The Role of the Size Effect on the Drying of Refractory Castables—How Its Under-standing Could Narrow the Gap between Laboratory Studies and Industrial Reality

Refractories have unique capabilities such as sustaining their shape and properties at extreme conditions such as the combination of high temperatures and thermal shock,contact with molten metals and slags and in some circumstances resistance to erosion from abrasive particles.Given the large processing output of the heavy industries such as the cement and steel ones which both require high temperature processes,the refractories structures span various meters and weight of several tons.As the water removal stage of hydraulic bonded castables in industrial sites takes hours(10-60 h)due to the risk of explosive spalling,efforts to mitigate it are commonly studied.This has provided theoretical understanding of the general aspects of drying and important tools,such as the thermogravimetry analysis(TGA),for the design of refractory compositions with higher explosive spalling resistance.However,the optimization of this process is still far from the industrial reality especially because the actual linings that require the drying are orders of magnitude larger than the samples considered in the laboratory tests.Therefore,this study proposed the analysis of the sample volume effect on the water removal dynamics through TGA of high alumina castables with calcium aluminate cement.Conventionalφ5 cm×5 cm cylindrical samples were assessed in a laboratory scale equipment whereas macro TGA were carried out considering 20 cm×20 cm×20 cm and 30 cm×30 cm×30 cm cubic samples.Additionally,the effect of polymeric fibers was also considered.It was found out that the different thermal gradients within the macro TGA samples resulted in an inflection on the sample’s heating rate and that the mass loss was affected by the volume considered,especially for the composition without additives.These findings highlight the requirement of carefully taking into consideration the different dimensional sizes and thermal gradients in the samples when analyzing and interpreting the laboratory studies,and especially when trying to extrapolate such results to the industrial reality.

Exploring Dry-out Behaviour and Explosion Resistance of Microsilica-gel Bonded No-cement Castables

Cement-free castables have attracted significant attention due to their superior thermal-mechanical properties and rapid dry-out in comparison to cement-bonded refractory castables.However,drying industrial-scale specimens can pose more challenges than lab-scale samples.In this study,the dry-out behavior and explosion resistance of microsilica-gel bonded nocement castables(NCCs)were investigated on both lab-and industrial-scale specimens,employing various drying agents.First,the fast dry-out mechanism was assessed using thermogravimetric analysis(TGA),differential scanning calorimetry(DSC),and scanning electron microscopy(SEM)on lab-scale small samples.Then,the drying behavior of industrial-scale large samples(300 mm×300 mm×300 mm cubes,approximately 80 kg)was studied using a unique macro-thermo-balance(macro-TGA).The results showed that EMSIL-DRY^(®)reduced the temperature level for maximum dewatering rate and effectively prevented explosions during heat-up,compared to other polymer fibres.The use of a specialty drying agent(EMSIL-DRY^(®))significantly improved the explosion resistance,as demonstrated by the production of a perfect 400 kg block fired to 850℃at a rate of 50℃·h^(-1).This research contributes to the understanding and application of cement-free castables in industrial settings.

Regulation of Pore Structure and Hightemperature Fracture Behavior of CACbonded Alumina-Spinel Castables Based on Hydration Design

The lamellar hydrates of CAC were designed with the introduction of nano CaCO_(3)or Mg-Al hydrotalcite(M-A-H),and the effects on the green strength,pore structures,and high-temperature fracture behavior of alumina-spinel castables were investigated.The results show that nano CaCO_(3)or M-A-H stimulates rapidly the hydration of CAC and the formation of lamellar C_(4)AcH_(11)or coexistence of C_(2)AH_(8)and C_(4)AcH_(11)at 25℃.The formation of lamellar hydrates can contribute to a more complicated pore structure,especially in the range of 400-2000 nm.Meanwhile,the incorporation of well-distributed CaO or MgO sources from nano CaCO_(3)or M-A-H also regulates the distribution of CA_(6)and spinel(pre-formed and in-situ).Consequently,the optimized microstructure and complicated pore structure can induce the deflection and bridging of cracks,thus facilitating the consumption of fracture energy and enhancing the resistance to thermal stress damage.

Effect of H_(2)O_(2) Addition on Anti-explosion Performance of p-Al_(2)O_(3) Bonded Corundum Castables

In order to improve the anti-explosion performance ofρ-Al_(2)O_(3) bonded corundum castables,H_(2)O_(2) was added(0,0.025%,0.050%,0.075%,0.100%and 0.125%,by mass)as the anti-explosion agent.After mixing and casting,specimens were prepared.Some specimens were cured at room temperature for 12 h and demoulded for the anti-explosion performance test at different temperatures(450,500,550,600,650,700,750 and 800℃);the other specimens were cured,dried and fired,and tested in terms of the apparent porosity,the density,the cold mechanical properties,the air permeability and the pore size distribution.The results show that:(1)with the increase of the H_(2)O_(2) addition,the anti-explosion performance of castables increases gradually,the average pore size increases gradually,and the density and the strength decrease gradually;(2)by comprehensive consideration,the appropriate addition of H_(2)O_(2) shall be within 0.075%.

Effect of Different Silica Fumes on Properties of Al_(2)O_(3)-SiC-C Castables for Iron Trough

In order to improve the performance of Al_(2)O_(3)-SiC-C castables for iron trough,samples were prepared using brown corundum,dense corundum,activated alumina micropowder,ball pitch,and silicon as main raw materials,calcium aluminate cement as the binder.Several kinds of silica fumes(93SiO_(2),96SiO_(2),and 99SiO_(2))with different particle size distributions and chemical composition were added to research the effects on the properties of castables.The results show that the sample with 99SiO_(2) fume has high water requirement for molding,but the bulk density is the lowest,the apparent porosity is the highest,the oxidation resistance is the worst,and the permanent linear change on heating is low after firing at 1 450 ℃ for 3 h.The bulk density and the apparent porosity of the sample with 93SiO_(2) fume or 96SiO_(2) fume are equivalent,the hot modulus of rupture of the sample with 93SiO_(2) fume is the lowest,and the slag resistance of the sample with 96SiO_(2) fume is the best.The comprehensive performance of the sample with 96SiO_(2) fume is the best.

Preparation of Lightweight Alumina-silica Castables by Replacing Closed-cell Perlite Aggregates with Coal Gangue Ceramsites

Lightweight alumina-silica castables were prepared using closed-cell perlite(2-4 mm),open-cell perlite(4-6 mm)and coal gangue ceramsites(2-5 mm)as aggregates,floating beads(0.3-0.5 mm),sinking beads(0.6-0.8 mm),silica micropowder,α-Al_(2)O_(3) micropowder,zirconia and zircon micropowder as fines,and Secar 71 cement(calcium aluminate cement)as the binder.The effects of the coal gangue ceramsites addition(0,6%,12%,18%and 24%,by mass)on the properties of the as-prepared lightweight alumina-silica castables were investigated.The results show that:(1)the addition of coal gangue ceramsites can reduce the sintering shrinkage of the specimens and help to improve the strength and thermal shock resistance;(2)the samples with the addition of coal gangue ceramsites can produce pores in the matrix of the sintered samples,which provides enough space for the growth of CA6 complex solid solution and expands the irregular lamellar structure;(3)with the addition of coal gangue ceramsites increasing,the linear shrinkage of the samples heat treated at 1000 or 1200℃firstly reduces and then increases,the bulk density increases and the apparent porosity decreases;the cold compression strength and the thermal shock resistance of the specimens heat treated at 1200℃firstly increase and then decrease.Thus,the optimal addition of coal gangue ceramsites is 18%.

Effect of Zirconia Corundum Addition on Properties of Chrome Corundum Castables

In order to investigate the effect of zirconia corundum on the preparation of chrome corundum castables,samples were prepared using tabular corundum,white fused corundum,active alumina micropowder,chromium oxide micropowder and fused ziconia corundum particles as the main raw materials,and pure calcium aluminate cement as the binder.The effects of the fused zirconia corundum particles addition(1-0.5 mm,0,4.5%,9%,and 18%,by mass)on the linear change rate,the apparent porosity,the cold modulus of rupture,and the thermal shock resistance of chrome corundum castables were studied,and the microstructure of the samples was analyzed.The results show that:(1)with the zirconia corundum addition increasing,the permanent linear change on heating of the samples gradually increases,the apparent porosity gradually increases,the cold modulus of rupture gradually decreases,and the thermal shock resistance gradually increases;(2)according to SEM,it can be found that the phase transformation of ZrO2 after heat treatment leads to a large number of microcracks in the material.On one hand,the cold modulus of rupture of the material is reduced;on the other hand,the thermal shock resistance of the material is improved.

Fabrication and Improving Properties of Lightweight Al_(2)O_(3)-MgO Castables for L adle Working Lining

Three lightweight Al_(2)O_(3)-MgO castables were fabricated with tabular alumina or microporous corundum as the aggregates,reactiveα-Al_(2)O_(3)micropowder,tabular alumina powder,and fused magnesia powder as the matrix,calcium aluminate cement as the binder,and MgO ultrafine powder(d50=5.4μm)and Al(OH)3 ultrafine powder(d50=8.2μm)as additives.The influence of aggregates and ultrafine powders on the properties,including pore size distribution,heat conductivity,thermal shock resistance,and slag resistance of lightweight refractory castables was investigated.The results show that the incorporation of microporous corundum reduces the bulk density of Al_(2)O_(3)-MgO castables,and MgO and Al(OH)3 ultrafine powders further increases the proportion of micropores in castables,which is beneficial to reducing the heat conductivity,and improving the thermal shock resistance and slag resistance of castables.Additionally,MgO ultrafine powder and Al(OH)3 ultrafine powder increase the fluidity and the strength of castables.

Binder Effect on Properties of Cr_(2)O_(3)-bearing Corundum-based Refractory Castables

Cr_(2)O_(3)-bearing castables bonded with reactive MgO(RM)or calcium aluminate cement(CAC)were studied to evaluate the binder effect on their performance in corrosive environments.The properties of the as-prepared castables were compared with respect to the differences in phase composition and microstructure.The corrosion behavior of the as-prepared castables by CaO-Al_(2)O_(3)-Fe_(2)O_(3)-SiO_(2)-based slag was systematically compared viarefractory cup testing at 1600℃with respect to the differences in phase composition and microstructure.The analysis indicates that RM bonded castables show higher apparent porosity,lower bulk density and strengths after drying at 110℃and firing at 1300℃,and higher permanent linear change after firing at 1300℃,but better slag corrosion and infiltration resistance compared with CAC bonded castables.

Effect of Boric Acid on Properties of Calcined Flint Clay-bauxite Castables

In order to prolong the working time of calcined flint clay-bauxite castables during construction at high temperature,boric acid was added into the castables. The effect of boric acid on working time and curing cold crushing strength of the castables at 25 ℃ and 35 ℃ were investigated. After 24 h curing in mould and another 24 h curing at 110 ℃ after demoulding,the specimens were heat treated at 1 000 ℃,1 300 ℃,and 1 500 ℃ for 3 h,respectively. The permanent linear change,bulk density,modulus of rupture,and cold crushing strength were determined. The result shows that there is no need to add boric acid when calcined flint clay-bauxite castables works at 25 ℃; when calcined flint clay-bauxite castables works at 35 ℃,boric acid can increase the working time of the castables,but decrease the curing cold crushing strength a little. Adding boric acid into calcined flint clay-bauxite castables doesn＇t worsen performance of the castables.

Thermal Behavior in Relation to Different Bindings of Alumina Based Castables from 20 to 1000℃

Thermal behavior and physical properties of castables during curing and drying-out are associated with their binding system. In this work, five alumina based （ Al2O3 〉 87% ） castables with different combinations of binding materials, i. e. , （ 1 ） CA cement （CA） ＋ Reactive alumina （ RA ） ＋ H2O ; （ 2 ） high level addi- tion of CA ＋ Microsilica （MS） ＋ H2O ; （ 3 ） low level addition of CA ＋ MS ＋ H2O ; （4） MS ＋ Hydratable alumina ＋ H20 and （ 5 ） MS ＋ Magnesia ＋ H2O, respectively, have been investigated on the flowability and thermal behavior during curing at room temperature, drying at 110% and heating from 200℃ to 1000℃ at an interval of 100℃ , in terms of water addition, vibration flow value, porosity, dehydration, explosion resistance, cold and hot bending strengths. Differences in dehydrating behavior and the mentioned properties have been revealed and correlated to the binding system.

Rheological Behavior of Bauxite-Based SiC-Containing Castables

Low cement (LC) and ultra low cement (ULC) bauxite SiC castables are important and high performance monolithic refractories and they have been widely used in iron making and incinerator linings. In this work, rheological behavior of LC and ULC bauxite based SiC containing castables has been studied, including the effects of SiC content and cement content on rheological properties of the castables. The results show that with an increase of SiC and cement content, rheological properties of the castables deteriorate. On the other hand, moderate amounts of SiC (4%～8%) and of calcium aluminate cement (2%～4%) have very slight influence on rheological properties, (i.e. when the castables are sheared their torque and yield torque only slightly increase with the shearing speed). The rheological characteristics of the castables follow Bingham fluid and always show shear thinning behavior.

Comparison of Setting Behaviour and Mechanical Properties of Various Silica-bonded No-cement Castables

Microsilica-gel bonded bauxite based no-cement refractory castables（NCCs）have been produced using two readily available dispersants.These NCCs were compared to NCC with Siox X-Zero,a purposely-developed product for microsilica-gel bonded no-cement castable systems to control flow properties and setting characteristics.Three mixing and curing temperatures were applied：5℃,20℃and 35℃.The results show that setting-behaviour and mechanical properties strongly vary with the type of dispersant and the curing temperature.However,both setting and strength are less temperature dependent in the castables with Siox X-Zero.Furthermore,the drying and firing of microsilica-gel bonded NCCs were investigated.Since microsilica-gel bond system contains only a small amount of bound water,the castables can be fired at very high heating rates,once the free water has been removed.

Effects of Nano Calcium Carbonate on Strength and Microstructure of Corundum-based Castables

The castables specimens were prepared using white fused alumina particle and powder, α-Al2O3 micropowder, hydrated alumina, nano calcium carbonate or calcium aluminate cement as starting materials. Effects of nano calcium carbonate addition on phase compositions, strength and microstructure of corundum based castables were studied. The calcium aluminate cement-containing corundum based castables with the same CaO amount was also tested for comparison. The results show that, when temperature is higher than 900 ℃ , the phase compositions of nano CaCO3-containing mixture and the calcium aluminate cement containing mixture are the same, but the forming mechanism, modality and distribution of new phases in the castables are different. With temperature rising, the hydration cement dehydrates and reacts inside cement forming calcium aluminate until the alumina in cement is not enough for the reaction （ternperature is 91 400 ℃ ） , then reacts with the surrounding alumina forming cluster CA6 in the castables. The change process of nano CaCO3 in corundum based enstables is that nano calcium carbonate decomposes to CaO after firing at 800℃ which reacts with Al2O3 forming amorphous calcium aluminate that causes an in-situ bonding. With temperature rising, the formed calcium aluminate reacts with Al2O3 in matrix and wholly forms tabular CA6 at 1 600 ℃ , which distributes uniformly in the castables. The cold and hot strength of the castables with nano calcium carbonate are obviously higher than those of the castables without nano calcium carbonate, especially at 800 -1 000 ℃ due to smaller size and higher dispersion of the nano calcium carbonate and its different reaction mechanism with Al2O3.

Comparisons Between Vibration and Self-Flowing Ultra-Low Cement Castables Properties in Al_2O_3-SiC-C System

In this study, the properties of self-flowing ultra-low cement castables in Al2O3-SiC-C system have been investigated and compared to vibration castables. The major physical and mechanical properties, microstructure and corrosion behavior of these castables against slag have been evaluated. The results showed that the microstructure of Al2O3-SiC-C self-flowing castable is more uniform than the vibrated structure. Also self-flowing castable has smaller pore size and more uniform pore size distribution. Hence, density, strength, oxidation and slag resistance of the self-flowing castables is higher than that of vibration castables. Therefore, besides other benefits such as noise free, easy installation, fewer mold defects and reduced installation costs, Al2O3-SiC-C self flowing ultra low cement castables will have longer service life in comparison with vibration casables.

Effect of Microsilica Addition on Properties of CMA72 Bonded Al2O3-MgO Castables

CMA72 bonded Al2 O3 - MgO castable is promising for application of steel ladle wall, because of unique combination of thermo-mechanical properties, slag corro- sion resistance and cost benefit. In these castables, mi- crosilica can be introduced to counterbalance the expan- sion generated by spinel formation. In this paper, the of microsilica dosage on properties of eastables was evaluated. Expansion, expressed by the permanent linear change （PLC）, is highly dependent on the dosage of microsilica. Unexpected expansion occurs when the dos- age of microsilica is too low due to dominant effect of spinel and CA6 formation. Too high dosage results in sintering shrinkage, which is related to amount of liquid phase generated by microsilica addition. In addition, HMOR declines dramatically with increasing microsilica dosage. Considering the balance between expansion con- trol and hot property retention, 1.0 mass% of microsili- ca is recommended for the castable containing 4 mass% of magnesia.

Pore Size Distribution and Its Quantitative Relationship with Strength of Corundum Based Castables

A series of corundum based castables with 0,2%,4%,6%,and 8% α-Al2O3 micropowders were prepared using tabular alumina aggregates （6-3,3-1 and ≤1 mm） and fines （≤0.088 and ≤0.045 mm）,calcium aluminate cement,and α-Al2O3 micropowders （d50=1.754 μm） as starting materials. Cold mechanical strength and pore size distribution of the castables specimens after heat treatment at 110,1 100 and 1 500 ℃ were tested,respectively. The quantitative relationship between strength and apparent porosity,and that between strength and median pore diameter were verified by Atzeni equation. The correlation between interval of pore size and mechanical strength of specimens was also studied by means of gray relational theory. The results show that：（1） the pore size distribution of castables is strongly influenced by both micropowders filling and matrix sintering; the addition of micropowders decreases median pore diameter while the sintering process increases it; （2） when adding a constant correction term,Atzeni equation can substantially describe the quantitative relationship between median pore diameter and strength of castables specimens after heat treatment at the same temperature; the significant differences of the gray relational degree between the interval of pore size and castables strength are characterized; it is also found that for the same interval of pore size,the gray relational degree isaffected by the heat treatment temperature; the pore size interval 〈0.5 μm has the highest gray relational degree with the strength at 110-1 500 ℃.

Effects of Spherical Aggregates Addition on Properties of Al2O3-SiO2 System Castables

Compared with traditional aggregates,spherical aggregates with high flowability,easy control of particle size distribution and favor of dense packing and so on,are expected to replace traditional aggregates as important raw materials for future high performance refractories. Therefore,investigation of effects of spherical aggregates addition on properties of refractories becomes very meaningful. Using A70 mullite traditional aggregates and A70 mullite spherical aggregates, bauxite homogenization powder,microsilica,and calcium aluminate cement as raw materials,different AlO-SiOsystem low cement castables were prepared by replacing conventional aggregates with spherical aggregates. The effect of spherical aggregates addition on workability and mechanical properties of castables after heated at different temperatures was researched,and microstructure of the specimen was analyzed by SEM. Compared with traditional irregularly shaped aggregates,spherical aggregates endow castables with better flowability and easy pump ability. By introduction of spherical aggregates into the castables,flowability and pumpability are significantly improved,and water addition and ball completely sunk time are reduced. The introduction of spherical aggregates is favorable to density and cold crushing strength of castables,but unfavorable to CMOR. The effect of spherical aggregates addition on HMOR at1 400 ℃ can be negligible. Microstructure analysis showsthat the boundary bonding between spherical aggregates and matrix is strong,similar to the traditional aggregates.

Flow and Flow Decay of Refractory Castables

Installation of refractory castables depend not only on flow , but also on how soon the flow is lost because of setting. The loss of flow (flow decay) has always been one of the main problems of refractory castable manufacturers , a problem that has not been too well described in literature . The flow decay has been studied for a castable system based on alumina , pointing out some general trends . The flow decay was found very temperature sensitive, being strongly accelerated by temperature increases. To compensate for excessive flow loss, a retarder like citric acid may be used. Thus flow decay was measured as a function of citric acid ( retarder) addition at 35℃.

Effect of MgCl2 Solution Impregnation Process on Properties of Alumina-spinel Castables

In order to improve the properties of purging plugs and to prolong their service life,this work attempted to impregnate alumina-spinel castables for purging plugs in refining ladle with saturated magnesium chloride solution under vacuum.After being impregnated for the first time,the specimens were treated in two different ways:(1)dried at 110℃for 24 h;(2)heated at 600℃for 3 h.Then they were impregnated for the second time.All specimens were heated at 1550℃for 3 h,then the cold properties and the high temperature properties were tested according to corresponding standards.Test results were compared and analyzed.The results show that:after being impregnated,the specimen have both better cold properties and high temperature properties,the microstructure analysis result proves that it is attributed to in situ formed spinel.However,because MgO produced by MgCl2-6H20 decomposing above 527℃can hydrate and destroy specimen microstructure,which can make the properties of specimens impregnated in the second way get worse.By comprehensive consideration,the first scheme way is more suitable.