Effect of Fused MgO-ZrO_2 Clinker Addition on Thermal Shock Resistance of MgO-ZrO_2 Unfired Bricks

MgO -ZrO2 unfired bricks with ZrO2 content up to 8% at the interval of 2% were prepared, using fused magnesia （ MgO ： 97% ） and fused MgO - ZrO2 clinker （ ZrO2 ： 14. 33% ） as starting materials and phenolic resin as binder. The effects of ZrO2 content on thermal shock resistance （TSR） and other properties such as cold and hot modulus of rupture have been investigated. Re- sidual cold modulus of rupture ratio after heating at 1 000 ℃ and quenching by air blowing was adopted to characterize TSR. Addition of the MgO -ZrO2 clinker improves TSR, attributing to the microcrack toughening effect by thermal expansion mismatch between different phases. When ZrO2 content goes above 4%. the impro- ving effect tends to be moderate. The introduction of MgO- ZrO2 clinker can also improve the HMOR at 1 500 ℃, while the increased ZrO2 content reduces CMOR of the bricks prefired at 1 600 ℃, due to the thermal expansion mismatch effect. Compromising the overall properties, the optimal ZrO2 content for such magnesia based unfired brick is suggested to be 4%.

A novel route to enhance high-temperature mechanical property and thermal shock resistance of low-carbon Mgo-C bricks by introducing ZrSiO_(4)

Conventional MgO-C bricks(graphite content>14 wt.%)produce a great deal of greenhouse gas emission,while low-carbon MgO-C bricks have serious thermal shock resistance during high-temperature service.To enhance the high-temperature mechanical property and thermal shock resistance of low-carbon MgO-C bricks,a novel route of introducing ZrSiO_(4) powder into low-carbon MgO-C bricks was reported in such refractories with 2 wt.% flaky graphite.The results indicate that the low-carbon MgO-C brick with 0.5 wt.%ZrSiO_(4) addition has the maximum hot modulus of rupture at 1400℃ and the corresponding specimen fired in the carbon embedded atmosphere has the maximum residual strength ratio(98.6%)after three thermal shock cycles.It is found that some needle-like AlON and plate-like Al_(2)O_(3)-ZrO_(2) composites were in situ formed in the matrices after the low-carbon MgO-C bricks were coked at 1400℃,which can enhance the high-temperature mechanical property and thermal shock resistance due to the effect of fiber toughening and particle toughening.Moreover,CO_(2) emission of the newly developed low-carbon MgO-C bricks is reduced by 58.3% per ton steel after using them as the working lining of a 90 t vacuum oxygen decarburization ladle.

Relation Between Sintering Reactivity of Matrix and Thermal Shock Resistance of Ultra-low Cement Bonded Corundum-spinel Castables for Fired Purging Plugs

Purging plugs installed in the bottom of steel ladles are widely used for the secondary refining of high quality steel grades.The dynamic service conditions and temperature gradients caused by the cold inert gas blown through the plug during stirring create a strong thermal shock impact on the materials.This can affect its service life and restrict the safety and efficiency of steel making if the plug fails during use.In this work,the influence of the particle size distribution (PSD) and amount of reactive alumina on the sintering behavior of ultra-low cement bonded corundum-spinel based castables was investigated on lab scale.The relationship between sintering reactivity of matrix and thermal shock resistance of castables was evaluated in detail.Results show that the sintering of castables can be intensified by using finer reactive alumina.However,excessive sintering of the castable through finer reactive alumina is negative for thermal shock resistance.The microstructure characterization reveals that castables with more intense sintering show denser matrix structure,which is less effective in hampering crack propagation and therefore results in decline of their thermal shock resistance.

Development of Thermal Shock Resistant and Low Creep Bricks for Hot Blast Stove

The paper describes the ries with high thermal shock development of brick seresistance and low creep rate for hot blast stove, including research target and research plan on the basis of analysis on how to enhance the thermal shock resistance and to lower creep rate of the bricks. Efforts have been made on the selection of starting materials such as corundum, mullite, andalusite and sillimanite etc., together with some measures taken on multi-grade formulation, homogenizing of the matrix of bricks and addition of some special additives. The results indicated that the bricks were with characteristics such as higher thermal shock resistance of 〉 30 cycles under quenching in water from 1000℃, and creep rate of 0. 2 under 1400℃ for 20 -50hrs with load of 0.2 MPa. Now a series of products of this kind have been developed and produced. The application of the products in Wuhan Iron and Steel Co. showed very prospective results. Now most of domestic large sized blast furnaces say ≥- 1000m^3, including those of Baoshan Iron and Steel Co. , have selected the series products made by Gongyi No. 5 Refractories Head Factory（GYWN） for their hot blast stoves.

轻质高强莫来石浇注料的组分优化和性能增强

为积极响应双碳政策,减少工业能源消耗,亟需开发轻质高强耐火材料。以微孔莫来石、莫来石细粉、氧化铝微粉、氧化铝空心球和二氧化硅微粉为原料,水泥为结合剂,制备了轻质莫来石质浇注料,研究了氧化铝空心球加入量(加入质量分数分别为0、3%、6%和9%)对莫来石浇注料性能的影响。结果表明:氧化铝空心球能提高试样的气孔率,并促进氧化铝微粉和二氧化硅微粉生成莫来石相,解决了试样因显气孔率增大而力学性能降低幅度较大的问题。随着氧化铝空心球加入量的增加,试样的显气孔率明显增加,体积密度降低,热导率显著下降,抗热震性提高,强度降低较少。当氧化铝空心球添加量为9%(w)时,试样经1400℃热处理后的显气孔率较高,体积密度和热导率较低,但常温强度仍然较高。

MgCl_(2)·6H_(2)O溶液对方镁石-镁铝尖晶石耐火材料性能的影响

以电熔镁砂和电熔镁铝尖晶石为原料,以18°Be’、24°Be’、30°Be’三种不同浓度的MgCl_(2)·6H_(2)O溶液和酚醛树脂为结合剂,制备方镁石-镁铝尖晶石耐火材料。以酚醛树脂为对照组,通过研究MgCl_(2)·6H_(2)O溶液对材料常温抗折强度、常温耐压强度、烧结性能、抗热震性能的影响,探明MgCl_(2)·6H_(2)O溶液对材料的作用机理。结果表明,在常温下MgCl_(2)·6H_(2)O溶液能与镁砂反应生成氯氧镁水泥(MOC),MOC在微观下表现为交错互锁的晶须结构,使得耐火材料在干燥后具有非常高的机械强度。当热处理温度为1 700℃、溶液浓度为24°Be’时,材料的常温耐压强度达到79.1 MPa,相较于酚醛树脂提高了58.2%;当热处理温度为1 700℃、溶液浓度为18°Be’时,材料的显气孔率达到16.8%,相较于酚醛树脂降低了13.4%。MgCl_(2)·6H_(2)O溶液浓度的增加有利于提高材料的断裂韧性。MOC和Mg(OH)_(2)在烧成过程中会分解产生活性MgO,促进材料的烧结。此外,分解产生的活性MgO呈类球状,它们分散填充在镁砂颗粒内部裂隙处,形成微孔结构,有利于减缓热震时的热应力冲击。

氧化锆-堇青石复相涂层对氧化铝基体影响的研究

在陶瓷材料表面引入压应力涂层已经被证明可以提高其强度和韧性。用高纯堇青石粉和氧化锆细粉制备了堇青石-氧化锆复相涂层浆料,将加工好的氧化铝样条浸润于浆料中,经过无压烧结制备出复相涂层增强的氧化铝材料。研究了不同氧化锆添加量(质量分数)的涂层对基体的整体性能的影响,结果表明,当复相涂层含质量分数为10%的氧化锆时其表面残余压应力为最大值1.34 GPa,相应地其弯曲强度也为最大值376.55 MPa,相比于未镀层的基体试样其弯曲强度增长了64.6%。此外,对试样还进行了高温弹性模量的试验,并分析了其弹性模量随温度变化的具体原因。镀层试样还进行了导热系数的试验,发现随着低热导率材料的加入,镀层试样的热导率也随之下降。最后由于表面残余压应力的存在,镀层试样相较于基体材料展现出了较好的抗热震性能,在900℃前,镀层试样水淬后的剩余强度均大于未镀层试样。

Influence of Ultra-Fine B_4C and Nano-SiO_2 on the Properties of Alumina-Graphite Refractories

The role of nano-SiO 2 and ultra-fine boron carbide on the properties of alumina-graphite materials was investigated. The study showed that the ultra-fine boron carbide added modified the microstructure of residual carbon and promoted the chemical bond between residual carbon from phenolic resin and flake graphite. The carbon white could strengthen the residual carbon from phenolic resin. These two additives improved the mechanical properties of AG refractories at both room temperature and high temperature, and thermal shock resistance was improved noticeably. When the two additives were doped together, carbon white could retard the evaporation of B 2O 3. Thermal shock resistance was guaranteed with a smaller amount of ultra-fine boron carbide.

Effect of Al_2O_3-SiC Composite Powder on Properties of Al_2O_3-SiC一C Bricks

Al2O3-SiC-C specimens were prepared using white fused corundum （3-1,≤1 and ≤0.044 mm）,Al2O3-SiC composite powders （d50 ≤ 5 μm）,α-Al2O3 micropowder （d50 =1.2 μm）,SiC powder （≤ 0.044 mm）,flake graphite （≤ 0.088 mm）,Si powder （d50 =42.8 μm） and B4C powder （d50 ≤10 μm） as main starting materials,and thermosetting phenolic resin as binder.4%,8%,12% and 16% （in mass,the same hereinafter） of Al2O3-SiC composite powders substituted the same quantity of α-Al2O3 micropowder ＋ SiC powder.Effects of composite powder additions on apparent porosity,bulk density,cold modulus of rupture,cold crushing strength,hot modulus of rupture （1 400 ℃）,thermal shock resistance （1 100 ℃,water quenching） and oxidation resistance （1 000 and 1 500 ℃） of Al2O3-SiC -C specimens after 180 ℃ curing,1 000 ℃ 3 h carbon-embedded firing and 1 500 ℃ 3 h carbon-embedded firing,respectively,were researched.The results indicate that：（1） with the increase of Al2O3-SiC composite powder,cold strengths of the cured specimens decline,those of the specimens fired at 1 000 ℃ change a little,and those of the specimens fired at 1 500 ℃ change a little except for an obvious improvement of cold crushing strength ; （2） with the increase of Al2O3-SiC composite powder,hot modulus of rupture at 1 400 ℃ decreases and thermal shock resistance enhances significantly; （3） when Al2O3-SiC composite powder addition is 4%,the oxidation resistance at 1 500 ℃ is the best,and the reason may be the composite powder is finer and more active,which is beneficial to form dense mullite protective layer to retard the O2 diffusion into the specimens.

Influence of Flotation Magnesia Particles and Al_(2)O_(3) Fines on Properties of Periclase-spinel Bricks

Periclase-spinel bricks were prepared using sintered magnesia,flotation magnesia,fused magnesium aluminate spinel and calcined Al_(2)O_(3)fines as the starting materials and calcium lignosulfonate as the binder,mixing,shaping and firing at 1650℃.Flotation magnesia particles were used to replace ordinary sintered magnesia particles and different amounts of calcined Al_(2)O_(3)fines were extra-added(0%,3%and 5%,by mass)to investigate their effects on the properties of periclase-spinel bricks.The results show that:the periclase-spinel bricks prepared with flotation magnesia particles have reduced apparent porosity and cold compressive strength,and enhanced bulk density,thermal shock resistance,hot strength and hot toughness.As the calcined Al_(2)O_(3)fines addition increases,the apparent porosity and the cold compressive strength decrease,and the bulk density,the thermal shock resistance,the hot strength and the hot toughness are improved.

Application Performance of Microporous Sintered Alumina in Alumina Magnesia Castables for Ladles

In this study,a kind of microporous sintered alumina was analyzed and applied.The microporous sintered alumina has a lot of nano and sub-micron closed pores in the crystals,the average pore size of 140 nm,and the thermal conductivity of 4.864 at 800℃,38%lower than that of common sintered alumina.The microporous sintered alumina was used as the aggregates in alumina magnesia castables for ladles to replace the common sintered alumina.The properties of the microporous alumina castable were measured,and the temperature field of the ladle outer wall was simulated and calculated.The results show that the refractoriness under load(T0.6)and the hot modulus of rupture(1400℃,0.5 h)of the microporous castable are the same as the common castable;the thermal conductivity at 800℃decreases by 15%;the retention ratio of modulus of rupture increases by about 5%after five thermal shock cycles(1100℃,water quenching);and the temperature of the ladle outer wall is reduced by 5-41℃.

Effect of Andalusite Addition on Properties of Chrome-corundum Bricks

In order to improve the thermal shock resistance of chrome-corundum bricks,different amounts of andalusite were added to the formulation of chrome-corundum bricks to replace the equivalent white fused corundum with the same particle size.After mixing,shaping,drying and firing,the density,the cold strength,the cold wear resistance,the hot modulus of rupture and the thermal shock resistance were tested.XRD,SEM and elemental surface scanning were used to characterize the specimens.The results show that:(1)the volume expansion of andalusite mullitization reduces the apparent porosity of chrome-corundum bricks;(2)the density and the hardness of mullite are lower than those of corundum so the decrease of the corundum content in brick leads to the decrease of the bulk density,the strength and the cold wear resistance;(3)the cross-distributed columnar mullite in the matrix can effectively improve the hot modulus of rupture and the thermal shock resistance of the specimens;(4)considering comprehensively,the andalusite addition shall not exceed 18%.

Fabrication and Properties of Aluminabased Reticulated Porous Ceramics

The primary impregnation slurry was prepared using active alumina(56.25 mass%),kaolin(15 mass%),zirconia(3.75 mass%),deionized water(25 mass%),and extra adding FS(0.2 mass%)and CMC(0.4 mass%).The effects of the active alumina particle size(d50=5.043,2.934,and 1.629μm)on the rheology and the thixotropy of the slurry were researched.It was found that the bimodal activeα-Al2O3(AMA-10)with d50=1.629μm was optimum.The secondary impregnation slurry was prepared using AMA-10,kaolin and zirconia as the main raw materials.Then the alumina-based reticulated porous ceramics were fabricated by the organic foam impregnation method combined with a secondary vacuum impregnation process.The influence of the AMA-10 content on the properties of the ceramics was studied.The residual stress of the specimens was analyzed by finite element analysis.The results show that the smaller alumina particle size and multimodal distribution are beneficial to the thixotropy of the primary impregnation slurry.The secondary vacuum impregnation technique can significantly improve the mechanical properties,the thermal shock resistance and the residual strength of the alumina-based reticulated porous ceramics.With the decrease of alumina content in the secondary impregnation slurry,the residual stress of the external layer of ceramic reinforcement gradually changes from tensile stress to compressive stress,which effectively inhibits the expansion of the surface crack,and remarkably improves the crushing strength retention ratio of alumina reticulated porous ceramics.

Influence of Glass Dust on Properties of Alumina-carbon Refractories

In order to improve the properties of alumina-carbon refractories,specimens were prepared using white fused corundum,zirconia-mullite and flake graphite as the raw materials,phenolic resin as the binder,adding different mass fractions(1.5%,2.0%,and 2.5%,respectively)of glass dust,cold isostatic pressing by 120 MPa,drying and firing at 900℃for 3 h.Effects of the glass dust addition on the apparent porosity,bulk density,cold modulus of rupture,hot modulus of rupture and thermal shock resistance were studied.The results show that the cold modulus of rupture of the specimens is improved significantly as the results of glass dust accelerating sintering.However,the hot modulus of rupture decreases.As the glass phase buffers the strain produced by thermal shock,the thermal shock resistance of alumina-carbon specimens is improved,especially for low carbon alumina-carbon materials.

稳定剂种类对高纯氧化锆空心球制品性能的影响

为制备隔热性能更好的高纯氧化锆空心球制品,分别以CaO稳定氧化锆空心球颗粒及细粉、Y_(2)O_(3)稳定氧化锆空心球颗粒及细粉、CaO+Y_(2)O_(3)复合稳定氧化锆空心球颗粒及细粉为主要原料,以工业级Y_(2)O_(3)微粉为烧结助剂,以水溶性树脂为结合剂,采用振动加压成型,于1800℃保温6 h烧成制备了含不同稳定剂的高纯氧化锆空心球制品。研究了稳定剂种类对这些制品性能的影响。结果表明:1)烧后各试样的物相主要为立方氧化锆;骨料与基质细粉都很好结合在一起,含CaO稳定剂试样的内部气孔相对狭长,呈相互贯通网络状,力学性能适中,抗热震性最优;含Y_(2)O_(3)稳定剂试样的内部气孔大小不均、分散孤立,力学性能最差;含CaO+Y_(2)O_(3)复合稳定剂试样的内部孔径更小、分布更均匀,致密化趋势明显,力学性能最优,但抗热震性最差。2)烧后试样的线膨胀率和热导率随温度升高均逐渐增大;在高温阶段,含CaO稳定剂试样的线膨胀率和热导率都最低。3)综合考虑,含CaO稳定剂试样的性能最佳。

钛铁渣加入量对Al_(2)O_(3)-SiC-C铁沟浇注料性能的影响

为合理利用钛铁渣进而缓解资源紧张,以矾土熟料、致密刚玉、SiC、α-Al_(2)O_(3)微粉、SiO_(2)微粉、Si粉为主要原料,添加质量分数分别为0、11.2%、22.4%、33.6%、44.8%和56.0%的钛铁渣等量替代矾土熟料,于1450℃保温3 h热处理后制备了Al_(2)O_(3)-SiC-C浇注料,研究钛铁渣的加入量对浇注料性能的影响。结果表明:1)随着钛铁渣加入量的增多,浇注料的体积密度降低,显气孔率增加,常温强度总体呈下降趋势,但同时会在一定程度上提高浇注料的高温抗折强度和抗热震性;2)钛铁渣的引入带来过多的气孔为氧气的扩散提供了更多通道,且经氧化处理后由钛铁渣引入的杂质会生成较多液相,使得浇注料结构疏松,显著降低抗氧化性能;3)钛铁渣与熔渣反应会生成镁铝尖晶石,能够阻止熔渣的进一步侵蚀,提高其抗渣侵蚀性。综合考虑,钛铁渣的最佳加入量为56.0%(w)。

氧化铝微粉粒度对铝锆碳滑板性能的影响

为了进一步改善铝锆碳材质的使用性能,以板状刚玉、锆莫来石为主要原料,酚醛树脂为结合剂,研究了5种不同的氧化铝微粉对铝锆碳滑板性能的影响;结果表明:1)随着氧化铝微粉粒度逐渐减小,试样的显气孔率增加,体积密度随之减小,试样的常温力学性能降低;2)CL-370因粒度分布为双峰,有效填充了气孔,最终导致试样A4的烧后体积密度和常温抗折强度大于试样A3的该值;3)随着氧化铝微粉粒度逐渐减小,试样的高温抗折强度变大,热震稳定性变小。

氧化铝-锂霞石复合陶瓷在钢水中抗热震性研究

为了提高氧化铝陶瓷的抗热震性,将具有负膨胀系数的锂霞石加入到Al2O3中,通过无压烧结工艺,制备出了氧化铝-锂霞石复合抗热震陶瓷。结果表明,锂霞石加入量w(锂霞石)=20%,烧结温度为1500℃时,陶瓷样品能够承受钢水中1500℃温差(空冷)的热震破坏。采用SEM对陶瓷进行组织结构分析,发现在基体内部形成片状组织,这样的显微组织对提高陶瓷的抗热震性具有重要作用。

Al_2O_3/堇青石陶瓷的制备和抗热震性能研究

为了解决氧化铝陶瓷抗热震性差的难题,将堇青石、纳米SiC加入到Al2O3中,通过无压烧结工艺,制备出了Al2O3/堇青石抗热震陶瓷.结果表明,w(堇青石)=10%、烧结温度为1 520℃时陶瓷可获得最高密度.陶瓷样品能够承受1 500℃温差(空冷)的热震破坏.采用SEM对陶瓷进行组织结构分析,发现堇青石与氧化铝形成长柱状固溶体,呈无规分布状态.这样的显微组织有利于缓解热应力和提高强度,对提高陶瓷的抗热震性具有重要作用.

氧化铝-钛酸铝-莫来石复相陶瓷抗热震性研究

为了提高氧化铝陶瓷的抗热震性,将具有低膨胀系数的钛酸铝和莫来石加入到Al2O3中,通过无压烧结工艺,制备出了氧化铝-钛酸铝-莫来石复相抗热震陶瓷.结果表明,钛酸铝加入量w（Al2O3.TiO2）=10%-20%、烧结温度为1470-1550℃时,陶瓷可获得较高密度.陶瓷样品能够承受1500℃温差（空冷）的热震破坏.采用SEM对陶瓷进行组织结构分析,发现在基体内部形成长柱状固溶体,并呈无规分布状态.这样的显微组织有利于缓解热应力和提高强度,对提高陶瓷的抗热震性具有重要作用.同时,在基体内部存在大量的微孔和微裂纹,使材料表现出更低的热膨胀.