory castables with spinel,periclase and dolomite additions

The modulus of rupture and creep behaviour of refractory castables at high temperature (1000–1400 °C) with additions of spinel, periclase and dolomite has been studied. Three processing routes for obtaining refractory concretes within the alumina-rich zone of the Al₂O₃–MgO–CaO ternary system were employed. To achieve high temperature mechanical properties special attention was paid to the processing route (synthetic spinel, periclase and dolomite additions), and the composition (effect of synthetic or self-forming spinel and CaO contents).The results demonstrate that these refractory castables show a highly viscoplasticity behaviour at temperatures >1100 °C and a hot bending strength depending on the loading rate. Refractory castables made with synthetic spinel have lower high temperature bending strength values than castables made with periclase additions owing to their less viscoplastic behaviour. In this work neither the amount of spinel nor processing route chosen were found to have any significant influence on the hot bending tests between 1100 and 1400 °C. The creep tests show that in the temperature range of 1100–1300 °C the main reaction governing deformation is the interaction between the alumina and the calcium aluminate cement phases. Above 1300 °C, castables made first with dolomite, then with periclase and finally with synthetic spinel are more prone to deformation in that order.     

Effect of micro-spinel powders addition on the microstructure and properties of alumina refractory castables

The microstructural evolution and comprehensive properties of alumina refractory bonded with calcium aluminate cement and silica sol have been studied. Results have been correlated with the microstructural and phase evolutions using X-ray diffraction and scanning electron microscopy, as function of the pre-formed spinel powders. Matrix samples were obtained for phase and microstructural characterization in details, and the results were compared with those corresponding to the refractory castables. The room temperature and high temperature properties, including permanent of linear change, mechanical properties, hot modulus of rupture (HMOR) and slag resistance were measured. The castables exhibited a microstructural optimization and properties enhancement due to the addition of pre-formed spinel. A lot of secondary spinel and CA₆ (CaO·6Al₂O₃) with small size were produced in the castables, and the contents of micro pores were greatly increased. As a result, the permanent of linear change of castables was decreased by 61%, while cold modulus of rupture (CMOR) and HMOR were increased more than 45% and 100%, respectively. The penetration indexes in the static slag resistance were decreased from 28.8% to 12.2%.     

Mullite–zirconia–zircon composites: Properties and thermal shock resistance

In the refractory field mullite and zirconia are the basis of materials used in the glass industry or when high chemical stability and corrosion resistance are necessary. In this work various mullite–zirconia/zircon compositions were investigated to improve the thermal shock (TS) resistance of dense composites produced by slip casting and sintering at 1600 °C. Zircon (SiZrO₄) acts as bonding phase and its thermal decomposition adds zirconia and silica to the material. Resultant composites were characterized by density and dilatometric measurements, XRD and SEM techniques. TS behavior was tested by quenching in water with quenching temperature differentials ΔT from 400 to 1200 °C. The degree of damage after the TS was experimentally evaluated through the variation of the elastic modulus E which is measured by the excitation technique. The severity of the TS test and the effect of the number of thermal cycles on E for each ΔT employed were determined.The tested materials retained their original mechanical properties for temperatures below a critical temperature ΔT_c near 600 °C. Materials quenched from ΔT of 1000 °C showed as much as 30% reduction in E indicating the important microstructure damage. The TS resistance improved with increasing zircon addition to 35 wt% in agreement with the behavior predicted from R parameter for crack initiation.     

Microstructural,mechanical and thermal shock properties of triple-layer TBCs with different thicknesses of bond coat and ceramic top coat deposited onto polyimide matrix composite

In this study, a triple-layer thermal barrier coating (TBC) of Cu-6Sn/NiCrAlY/YSZ was deposited onto a carbon-fiber reinforced polyimide matrix composite. Effects of different thicknesses of YSZ ceramic top coat and NiCrAlY intermediate layer on microstructural, mechanical and thermal shock properties of the coated samples were examined. The results revealed that the TBC systems with up to 300 µm top coat thicknesses have clean and adhesive coating/substrate interfaces whereas cracks exist along coating/substrate interface of the TBC system with 400 µm thick YSZ. Tensile adhesion test (TAT) indicated that adhesion strength values of the coated samples are inversely proportional to the ceramic top coat thickness. Contrarily, thermal shock resistance of the coated samples enhanced with increase in thickness of the ceramic coating. Investigation of the TBCs with different thicknesses of NiCrAlY and 300 µm thick YSZ layers revealed that the TBC system with 100 µm thick NiCrAlY layer exhibited the best adhesion strength and thermal shock resistance. It was inferred that thermal mismatch stresses and oxidation of the bond coats were the main factors causing failure in the thermal shock test.     

B4C mineralizing role for mullite generation in Al2O3-SiO2 refractory castables

Based on refractory end-users’ requirements, continuous efforts have been made to design engineered products able to withstand high temperatures (800–1500 °C) and severe thermal gradients. One alternative to enhance the mechanical properties of alumina-based compositions consists of inducing in situ generation of phases with platelet or acicular shape within their matrix fraction, which may improve crack deflection and grain bridging mechanisms. Mullite and Al₁₈B₄O₃₃ are some compounds that present such interesting features. Thus, this work addresses the evaluation of alumina refractory castables bonded with SioxX-Zero and/or microsilica, containing 0 or 1 wt% of B₄C (sintering additive), aiming to: (i) induce transient liquid sintering, (ii) point out which silica source could favor a more effective mullite formation at high temperatures, and (iii) analyze the influence of B₄C in the phase transformation and thermo-mechanical properties of the designed compositions. Comparing SioxX-Zero and microsilica-bonded refractories, the latter showed more likelihood to give rise to the mullite phase during the samples’ thermal treatments. Moreover, adding B₄C to the castables containing 3 wt% of SiO₂ induced the generation of a boron-rich liquid phase with transient features during the samples’ firing step, favoring earlier sintering and faster mullite and Al₁₈B₄O₃₃ formation. These transformations resulted in refractories with enhanced creep, thermal shock resistance and HMOR behavior in a broader temperature range (600–1550 °C), which may enable them to be used in various industrial applications (petrochemical, steel-making, etc.).     

Enhanced formation of magnesium silica hydrates (M-S-H) using sodium metasilicate and caustic magnesia in magnesia castables

Magnesium-silica-hydrates (M-S-H) is a promising binder for magnesia castables due to its bonding strength and progressive dehydration behavior over a wide temperature range during the heating-up stage. Sodium metasilicate and caustic magnesia were used to form M-S-H in magnesia castables. The results showed that M-S-H was remarkably produced in the caustic magnesia-microsilica slurries containing sodium metasilicate with increasing pH value, which activated the hydrolysis of microsilica into silicic ions and enhanced the M-S-H formation. When 0.3 wt% caustic magnesia and 0.05 wt% sodium metasilicate as additives were incorporated into magnesia castables, the cold crushing strength and cold modulus of rupture of castables after drying at 110 °C reached the maximum value of 68.3 MPa, which corresponded to ~ 40% improvement in comparison with those of caustic magnesia and sodium metasilicate-free magnesia castables. Besides, the enhanced formation of M-S-H bonding system contributed to a better explosion resistance of magnesia castables.     

Effect of microsilica addition on the properties of colloidal silica bonded bauxite-andalusite based castables

Colloidal silica bonded bauxite-andalusite based castables were prepared using homogenized bauxite and andalusite as aggregates, andalusite fines, corundum fines, ultrafine Al₂O₃ as matrixes and colloidal silica as binders. Effects of microsilica addition on the green strength, physical properties, hot strength and thermal shock resistance of castables were investigated. Moreover, phase composition and morphological evolution of specimens were characterized by XRD and SEM analysis. Green strength after demoulding, cold strength and hot strength as well as thermal shock resistance of the castables are enhanced with microsilica addition, which attribute to generating more chemical bond (–Si–O–Si–) after demoulding and heating at intermediate temperature (up to 1100 °C), and creating a stronger mullite bonding at higher temperature (1400 °C) compare to the specimens without microsilica.     

An approach for matrix densification based on particle packing and its effect on lightweight Al2O3-MgO castables

For lightweight refractory containing lightweight aggregates, the properties of the matrix are decisive to its performance. In the present work, Dinger–Funk equation was adopted to calculate the theoretical packing density of a castables matrix based on Stovall linear packing model and to design its particle size distribution. Four lightweight Al₂O₃-MgO castables with different particle size distribution (represented by q-value) were prepared and examined. Results show that a suitable q-value was needed to ensure acceptable properties including sintering characteristics, strength and slag resistance, which deteriorated distinctly at high q (>=0.31). For the sample with q=0.28, the matrix showed dense and uniform mirostructure, and the properties of castable reached a favourable compromise among sintering characteristics (apparent porosity=14.8%, bulk density=3.02 g cm⁻³, permanent linear change<0.6%), strength (cold modulus of rapture=12.4 MPa, cold crashing strength=155.5 MPa), and resistance against both slag corrosion (I_c=22.4%) and penetration (I_p=11.5%). The sample with q=0.25 showed the highest strength and resistance against slag corrosion (matrix dissolved in slag), but its slag penetration resistance was lower due to the existence of cracks between aggregates and matrix.     

Biomechanical three-dimensional finite element analysis of monolithic zirconia crown with different cement thickness

Limited information is available on the optimal cement thickness of monolithic zirconia crowns. This study was designed to evaluate the stress distribution in the posterior monolithic zirconia crowns with different cement thicknesses under masticatory force and maximum bite force using three-dimensional finite element analysis. The prepared and unprepared mandibular right first molar models were scanned and exported to the computer-aided design system. Solid models of monolithic zirconia crowns, which were cemented on prepared teeth were generated. Four models were fabricated applying different cement thicknesses (100 µm, 200 µm, 400 µm, and 600 µm). The solid models were imported into the finite element analysis software and meshed into tetrahedral elements. Four three-dimensional finite element models were simulated under masticatory force and maximum bite force: vertical (axial), angular (45°) and horizontal loads of 280 N at 5 points; vertical load of 700 N at 8 points were loaded, respectively. The stress distribution varied with the different cement thicknesses and directions of applied loads. The monolithic zirconia crowns with cement thicknesses exceeding 200 µm had wider distributions of peak maximum principal stress under the same loading conditions. Monolithic zirconia crowns have more stress concentrations on the occlusal surfaces, while the cement layers have more stress concentrations on the cervical areas. Thicker cement layers were associated with more concentrated stresses on the buccal and lingual cervical areas. The test results show that the cement thickness plays an essential role in the success of monolithic zirconia restorations in terms of reducing cement wash-out. Cement thickness of 100 µm is recommended for monolithic zirconia crowns.     

Fracture behavior and thermal shock resistance of alumina-spinel castables-Effect of added fused zirconia-alumina

This study aims to clarify the influence of fused zirconia-alumina (FZA) on the fracture behavior and thermal shock resistance (TSR) of alumina-spinel castables, and discover the relationship between toughness parameters and TSR. Alumina-spinel castables with different FZA contents (0, 2, 4, 6, 8, and 10 wt.%) were prepared using tabular alumina, fused spinel, calcium aluminate cement, ultrafine alumina powder, and FZA as raw materials. The fracture behavior and TSR of alumina-spinel castables were determined by a wedge splitting test (WST) and a water quenching test, respectively. The results show that the flexibility of alumina-spinel castables can be significantly enhanced by introducing FZA. With increasing FZA content, the load-displacement curves change from typical brittle fracture behavior to non-linear fracture behavior. The flexibility parameter (ratio of G_F/σ_NT) of the castables increases from 8.3 μm to 13.6 μm when FZA content increases from 0 wt.% to 10 wt.%. The flexibility improvement of castables containing FZA can be attributed to the formation of microcracks caused by the transformation of ZrO₂. The TSR of alumina-spinel castables can also be significantly improved by adding FZA. The ratio of residual cold modulus of rupture (CMOR) of the castables increases from 12.3% to 34.2% when FZA content increases from 0 wt.% to 10 wt.%. The improvement in TSR can be attributed to a decrease in the stored elastic energy and a subsequent increase in the specific fracture energy of the castables. Generally, alumina-spinel castables with non-linear fracture behavior have good thermal shock resistance. There is a significant correlation between the flexibility parameter (G_F/σ_NT ratio) and the ratio of residual CMOR; the correlation coefficient is 0.96.     

原位生成非氧化物对刚玉基浇注料性能的影响

为了进一步提高刚玉基浇注料的高温使用性能,在超低水泥刚玉浇注料中加入质量分数分别为0、4%、6%、8%、10%的硅粉,经振动浇注成型、养护、烘干后,在氮气气氛中于1 450℃氮化处理40 h,测定试样的加热永久线变化及烧后试样的显气孔率、体积密度、常温抗折强度和不同温度(分别为1 000、1 200、1 300和1 400℃)下的热态抗折强度,并对部分氮化后试样进行XRD和SEM分析。结果表明:1)随着硅粉加入量的增加,试样在氮化处理过程中从发生微收缩到发生微膨胀,显气孔率略有增大,体积密度和常温抗折强度下降,热态抗折强度显著提高;2)氮化处理后,试样中原位生成了非氧化物β-SiAlON、O’-SiAlON和α-Si3N4等。     

Thermal shock damage evaluation of refractory castables via hot elastic modulus measurements

When refractory castables are submitted to continuous thermal changes, crack nucleation and/or propagation can take place resulting in a loss of mechanical strength and overall degradation of such materials. This work evaluates the thermal shock damage cycling of high-alumina and mullite refractory castables designed for petrochemical application. Hot elastic modulus analyses were carried out after 0, 2, 4, 6, 8 and 10 thermal cycles (ΔT=800 °C) in order to investigate the microcracking evolution due to the temperature changes. Additionally, apparent porosity, hot modulus of rupture, erosion and work of fracture measurements were also performed. According to the attained results, it was detected at which temperature range the stiffening or embrittlement took place in the mullite-based refractory (M-SA) microstructure. Nevertheless, the damage induced by the thermal shock tests was not permanent, as further increase of the elastic modulus results was observed for all evaluated samples after annealing. On the other hand, the alumina-based composition containing a sintering additive (TA-SA) presented enhanced mechanical strength, high thermal stability and E values. Simulations indicated that refractories with high E values (∼140 GPa, such as those attained for alumina-based castable) showed a reduced amount of stored elastic strain energy even under severe thermal stresses, which seems to be a key aspect for the engineered design of thermal shock resistance materials.     

Fabrication of surface-treated BN/ETDS composites for enhanced thermal and mechanical properties

The ceramic/polymer composites based on epoxy-terminated dimethylsiloxane (ETDS) and boron nitride (BN) were prepared for use as thermal interface materials (TIMs). 250 µm-sized BN was used as a filler to achieve high-thermal-conductivity composites. To improve the interfacial adhesion between the BN particles and the ETDS matrix, the surface of BN particles were modified with silica via the sol–gel method with tetraethyl orthosilicate (TEOS). The interfacial adhesion properties of the composites were determined by the surface free energy of the particles using a contact angle test. The surface-modified BN/ETDS composites exhibited thermal conductivities ranging from 0.2 W/m K to 3.1 W/m K, exceeding those of raw BN/ETDS composites at the same weight fractions. Agari׳s model was used to analyze the measured thermal conductivity as a function of the SiO₂-BN concentration. Moreover, the storage modulus of the BN/ETDS composites was found to increase with surface modification of the BN particles.     

Effect of particle size on dry sliding wear behaviour of sillimanite reinforced aluminium matrix composites

Present work describes the development of Al-Si/sillimanite reinforced composites via stir casting route. Sillimanite is abundant mineral available in coastal regions of India and has not been explored much as reinforced mineral for the development of composites. In the present work, dry sliding wear behaviour of LM30 aluminium alloy reinforced with sillimanite has been investigated. Composites reinforced with sillimanite in different weight percentage (3–18 wt percentage) and particle size range (fine: 1–20 µm, medium: 32–50 µm, and coarse: 75–106 µm) were prepared. Microstructural studies revealed uniform distribution of sillimanite particles in the matrix of composites. Nanoindentation taken at different phases indicated good bonding between reinforced particles and matrix. Fine particles (1–20 µm) reinforced composites containing 15 wt% sillimanite exhibited higher wear resistance which is 55% more compared to base LM30 alloy. Beyond this reinforcement level, wear resistance deteriorated because of agglomeration of the fine particles. Analysis of wear track and debris revealed that at low applied loads, abrasive wear was predominant whereas at higher applied loads, adhesive wear was dominating factor.