Nanocrystalline calcium aluminates with different CaO/Al2O3 ratios were prepared by a facile co-precipitation method using Poly（ethylene glycol）-block-poly（propylene glycol）-block-poly（ethylene glycol） （PEG-PPG...Nanocrystalline calcium aluminates with different CaO/Al2O3 ratios were prepared by a facile co-precipitation method using Poly（ethylene glycol）-block-poly（propylene glycol）-block-poly（ethylene glycol） （PEG-PPG-PEG, MW： 5800） as a surfactant. They were employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by X-ray diffraction （XRD）, N2 adsorption （BET）, temperature-programmed reduction and oxidation （TPR-TPO）, and scanning electron microscopy （SEM） techniques. Catalysts showed a relatively high catalytic activity and stability. TPR analysis revealed that the catalysts with higher CaO content are more difficult to be reduced. TPO analysis showed that the 5 wt%Ni/CA and 5 wt%Ni/C12A7 catalysts with higher CaO amount were effective against coke deposition.展开更多
Dissolution kinetics of CaO·2Al_(2)O_(3)(CA_(2))particles in a synthetic CaO-Al_(2)O_(3)-SiO_(2)steelmaking slag system have been investigated using the high-temperature confocal laser scanning microscope.Effects...Dissolution kinetics of CaO·2Al_(2)O_(3)(CA_(2))particles in a synthetic CaO-Al_(2)O_(3)-SiO_(2)steelmaking slag system have been investigated using the high-temperature confocal laser scanning microscope.Effects of temperature(i.e.,1500,1550,and 1600℃)and slag composition on the dissolution time of CA_(2)particles are investigated,along with the time dependency of the projection area of the particle during the dissolution process.It is found that the dissolution rate was enhanced by either an increase in temperature or a decrease in slag viscosity.Moreover,a higher ratio of CaO/Al_(2)O_(3)(C/A)leads to an increased dissolution rate of CA_(2)particle at 1600℃.Thermodynamic calculations suggested the dissolution product,i.e.,melilite,formed on the surface of the CA_(2)particle during dissolution in slag with a C/A ratio of 3.8 at 1550℃.Scanning electron microscopy equipped with energy dispersive X-ray spectrometry analysis of as-quenched samples confirmed the dissolution path of CA_(2)particles in slags with C/A ratios of 1.8 and 3.8 as well as the melilite formed on the surface of CA_(2)particle.The formation of this layer during the dissolution process was identified as a hindrance,impeding the dissolution of CA_(2)particle.A valuable reference for designing or/and choosing the composition of top slag for clean steel production is provided,especially using calcium treatment during the secondary refining process.展开更多
In order to remove or reduce the negative effect of MgO in calcium aluminate slags, the method of adding Na2O into calcium aluminate slags was studied and its effect on leaching mechanism was also analyzed. The result...In order to remove or reduce the negative effect of MgO in calcium aluminate slags, the method of adding Na2O into calcium aluminate slags was studied and its effect on leaching mechanism was also analyzed. The results show that the alumina leaching efficiency of the calcium aluminate slag increases from 68.73% to 80.86% with Na2O content increasing from 0 to 4% when MgO content is 3%. The XRD results show that the quaternary compound C20A13M3S3 disappears when Na2O content increases to 4%. The addition of Na2O cannot remove the negative effect of MgO on leachability completely. XRD and EDS results indicate that Na2O can come into the lattice of 12CaO·7Al2O3 and promote the formation of 12CaO·7Al2O3展开更多
SiO2 in calcium aluminate slag exists in the form of γ-2CaO·SiO2 which is more stable than β-2CaO·SiO2. However, it is decomposed by sodium carbonate solution during leaching process, leading to the second...SiO2 in calcium aluminate slag exists in the form of γ-2CaO·SiO2 which is more stable than β-2CaO·SiO2. However, it is decomposed by sodium carbonate solution during leaching process, leading to the secondary reaction. The extent of secondary reaction and reaction mechanism of calcium aluminate slag were studied using XRD. The results show that the decomposition rate of γ-2CaO·SiO2 increases with the increase in leaching time and sodium carbonate concentration. The main products of secondary reaction are the mixture of hydrogarnet and sodium hydrate alumina-silicate. SiO2 concentration rises firstly and then drops with the increase of leaching temperature. XRD results indicate that the stable product of secondary reaction at low temperature is hydrogarnet. But hydrogarnet is transformed into sodium hydrate alumina-silicate at high temperature.展开更多
The mineral transition mechanism and physicochemical property of calcium aluminate clinker sintered at 1350 ℃ were systematically studied using analytical reagent α-Al 2O 3,CaCO 3 and SiO 2 when the molar ratio of C...The mineral transition mechanism and physicochemical property of calcium aluminate clinker sintered at 1350 ℃ were systematically studied using analytical reagent α-Al 2O 3,CaCO 3 and SiO 2 when the molar ratio of CaO to Al 2O 3 is 1.0.The results show that the formation of Ca 2SiO 4 accelerates the diffusion of CaO and Al 2O 3,which promotes the formation of CaAl 2O 4 determined by dilatometer,X-ray diffraction,Fourier transform infrared spectroscopy and scanning electron microscopy methods.CaAl 4O 7,Ca 3Al 2O 6,Ca 3SiO 5 and Ca 2Al 2SiO 7 only exist in the initial stage of reactions,the amounts of which decrease with the increase of sintering duration.Ca 3Al 2O 6 and Ca 12Al 14O 33 react with Al 2O 3 and CaAl 4O 7 to form CaAl 2O 4,while Ca 2Al 2SiO 7 reacts with CaO and Ca 12Al 14O 33 to form Ca 2SiO 4 and CaAl 2O 4.The sintered clinker contains CaAl 2O 4 and γ-Ca 2SiO 4 as well as some Ca 12Al 14O 33 when the sintering duration is longer than 1.0 h.The differential scanning calorimetry results reveal that Ca 2SiO 4,Ca 2Al 2SiO 7 and CaAl 2O 4 are formed at985 ℃,1045℃ and 1339 ℃,respectively.Increasing the sintering duration contributes to the transition of β-Ca 2SiO 4 to γ-Ca 2SiO 4,which improves the pulverization and alumina leaching property of the sintered clinker.展开更多
Calcium aluminate clinkers doped with Na2O were synthesized using analytically pure reagents CaCO3, Al2O3, SiO2 and Na2CO3. The effects of Na2O-doping on the formation mechanism of calcium aluminate compounds and the ...Calcium aluminate clinkers doped with Na2O were synthesized using analytically pure reagents CaCO3, Al2O3, SiO2 and Na2CO3. The effects of Na2O-doping on the formation mechanism of calcium aluminate compounds and the crystal property of 12CaO·7Al2O3 (C12A7) cell were studied. The results show that the minerals containing Na2O mainly include 2Na2O·3CaO·5Al2O3 and Na2O·Al2O3, when the Na2O content in clinkers is less than 4.26% (mass fraction). The rest of Na2O is mainly doped in 12CaO·7Al2O3, which results in the decrease of the crystallinity of 12CaO·7Al2O3. The crystallinity of 2Na2O·3CaO·5Al2O3 is also inversely proportional to the Na2O content in clinkers. The formation processes of 2Na2O·3CaO·5Al2O3 and 12CaO·7Al2O3 can be divided into two ways, which are the direct reactions of raw materials and the transformation of CaO·Al2O3, respectively. The simulation shows that the covalency of O-Na bond in Na2O-doped 12CaO·7Al2O3 cell is weaker than those of O-Ca and O-Al bonds. The free energy of the unit cell increases because of Na2O doping, which results in the improvement of chemical activity of 12CaO·7Al2O3. The leaching efficiency of Al2O3 in clinker is improved from 34.81% to 88.17% when the Na2O content in clinkers increases from 0 to 4.26%.展开更多
The sintering characteristics at 1350℃ and leaching property at 80℃ of calcium aluminate clinkers in the CaO-Al2O3-SiO2 （C-A-S） system with different additions of FeO and Fe2O3 were investigated. FeO inhibits the ...The sintering characteristics at 1350℃ and leaching property at 80℃ of calcium aluminate clinkers in the CaO-Al2O3-SiO2 （C-A-S） system with different additions of FeO and Fe2O3 were investigated. FeO inhibits the conversion of β-Ca2SiO4 to γ-Ca2SiO4 and makes the clinker not pulverizable. FeO and Fe2O3 inhibit the formation of CaAl2O4, but promote the formation of Ca12Al14O33. The interplanar spacing at （2 1 1） crystal face of Ca12 Al14O33 in the clinker increases with the increase of FeO addition, which indicates that FeO forms solid solutions in Ca12Al14O33. The clinkers with Fe2O3 addition form a new phase Ca2Fe2O5, and the amount of Ca2Fe2o5 increases with the in crease of Fe2O3 addition. Both FeO and Fe2O3 do not affect the Al2O3 leaching rate of calcium aluminate clinker in sodium carbonate solution, but they increase the molar ratio of caustic Na2O to Al2O3 in the leached liquor.展开更多
The mineral transition and formation mechanism of calcium aluminate compounds in CaO-Al2O3-Na2O system during the hightemperature sintering process were systematically investigated using DSC-TG,XRD,SEM-EDS,FTIR,and Ra...The mineral transition and formation mechanism of calcium aluminate compounds in CaO-Al2O3-Na2O system during the hightemperature sintering process were systematically investigated using DSC-TG,XRD,SEM-EDS,FTIR,and Raman spectra,and the crystal structure of Na4Ca3(AlO2)10 was also simulated by Material Studio software.The results indicated that the minerals formed during the sintering process included Na4Ca3(AlO2)10,CaO·Al2O3,and 12 CaO·7 Al2O3,and the content of Na4Ca3(AlO2)10 could reach 92 wt%when sintered at 1200°C for 30 min.The main formation stage of Na4Ca3(AlO2)10 occurred at temperatures from 970 to 1100°C,and the content could reach82 wt%when the reaction temperature increased to 1100°C.The crystal system of Na4Ca3(AlO2)10 was tetragonal,and the cells preferred to grow along crystal planes(110)and(210).The formation of Na4Ca3(AlO2)10 was an exothermic reaction that followed a secondary reaction model,and its activation energy was 223.97 kJ/mol.展开更多
This paper describes a study on the corrosion behavior of steel reinforcement in CAC mortars via electrochemical methods including corrosion potential,electrochemical impedance,and linear polarization evaluation.Resul...This paper describes a study on the corrosion behavior of steel reinforcement in CAC mortars via electrochemical methods including corrosion potential,electrochemical impedance,and linear polarization evaluation.Results indicate that there is a non-linear relationship between the corrosion degree of steel reinforcement in CAC mortar and the concentration of NaCl solution.The electrochemical parameters of specimens immersed in 3%NaCl solution suddenly drop at 40 days,earlier than 60 days of the reference.And the charge transfer resistivity of the specimen has decreased by 11 orders of magnitude at 40 days,showing an evident corrosion on steel reinforcement.However,it is interesting to notice that the corrosion is delayed by high external chloride concentration.The specimens immersed in 9%and 15%NaCl solutions remain in a relatively stable state within 120 days with slight pitting.The great corrosion protection of CAC concrete to embedded steel bars enables its wide application in marine.展开更多
In order to study the effect of the curing temperature on the intermediate temperature properties of calcium aluminate cement bonded corundum castables,the prepared castables were cured at 5,10,25,40 and 50℃,respecti...In order to study the effect of the curing temperature on the intermediate temperature properties of calcium aluminate cement bonded corundum castables,the prepared castables were cured at 5,10,25,40 and 50℃,respectively,dried at 110℃ for 24 h and heat treated at 800 and 1100 ℃,respectively.Then the apparent porosity,the cold modulus of rupture and the cold crushing strength were measured.The phase composition of castable matrix specimens treated under the same conditions and the influence of the curing temperature on the intermediate temperature strength of the castables were also analyzed.The results show that with the increase of the curing temperature,the hydration degree of calcium aluminate cement increases,which promotes the uniform distribution of hydration products with AI203 after decomposition,thus enhancing the intermediate temperature strength of castables.展开更多
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 ca...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.展开更多
The early hydration of calcium aluminate cement (CAC) with different kinds of zinc (II),such as ZnSO4g7H2O,ZnO,Zn(NO3)2·6H2O and ZnCl2,was analyzed.Changes in consistency,setting time,hydration heat flow,hydratio...The early hydration of calcium aluminate cement (CAC) with different kinds of zinc (II),such as ZnSO4g7H2O,ZnO,Zn(NO3)2·6H2O and ZnCl2,was analyzed.Changes in consistency,setting time,hydration heat flow,hydration heat amount,ion concentration in solution,and hydration products were found upon the addition of different Zn^2+.The water consumption of standard consistency of CAC is decreased with different Zn^2+.Zn^2+ can delay the initial hydration of CAC.The induction period of cement with Zn^2+ is longer than that of CAC,especially the reaction time of the acceleration period is extended.Zn^2+ can promote hydration hydrate of CAC at 24 h.The characteristic diffraction peaks of CA and CA2 in CAC with different Zn^2+ are significantly reduced.It can inhibit the formation of CAH10 and promote the formation C3AH6 and AH3 in hydration products at 24 h.展开更多
A high-temperature reduction and smelting process was used to recover iron and calcium aluminate slag from high-ferrous bauxite. The effects of w（CaO）/w（SiO_2） ratio, anthracite ratio, and reduction temperature an...A high-temperature reduction and smelting process was used to recover iron and calcium aluminate slag from high-ferrous bauxite. The effects of w（CaO）/w（SiO_2） ratio, anthracite ratio, and reduction temperature and time on the recovery and size of iron nuggets and on the Al_2O_3 grade of the calcium aluminate slag were investigated through thermodynamic calculations and experiments. The optimized process conditions were the bauxite/anthracite/slaked lime weight ratio of 100：16.17：59.37, reduction temperature of 1450°C and reduction time of 20 min. Under these conditions, high-quality iron nuggets and calcium aluminate slag were obtained. The largest size and the highest recovery rate of iron nuggets were 11.42 mm and 92.79wt%, respectively. The calcium aluminate slag mainly comprised Ca_2 SiO_4 and Ca_（12）Al_（14）O_（33）, with small amounts of Fe Al_2O_4, CaAl_2O_4, and Ca_2Al_2SiO_7.展开更多
We focused on the efflorescence induced microstructural evolution of ettringite-rich systems prepared with calcium aluminate cement(CAC)and anhydrite.The effects of anhydrite on the visible efflorescence,and the corre...We focused on the efflorescence induced microstructural evolution of ettringite-rich systems prepared with calcium aluminate cement(CAC)and anhydrite.The effects of anhydrite on the visible efflorescence,and the corresponding capillary absorption of CAC-anhydrite mortars were revealed.The composition and microstructure of efflorescence-causing substances were investigated by optical microscope,in-situ Raman spectroscopy,scanning electron microscope,energy dispersive spectrometer,thermogravimetric analysis,and differential scanning calorimetry,at multi-scales.Results indicate that,besides the calcium carbonate,ettringite is another main component of efflorescence-causing substances.Compared with the neat CAC mortars,the addition of anhydrite has a significant effect on the degree of efflorescence by acting on the composition of hydration products and pore structure.In addition,methods are proposed for the prevention of efflorescence of CAC-anhydrite binary system.展开更多
The crystallization kinetics of 38.0CaO-38.0Al2O3-10.5BaO-6.5MgO-6.0Y2O3-1.0（Na2O＋K2O） （wt%） glass was studied by differential scanning calorimeter （DSC） and X-ray diffraction （XRD） techniques. Tile results s...The crystallization kinetics of 38.0CaO-38.0Al2O3-10.5BaO-6.5MgO-6.0Y2O3-1.0（Na2O＋K2O） （wt%） glass was studied by differential scanning calorimeter （DSC） and X-ray diffraction （XRD） techniques. Tile results showed that DSC curves of calcium aluminate glass have a single glass transition temperature followed by one crystallization peak for the heating rates β = 5 K/min and two crystallization temperatures T1 and T2 for β≥ 10 K/min. The activation energies of crystallization obtained from the Gao-Wang model of the first exothermal peak and the second exothermal peak of calcium aluminate glass are 340 and 662 kJ/mol, respectively. The Avrami exponents of the both crystallization peaks are approximately 2, indicating the two- dimensional crystalline growth during its transformation from amorphous to crystalline. Ca12Al14O33, Ca3Al2O6 and unknown crystalline phases firstly appear when calcium aluminate glass is heat-treated. With the extending of heat-treatment duration, BaAl2O4 phase comes out.展开更多
Understanding the interactive forces of inclusions on the surface of molten nickel-based superalloys and finding methods to disperse these inclusions help improve performance and service life.The aggregation behavior ...Understanding the interactive forces of inclusions on the surface of molten nickel-based superalloys and finding methods to disperse these inclusions help improve performance and service life.The aggregation behavior of aluminum oxide(Al_(2)O_(3))and calcium aluminate inclusions with different sizes and spacings on the surface of molten nickel-based superalloys was observed in-situ using a high-temperature confocal laser scan microscope.The attractive force acted on Al2O3 inclusions with radii of 3.5-6μm was found ranging from 6.2×10-18 to 3.6×10-15 N,and that of CaO·2Al2O3(CA2)inclusions with radii of 3-5.5μm ranging from 3.5×10-19 to 8.3×10-15 N.The capillary force acted on inclusions on the surface of nickel-based superalloy was calculated based on the Kralchevsky-Paunov model and investigated as a function of inclusion size,spacing,and composition.The calculated results were in the same trend as the experimental results.The capillary force acted on inclusions was also affected by their contact angle,the density,surface energy,and oxygen content of the molten alloy.It decreased with increasing alloy density and decreasing contact angle between inclusion with alloy.Thus,the attractive force acted on Al2O3 inclusions was smaller on the surface of molten nickel-based superalloy than that of molten steel.Decreasing the oxygen content in the molten nickel-based alloy could increase its surface energy,and the attractive force acted on the inclusions would decrease.When the oxygen content in the molten nickel-based alloy decreased from 0.05 to 0.0001 wt.%,the capillary force acted on the Al2O3 inclusions decreased from 1.7×10-18 to 3.6×10-19 N,reduced by 79%(1.4×10-18 N).展开更多
Two kinds of CACs with different monocalcium aluminate（CA） contents were used in the PC/CAC（PAC） mixtures. Effects of CA and CACs on the properties of PAC were analyzed by setting times and the compressive strengt...Two kinds of CACs with different monocalcium aluminate（CA） contents were used in the PC/CAC（PAC） mixtures. Effects of CA and CACs on the properties of PAC were analyzed by setting times and the compressive strength tests, and also by means of calorimetry, XRD, DTA-TG and ESEM. The experimental results show that the compressive strength of the PAC mortars decreases with increasing content of CAC while it declines sharply with a higher content of CA in CAC. Compared with neat PC paste, the content of calcium hydroxide in hydrates of PAC paste decreases significantly, and the hydration time of PC is prominently prolonged. Additionally, the higher the content of CA in CAC, the more obviously the hydration of PC is delayed, confi rming that the CA phase in CAC plays an important role in the delay of PC hydration.展开更多
Saturated Ca（OH）2 and AlCl3 solutions were used to synthesize calcium aluminate hydrate precipitates at room temperature; high purity calcium aluminate powders with stable phases were made by calcination of the prec...Saturated Ca（OH）2 and AlCl3 solutions were used to synthesize calcium aluminate hydrate precipitates at room temperature; high purity calcium aluminate powders with stable phases were made by calcination of the precursors at a temperature as low as 1100℃. PSD and BET analysis revealed the particles with sizes ranging from submicrometer to several micrometers and with a specific area of 13 m^2/g. The measurement of hydraulic exotherm revealed that the exothennal rate is in peak for about 2 h. The exothermal quantities are 449.24 J/g at 12 h and 488.38 J/g at 24 h. Its strength development is quick and the 1 day curing strength is almost equal to 100% of the 3 days curing strength in the mortar test.展开更多
Calcium aluminate cement bonded corundum castable specimens were prepared using brown fused corundum （8 - 5, 5 - 3, 3 - 1 mm ） , white fused corundum （ ≤ 1, ≤0. 045 mm）, micro-sized α-Al2O3 and microsilica as s...Calcium aluminate cement bonded corundum castable specimens were prepared using brown fused corundum （8 - 5, 5 - 3, 3 - 1 mm ） , white fused corundum （ ≤ 1, ≤0. 045 mm）, micro-sized α-Al2O3 and microsilica as starting materials. This work focused on investigating the relationship between the bond change in the castable matrix and the strength of the castable with 5 mass% microsilica or without microsilica after heat treatment at 110, 800 and 1 000 ℃, respectively. Chemical bond changes between the microsilica and hy- drates of calcium aluminate cement after drying at 110 ℃ or firing at 800 ℃ were investigated by XPS and FTIR. The results show that Si-O-Al bonds form be- tween the microsilica and hydrates of calcium aluminate cement after drying at 110 ℃ or firing at 800 ℃. Therefore, the increased strength of castable specimens is attributed to the formation of Si-O-Al bonds from 110 ℃ to 800 ℃.展开更多
Calcium aluminate cement(CAC)bonded corundum based castables were prepared using tabular corundum and activated alumina as the starting materials,CAC as the binder,zinc hydroxide(Zn(OH)_(2))and basic zinc carbonate(BZ...Calcium aluminate cement(CAC)bonded corundum based castables were prepared using tabular corundum and activated alumina as the starting materials,CAC as the binder,zinc hydroxide(Zn(OH)_(2))and basic zinc carbonate(BZC)as the ZnO precursors.The effects of the two ZnO precursors on the phase composition and the microstructure of the CAC bonded corundum based castable matrix specimens were analyzed,and the reasons affecting the hot performance of the castables were studied.The results show that Zn(OH)_(2) with a smaller particle size(d_(50)=1.26μm)is prone to agglomerate during sample preparation and generates ZnAl_(2)O_(4) spinel grains after firing,hindering the growth of CA_(6),thus decreasing the mechanical strength of the castables.BZC with a larger particle size(d_(50)=2.91μm),which shows a sound dispersity,in-situ generates nano-sized ZnO after firing,and ZnO or Zn^(2+)diffuses into calcium aluminates,promoting the sintering of CA_(2) and CA_(6),thereby enhancing the hot properties of the CAC-bonded corundum based castables.展开更多
文摘Nanocrystalline calcium aluminates with different CaO/Al2O3 ratios were prepared by a facile co-precipitation method using Poly（ethylene glycol）-block-poly（propylene glycol）-block-poly（ethylene glycol） （PEG-PPG-PEG, MW： 5800） as a surfactant. They were employed as catalyst support for nickel catalysts in methane reforming with carbon dioxide. The prepared samples were characterized by X-ray diffraction （XRD）, N2 adsorption （BET）, temperature-programmed reduction and oxidation （TPR-TPO）, and scanning electron microscopy （SEM） techniques. Catalysts showed a relatively high catalytic activity and stability. TPR analysis revealed that the catalysts with higher CaO content are more difficult to be reduced. TPO analysis showed that the 5 wt%Ni/CA and 5 wt%Ni/C12A7 catalysts with higher CaO amount were effective against coke deposition.
基金the Natural Sciences and Engineering Research Council of Canada(NSERC)for funding this researchThis research used a high temperature confocal laser scanning microscope-VL2000DX-SVF17SP funded by Canada Foundation for Innovation John Evans Leaders Fund(CFI JELF,Project Number:32826),a PANalytical X’Pert diffraction instrument located at the Centre for crystal growth,Brockhouse Institute for Materials Research,and a scanning electron microscope-JEOL 6610 located at the Canadian Centre for Electron Microscopy at McMaster University.W.Mu would like to acknowledge Swedish Iron and Steel Research Office(Jernkonteret),STINT and SSF for supporting the time for international collaboration research regarding clean steel.
文摘Dissolution kinetics of CaO·2Al_(2)O_(3)(CA_(2))particles in a synthetic CaO-Al_(2)O_(3)-SiO_(2)steelmaking slag system have been investigated using the high-temperature confocal laser scanning microscope.Effects of temperature(i.e.,1500,1550,and 1600℃)and slag composition on the dissolution time of CA_(2)particles are investigated,along with the time dependency of the projection area of the particle during the dissolution process.It is found that the dissolution rate was enhanced by either an increase in temperature or a decrease in slag viscosity.Moreover,a higher ratio of CaO/Al_(2)O_(3)(C/A)leads to an increased dissolution rate of CA_(2)particle at 1600℃.Thermodynamic calculations suggested the dissolution product,i.e.,melilite,formed on the surface of the CA_(2)particle during dissolution in slag with a C/A ratio of 3.8 at 1550℃.Scanning electron microscopy equipped with energy dispersive X-ray spectrometry analysis of as-quenched samples confirmed the dissolution path of CA_(2)particles in slags with C/A ratios of 1.8 and 3.8 as well as the melilite formed on the surface of CA_(2)particle.The formation of this layer during the dissolution process was identified as a hindrance,impeding the dissolution of CA_(2)particle.A valuable reference for designing or/and choosing the composition of top slag for clean steel production is provided,especially using calcium treatment during the secondary refining process.
基金Project (51104053) supported by the National Natural Science Foundation of ChinaProject (XL200921) supported by the Foundation Research funds for Hebei University of Science and Technology, China
文摘In order to remove or reduce the negative effect of MgO in calcium aluminate slags, the method of adding Na2O into calcium aluminate slags was studied and its effect on leaching mechanism was also analyzed. The results show that the alumina leaching efficiency of the calcium aluminate slag increases from 68.73% to 80.86% with Na2O content increasing from 0 to 4% when MgO content is 3%. The XRD results show that the quaternary compound C20A13M3S3 disappears when Na2O content increases to 4%. The addition of Na2O cannot remove the negative effect of MgO on leachability completely. XRD and EDS results indicate that Na2O can come into the lattice of 12CaO·7Al2O3 and promote the formation of 12CaO·7Al2O3
基金Project(51104053)supported by the National Natural Science Foundation of ChinaProject(E2012208047)supported by the Natural Science Foundation of Hebei Province,China
文摘SiO2 in calcium aluminate slag exists in the form of γ-2CaO·SiO2 which is more stable than β-2CaO·SiO2. However, it is decomposed by sodium carbonate solution during leaching process, leading to the secondary reaction. The extent of secondary reaction and reaction mechanism of calcium aluminate slag were studied using XRD. The results show that the decomposition rate of γ-2CaO·SiO2 increases with the increase in leaching time and sodium carbonate concentration. The main products of secondary reaction are the mixture of hydrogarnet and sodium hydrate alumina-silicate. SiO2 concentration rises firstly and then drops with the increase of leaching temperature. XRD results indicate that the stable product of secondary reaction at low temperature is hydrogarnet. But hydrogarnet is transformed into sodium hydrate alumina-silicate at high temperature.
基金financial support of the project from the National Natural Science Foundation of China (Nos.51174054,51104041 and 51374065)the Fundamental Research Funds for the Central Universities (No.N130402010)
文摘The mineral transition mechanism and physicochemical property of calcium aluminate clinker sintered at 1350 ℃ were systematically studied using analytical reagent α-Al 2O 3,CaCO 3 and SiO 2 when the molar ratio of CaO to Al 2O 3 is 1.0.The results show that the formation of Ca 2SiO 4 accelerates the diffusion of CaO and Al 2O 3,which promotes the formation of CaAl 2O 4 determined by dilatometer,X-ray diffraction,Fourier transform infrared spectroscopy and scanning electron microscopy methods.CaAl 4O 7,Ca 3Al 2O 6,Ca 3SiO 5 and Ca 2Al 2SiO 7 only exist in the initial stage of reactions,the amounts of which decrease with the increase of sintering duration.Ca 3Al 2O 6 and Ca 12Al 14O 33 react with Al 2O 3 and CaAl 4O 7 to form CaAl 2O 4,while Ca 2Al 2SiO 7 reacts with CaO and Ca 12Al 14O 33 to form Ca 2SiO 4 and CaAl 2O 4.The sintered clinker contains CaAl 2O 4 and γ-Ca 2SiO 4 as well as some Ca 12Al 14O 33 when the sintering duration is longer than 1.0 h.The differential scanning calorimetry results reveal that Ca 2SiO 4,Ca 2Al 2SiO 7 and CaAl 2O 4 are formed at985 ℃,1045℃ and 1339 ℃,respectively.Increasing the sintering duration contributes to the transition of β-Ca 2SiO 4 to γ-Ca 2SiO 4,which improves the pulverization and alumina leaching property of the sintered clinker.
基金Projects(51174054,51104041,51374065)supported by the National Natural Science Foundation of ChinaProject(N130402010)supported by the Fundamental Research Funds for the Central Universities of China
文摘Calcium aluminate clinkers doped with Na2O were synthesized using analytically pure reagents CaCO3, Al2O3, SiO2 and Na2CO3. The effects of Na2O-doping on the formation mechanism of calcium aluminate compounds and the crystal property of 12CaO·7Al2O3 (C12A7) cell were studied. The results show that the minerals containing Na2O mainly include 2Na2O·3CaO·5Al2O3 and Na2O·Al2O3, when the Na2O content in clinkers is less than 4.26% (mass fraction). The rest of Na2O is mainly doped in 12CaO·7Al2O3, which results in the decrease of the crystallinity of 12CaO·7Al2O3. The crystallinity of 2Na2O·3CaO·5Al2O3 is also inversely proportional to the Na2O content in clinkers. The formation processes of 2Na2O·3CaO·5Al2O3 and 12CaO·7Al2O3 can be divided into two ways, which are the direct reactions of raw materials and the transformation of CaO·Al2O3, respectively. The simulation shows that the covalency of O-Na bond in Na2O-doped 12CaO·7Al2O3 cell is weaker than those of O-Ca and O-Al bonds. The free energy of the unit cell increases because of Na2O doping, which results in the improvement of chemical activity of 12CaO·7Al2O3. The leaching efficiency of Al2O3 in clinker is improved from 34.81% to 88.17% when the Na2O content in clinkers increases from 0 to 4.26%.
基金Item Sponsored by National Natural Science Foundation of China(51174054,51104041,51374065)
文摘The sintering characteristics at 1350℃ and leaching property at 80℃ of calcium aluminate clinkers in the CaO-Al2O3-SiO2 （C-A-S） system with different additions of FeO and Fe2O3 were investigated. FeO inhibits the conversion of β-Ca2SiO4 to γ-Ca2SiO4 and makes the clinker not pulverizable. FeO and Fe2O3 inhibit the formation of CaAl2O4, but promote the formation of Ca12Al14O33. The interplanar spacing at （2 1 1） crystal face of Ca12 Al14O33 in the clinker increases with the increase of FeO addition, which indicates that FeO forms solid solutions in Ca12Al14O33. The clinkers with Fe2O3 addition form a new phase Ca2Fe2O5, and the amount of Ca2Fe2o5 increases with the in crease of Fe2O3 addition. Both FeO and Fe2O3 do not affect the Al2O3 leaching rate of calcium aluminate clinker in sodium carbonate solution, but they increase the molar ratio of caustic Na2O to Al2O3 in the leached liquor.
基金financially supported by the National Key R&D Program of China(No.2018YFC1901903)the National Nature Science Foundation of China(Nos.51674075 and 51774079)the Fundamental Research Funds for the Central Universities,China(No.N182508026)。
文摘The mineral transition and formation mechanism of calcium aluminate compounds in CaO-Al2O3-Na2O system during the hightemperature sintering process were systematically investigated using DSC-TG,XRD,SEM-EDS,FTIR,and Raman spectra,and the crystal structure of Na4Ca3(AlO2)10 was also simulated by Material Studio software.The results indicated that the minerals formed during the sintering process included Na4Ca3(AlO2)10,CaO·Al2O3,and 12 CaO·7 Al2O3,and the content of Na4Ca3(AlO2)10 could reach 92 wt%when sintered at 1200°C for 30 min.The main formation stage of Na4Ca3(AlO2)10 occurred at temperatures from 970 to 1100°C,and the content could reach82 wt%when the reaction temperature increased to 1100°C.The crystal system of Na4Ca3(AlO2)10 was tetragonal,and the cells preferred to grow along crystal planes(110)and(210).The formation of Na4Ca3(AlO2)10 was an exothermic reaction that followed a secondary reaction model,and its activation energy was 223.97 kJ/mol.
基金Funded by National Natural Science Foundation of China(Nos.51772212,51402216,51978505)。
文摘This paper describes a study on the corrosion behavior of steel reinforcement in CAC mortars via electrochemical methods including corrosion potential,electrochemical impedance,and linear polarization evaluation.Results indicate that there is a non-linear relationship between the corrosion degree of steel reinforcement in CAC mortar and the concentration of NaCl solution.The electrochemical parameters of specimens immersed in 3%NaCl solution suddenly drop at 40 days,earlier than 60 days of the reference.And the charge transfer resistivity of the specimen has decreased by 11 orders of magnitude at 40 days,showing an evident corrosion on steel reinforcement.However,it is interesting to notice that the corrosion is delayed by high external chloride concentration.The specimens immersed in 9%and 15%NaCl solutions remain in a relatively stable state within 120 days with slight pitting.The great corrosion protection of CAC concrete to embedded steel bars enables its wide application in marine.
基金The authors appreciate the financial support from National Natural Science Foundation of China(No.5157244,U1604252 and 5167225).
文摘In order to study the effect of the curing temperature on the intermediate temperature properties of calcium aluminate cement bonded corundum castables,the prepared castables were cured at 5,10,25,40 and 50℃,respectively,dried at 110℃ for 24 h and heat treated at 800 and 1100 ℃,respectively.Then the apparent porosity,the cold modulus of rupture and the cold crushing strength were measured.The phase composition of castable matrix specimens treated under the same conditions and the influence of the curing temperature on the intermediate temperature strength of the castables were also analyzed.The results show that with the increase of the curing temperature,the hydration degree of calcium aluminate cement increases,which promotes the uniform distribution of hydration products with AI203 after decomposition,thus enhancing the intermediate temperature strength of castables.
文摘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.
基金Funded by National Natural Science Foundation of China(No.51802235)State Key Laboratory of Silicate Materials for ArchitecturesWuhan University of Technology(No.SYSJJ2015-07)。
文摘The early hydration of calcium aluminate cement (CAC) with different kinds of zinc (II),such as ZnSO4g7H2O,ZnO,Zn(NO3)2·6H2O and ZnCl2,was analyzed.Changes in consistency,setting time,hydration heat flow,hydration heat amount,ion concentration in solution,and hydration products were found upon the addition of different Zn^2+.The water consumption of standard consistency of CAC is decreased with different Zn^2+.Zn^2+ can delay the initial hydration of CAC.The induction period of cement with Zn^2+ is longer than that of CAC,especially the reaction time of the acceleration period is extended.Zn^2+ can promote hydration hydrate of CAC at 24 h.The characteristic diffraction peaks of CA and CA2 in CAC with different Zn^2+ are significantly reduced.It can inhibit the formation of CAH10 and promote the formation C3AH6 and AH3 in hydration products at 24 h.
基金financially supported by the International Scientific and Technological Cooperation and Exchange Projects of China (No. 2013DFG50640)
文摘A high-temperature reduction and smelting process was used to recover iron and calcium aluminate slag from high-ferrous bauxite. The effects of w（CaO）/w（SiO_2） ratio, anthracite ratio, and reduction temperature and time on the recovery and size of iron nuggets and on the Al_2O_3 grade of the calcium aluminate slag were investigated through thermodynamic calculations and experiments. The optimized process conditions were the bauxite/anthracite/slaked lime weight ratio of 100：16.17：59.37, reduction temperature of 1450°C and reduction time of 20 min. Under these conditions, high-quality iron nuggets and calcium aluminate slag were obtained. The largest size and the highest recovery rate of iron nuggets were 11.42 mm and 92.79wt%, respectively. The calcium aluminate slag mainly comprised Ca_2 SiO_4 and Ca_（12）Al_（14）O_（33）, with small amounts of Fe Al_2O_4, CaAl_2O_4, and Ca_2Al_2SiO_7.
基金Funded by the National Key Research and Development Program of China(No.2022YFC3803400)National Natural Science Foundation of China(Nos.52378255,52278270)+1 种基金Shanghai Municipal Science and Technology Major Project(No.2021SHZDZX0100)the Fundamental Research Funds for the Central Universities and the Experimental Center of Materials Science and Engineering in Tongji University。
文摘We focused on the efflorescence induced microstructural evolution of ettringite-rich systems prepared with calcium aluminate cement(CAC)and anhydrite.The effects of anhydrite on the visible efflorescence,and the corresponding capillary absorption of CAC-anhydrite mortars were revealed.The composition and microstructure of efflorescence-causing substances were investigated by optical microscope,in-situ Raman spectroscopy,scanning electron microscope,energy dispersive spectrometer,thermogravimetric analysis,and differential scanning calorimetry,at multi-scales.Results indicate that,besides the calcium carbonate,ettringite is another main component of efflorescence-causing substances.Compared with the neat CAC mortars,the addition of anhydrite has a significant effect on the degree of efflorescence by acting on the composition of hydration products and pore structure.In addition,methods are proposed for the prevention of efflorescence of CAC-anhydrite binary system.
基金Funded by the National Natural Science Foundation of China(No.60808024)
文摘The crystallization kinetics of 38.0CaO-38.0Al2O3-10.5BaO-6.5MgO-6.0Y2O3-1.0（Na2O＋K2O） （wt%） glass was studied by differential scanning calorimeter （DSC） and X-ray diffraction （XRD） techniques. Tile results showed that DSC curves of calcium aluminate glass have a single glass transition temperature followed by one crystallization peak for the heating rates β = 5 K/min and two crystallization temperatures T1 and T2 for β≥ 10 K/min. The activation energies of crystallization obtained from the Gao-Wang model of the first exothermal peak and the second exothermal peak of calcium aluminate glass are 340 and 662 kJ/mol, respectively. The Avrami exponents of the both crystallization peaks are approximately 2, indicating the two- dimensional crystalline growth during its transformation from amorphous to crystalline. Ca12Al14O33, Ca3Al2O6 and unknown crystalline phases firstly appear when calcium aluminate glass is heat-treated. With the extending of heat-treatment duration, BaAl2O4 phase comes out.
基金supported by the National Natural Science Foundation of China(Nos.52064011 and 52264041)Guizhou Provincial Science and Technology Projects(No.Qian Ke He Ji Chu ZK[2021]258 and Qian Ke He Cheng Guo[2022]089).
文摘Understanding the interactive forces of inclusions on the surface of molten nickel-based superalloys and finding methods to disperse these inclusions help improve performance and service life.The aggregation behavior of aluminum oxide(Al_(2)O_(3))and calcium aluminate inclusions with different sizes and spacings on the surface of molten nickel-based superalloys was observed in-situ using a high-temperature confocal laser scan microscope.The attractive force acted on Al2O3 inclusions with radii of 3.5-6μm was found ranging from 6.2×10-18 to 3.6×10-15 N,and that of CaO·2Al2O3(CA2)inclusions with radii of 3-5.5μm ranging from 3.5×10-19 to 8.3×10-15 N.The capillary force acted on inclusions on the surface of nickel-based superalloy was calculated based on the Kralchevsky-Paunov model and investigated as a function of inclusion size,spacing,and composition.The calculated results were in the same trend as the experimental results.The capillary force acted on inclusions was also affected by their contact angle,the density,surface energy,and oxygen content of the molten alloy.It decreased with increasing alloy density and decreasing contact angle between inclusion with alloy.Thus,the attractive force acted on Al2O3 inclusions was smaller on the surface of molten nickel-based superalloy than that of molten steel.Decreasing the oxygen content in the molten nickel-based alloy could increase its surface energy,and the attractive force acted on the inclusions would decrease.When the oxygen content in the molten nickel-based alloy decreased from 0.05 to 0.0001 wt.%,the capillary force acted on the Al2O3 inclusions decreased from 1.7×10-18 to 3.6×10-19 N,reduced by 79%(1.4×10-18 N).
基金Funded by the National Key Technology R&D Programs in the12th Five-year Plan of China(2012BA20B02)
文摘Two kinds of CACs with different monocalcium aluminate（CA） contents were used in the PC/CAC（PAC） mixtures. Effects of CA and CACs on the properties of PAC were analyzed by setting times and the compressive strength tests, and also by means of calorimetry, XRD, DTA-TG and ESEM. The experimental results show that the compressive strength of the PAC mortars decreases with increasing content of CAC while it declines sharply with a higher content of CA in CAC. Compared with neat PC paste, the content of calcium hydroxide in hydrates of PAC paste decreases significantly, and the hydration time of PC is prominently prolonged. Additionally, the higher the content of CA in CAC, the more obviously the hydration of PC is delayed, confi rming that the CA phase in CAC plays an important role in the delay of PC hydration.
基金financially supported by the National Natural Science Foundation of China Key Program (No. 50332010)the National Natural Science Foundation of China (No. 50172007)
文摘Saturated Ca（OH）2 and AlCl3 solutions were used to synthesize calcium aluminate hydrate precipitates at room temperature; high purity calcium aluminate powders with stable phases were made by calcination of the precursors at a temperature as low as 1100℃. PSD and BET analysis revealed the particles with sizes ranging from submicrometer to several micrometers and with a specific area of 13 m^2/g. The measurement of hydraulic exotherm revealed that the exothennal rate is in peak for about 2 h. The exothermal quantities are 449.24 J/g at 12 h and 488.38 J/g at 24 h. Its strength development is quick and the 1 day curing strength is almost equal to 100% of the 3 days curing strength in the mortar test.
文摘Calcium aluminate cement bonded corundum castable specimens were prepared using brown fused corundum （8 - 5, 5 - 3, 3 - 1 mm ） , white fused corundum （ ≤ 1, ≤0. 045 mm）, micro-sized α-Al2O3 and microsilica as starting materials. This work focused on investigating the relationship between the bond change in the castable matrix and the strength of the castable with 5 mass% microsilica or without microsilica after heat treatment at 110, 800 and 1 000 ℃, respectively. Chemical bond changes between the microsilica and hy- drates of calcium aluminate cement after drying at 110 ℃ or firing at 800 ℃ were investigated by XPS and FTIR. The results show that Si-O-Al bonds form be- tween the microsilica and hydrates of calcium aluminate cement after drying at 110 ℃ or firing at 800 ℃. Therefore, the increased strength of castable specimens is attributed to the formation of Si-O-Al bonds from 110 ℃ to 800 ℃.
文摘Calcium aluminate cement(CAC)bonded corundum based castables were prepared using tabular corundum and activated alumina as the starting materials,CAC as the binder,zinc hydroxide(Zn(OH)_(2))and basic zinc carbonate(BZC)as the ZnO precursors.The effects of the two ZnO precursors on the phase composition and the microstructure of the CAC bonded corundum based castable matrix specimens were analyzed,and the reasons affecting the hot performance of the castables were studied.The results show that Zn(OH)_(2) with a smaller particle size(d_(50)=1.26μm)is prone to agglomerate during sample preparation and generates ZnAl_(2)O_(4) spinel grains after firing,hindering the growth of CA_(6),thus decreasing the mechanical strength of the castables.BZC with a larger particle size(d_(50)=2.91μm),which shows a sound dispersity,in-situ generates nano-sized ZnO after firing,and ZnO or Zn^(2+)diffuses into calcium aluminates,promoting the sintering of CA_(2) and CA_(6),thereby enhancing the hot properties of the CAC-bonded corundum based castables.
