CN108484186A - 一种钛铝酸钙-碳化硅复相耐火材料及其制备方法 - Google Patents

一种钛铝酸钙-碳化硅复相耐火材料及其制备方法 Download PDF

Info

Publication number
CN108484186A
CN108484186A CN201810322893.XA CN201810322893A CN108484186A CN 108484186 A CN108484186 A CN 108484186A CN 201810322893 A CN201810322893 A CN 201810322893A CN 108484186 A CN108484186 A CN 108484186A
Authority
CN
China
Prior art keywords
calcium aluminate
raw material
silicon carbide
titanium calcium
multiple phase
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810322893.XA
Other languages
English (en)
Inventor
赵惠忠
陈建威
张寒
余俊
刘艳丽
冯立
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JINZHOU GUOTAI INDUSTRIAL Co Ltd
Wuhan University of Science and Engineering WUSE
Wuhan University of Science and Technology WHUST
Original Assignee
JINZHOU GUOTAI INDUSTRIAL Co Ltd
Wuhan University of Science and Engineering WUSE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JINZHOU GUOTAI INDUSTRIAL Co Ltd, Wuhan University of Science and Engineering WUSE filed Critical JINZHOU GUOTAI INDUSTRIAL Co Ltd
Priority to CN201810322893.XA priority Critical patent/CN108484186A/zh
Publication of CN108484186A publication Critical patent/CN108484186A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/44—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3817—Carbides
    • C04B2235/3826—Silicon carbides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428—Silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/447—Phosphates or phosphites, e.g. orthophosphate, hypophosphite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5427—Particle size related information expressed by the size of the particles or aggregates thereof millimeter or submillimeter sized, i.e. larger than 0,1 mm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/606—Drying
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Products (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

本发明涉及一种钛铝酸钙‑碳化硅复相耐火材料及其制备方法。其技术方案是：以18～23wt％的α‑Al2O3粉体、5～10wt％的硅微粉和1～3wt％的五氧化二钒为原料Ⅰ，以55～60wt％的钛铝酸钙颗粒、5～10wt％的碳化硅颗粒和4～6wt％的碳化硅细粉为原料Ⅱ，原料Ⅰ和原料Ⅱ之和为原料；将原料Ⅱ、球磨后的原料Ⅰ和占原料3～4wt％的磷酸二氢铝溶液混辗，成型，干燥；再将干燥后的坯体置于底部铺有鳞片石墨的氧化铝匣钵中，用鳞片石墨填充掩埋，然后于1400～1450℃条件下保温3～4小时，随炉冷却，制得钛铝酸钙‑碳化硅复相耐火材料。本发明具有资源综合利用和节能环保的特点，所制制品抗折强度高、耐压强度大、导热系数较低、抗热震性优良和抗碱性气体侵蚀性能好。

Description

一种钛铝酸钙-碳化硅复相耐火材料及其制备方法
技术领域
本发明属于耐火材料技术领域。具体涉及一种钛铝酸钙-碳化硅复相耐火材料及其制备方法。
背景技术
钛铝酸钙是将冶炼钛铁合金后产生的钛铁渣经过除铁、降硅、均化和熔融等工艺处理后得到的一种以CA6和Ca((Al0.84Ti0.16)2)6O19为主晶相的多相耐火材料，且在加热过程中，Ca((Al0.84Ti0.16)2)6O19会转变成CA6。此外，水泥回转窑过渡带用耐火材料在服役过程中，易遭受燃料中的碱、氯和硫等组分的侵蚀，而导致窑衬的损毁。过渡带用的莫来石-碳化硅复相耐火材料虽然具有较好的抗热震性能，但是材料的导热系数较大且服役过程中难以形成稳定的窑皮而导致热量损失较大，而且碱侵蚀也较严重。
“高耐磨硅莫砖及其制备工艺”(CN103833387A)专利技术，采用矾土熟料、碳化硅细粉、电熔白刚玉粉、红柱石粉等作为原料制备高耐磨硅莫砖，虽然材料的耐磨性高和抗热震性优良，但未针对材料的抗碱性气体侵蚀性能进行优化，导致材料易遭受碱性气体的侵蚀而损毁；“高强致密硅莫砖及其制作方法”(CN101492301A)专利技术，采用高铝矾土熟料、氧化硅微粉、碳化硅、α-Al2O3等作为原料制备高强致密硅莫砖，虽然材料的耐压强度较高，但是该材料中致密高铝矾土骨料所占的比例较高，提高了材料的导热系数，且未解决抗碱性气体侵蚀性能差的问题。
发明内容
本发明旨在克服现有技术缺陷，目的在于提供一种资源综合利用和节能环保的钛铝酸钙-碳化硅复相耐火材料的制备方法，用该方法制备的钛铝酸钙-碳化硅复相耐火材料抗折强度高、耐压强度大、导热系数较低、抗热震性优良和抗碱性气体侵蚀性能好。
为实现上述目的，本发明采用的技术方案是：
以18～23wt％的α-Al2O3粉体、5～10wt％的硅微粉和1～3wt％的五氧化二钒为原料Ⅰ，以55～60wt％的钛铝酸钙颗粒、5～10wt％的碳化硅颗粒和4～6wt％的碳化硅细粉为原料Ⅱ，原料Ⅰ和原料Ⅱ之和为原料；先将所述原料Ⅰ球磨2～3小时，再将球磨后的原料Ⅰ、所述原料Ⅱ和占所述原料3～4wt％的磷酸二氢铝溶液混合，混辗8～10min，得到混合料。
将所述混合料于160～180MPa条件下机压成型，在90～110℃条件下干燥20～30小时，得到干燥后的坯体。
将所述干燥后的坯体置于底部铺有鳞片石墨的氧化铝匣钵中，再用鳞片石墨填充掩埋，然后将填充鳞片石墨后的氧化铝匣钵于1400～1450℃条件下保温3～4小时，随炉冷却，制得钛铝酸钙-碳化硅复相耐火材料。
所述α-Al2O3粉体的Al2O3含量≥98.7wt％；所述α-Al2O3粉体的粒度≤0.058mm。
所述硅微粉的SiO2含量≥94.8wt％；所述硅微粉的粒度≤0.058mm。
所述五氧化二钒的V2O5含量≥99.9wt％；所述五氧化二钒的粒度≤0.058mm。
所述钛铝酸钙颗粒的主要化学成分是：Al2O3≥74.18wt％，CaO≥11.69wt％，TiO2≥11.08wt％；所述钛铝酸钙颗粒的粒度≤3mm。
所述碳化硅颗粒的SiC含量≥98.8wt％；所述碳化硅颗粒的粒度≤3mm。
所述碳化硅细粉的SiC含量≥98.8wt％；所述碳化硅细粉的粒度≤0.088mm。
所述磷酸二氢铝溶液的浓度≥50wt％。
由于采用上述技术方案，本发明与现有技术相比具有以下优点：
1、本发明以钛铝酸钙为主要原料，具有资源综合利用和节能环保的特点。
2、本发明中的α-Al2O3与硅微粉在五氧化二钒作催化剂的情况下，原位反应生成莫来石。一方面，形成的莫来石相的陶瓷结合有利于提高钛铝酸钙-碳化硅复相耐火材料的抗折强度和耐压强度；另一方面，具有长径比的莫来石晶须能提高钛铝酸钙-碳化硅复相耐火材料的抗热震性能和抗折强度。
3、本发明在埋碳气氛下烧成，能有效地降低碳化硅的氧化，从而减弱钛铝酸钙中的CA6向钙长石的转变；此外，外加的硅微粉与钛铝酸钙中的游离氧化钙易形成钙硅液相，从而促进钛铝酸钙-碳化硅复相耐火材料的烧结致密化，提高钛铝酸钙-碳化硅复相耐火材料的抗碱性气体侵蚀性能。
4、本发明采用的钛铝酸钙中的CA6具有较低的导热系数、优良的抗热震性能和抗碱性气体侵蚀性能；当钛铝酸钙-碳化硅复相耐火材料遭受碱侵蚀时，一方面，钛铝酸钙中的开口气孔和CA6晶粒的间隙位置能有效地沉积碱性气体；另一方面，钛铝酸钙中的微量的钙长石与碱性气体反应后产生的钙硅钾液相能进一步阻碍碱性气体向材料内部的侵蚀，显著提高钛铝酸钙-碳化硅复相耐火材料的抗碱性气体侵蚀性能。
本发明所制备的钛铝酸钙-碳化硅复相耐火材料经检测：抗折强度为18～23MPa；耐压强度为115～125MPa；导热系数为1.1～1.6W·m-1·K-1(1000℃)；热震(ΔT＝1100℃，风冷10次)后强度保持率为80～85％；1300℃时抗钾、钠、氯化物、硫化物气体侵蚀性能优异。
因此，本发明具有资源综合利用和节能环保的特点，所制备的钛铝酸钙-碳化硅复相耐火材料抗折强度高、耐压强度大、导热系数较低、抗热震性优良和抗碱性气体侵蚀性能好。
具体实施方式
下面结合具体实施方式对本发明作进一步的描述，并非对其保护范围的限制。
为避免重复，先将本具体实施方式所涉及的物料统一描述如下，实施例中不再赘述：
所述α-Al2O3粉体的Al2O3含量≥98.7wt％；所述α-Al2O3粉体的粒度≤0.058mm。
所述硅微粉的SiO2含量≥94.8wt％；所述硅微粉的粒度≤0.058mm。
所述五氧化二钒的V2O5含量≥99.9wt％；所述五氧化二钒的粒度≤0.058mm。
所述钛铝酸钙颗粒的主要化学成分是：Al2O3≥74.18wt％，CaO≥11.69wt％，TiO2≥11.08wt％；所述钛铝酸钙颗粒的粒度≤3mm。
所述碳化硅颗粒的SiC含量≥98.8wt％；所述碳化硅颗粒的粒度≤3mm。
所述碳化硅细粉的SiC含量≥98.8wt％；所述碳化硅细粉的粒度≤0.088mm。
所述磷酸二氢铝溶液的浓度≥50wt％。
实施例1
一种钛铝酸钙-碳化硅复相耐火材料及其制备方法。本实施例所述制备方法是：
以18～20wt％的α-Al2O3粉体、8～10wt％的硅微粉和1～1.6wt％的五氧化二钒为原料Ⅰ，以55～57wt％的钛铝酸钙颗粒、8～10wt％的碳化硅颗粒和4～4.6wt％的碳化硅细粉为原料Ⅱ，原料Ⅰ和原料Ⅱ之和为原料；先将所述原料Ⅰ球磨2～3小时，再将球磨后的原料Ⅰ、所述原料Ⅱ和占所述原料3～4wt％的磷酸二氢铝溶液混合，混辗8～10min，得到混合料。
将所述混合料于160～180MPa条件下机压成型，在90～110℃条件下干燥20～30小时，得到干燥后的坯体。
将所述干燥后的坯体置于底部铺有鳞片石墨的氧化铝匣钵中，再用鳞片石墨填充掩埋，然后将填充鳞片石墨后的氧化铝匣钵于1400～1430℃条件下保温3～4小时，随炉冷却，制得钛铝酸钙-碳化硅复相耐火材料。
本发明所制备的钛铝酸钙-碳化硅复相耐火材料经检测：抗折强度为19～21MPa；耐压强度为117～121MPa；导热系数为1.4～1.6W·m-1·K-1(1000℃)；热震(ΔT＝1100℃，风冷10次)后强度保持率为82～84％；1300℃时抗钾、钠、氯化物、硫化物气体侵蚀性能优异。
实施例2
一种钛铝酸钙-碳化硅复相耐火材料及其制备方法。本实施例所述制备方法是：
以19～21wt％的α-Al2O3粉体、7～9wt％的硅微粉和1.5～2.1wt％的五氧化二钒为原料Ⅰ，以56～58wt％的钛铝酸钙颗粒、7～9wt％的碳化硅颗粒和4.5～5.1wt％的碳化硅细粉为原料Ⅱ，原料Ⅰ和原料Ⅱ之和为原料；先将所述原料Ⅰ球磨2～3小时，再将球磨后的原料Ⅰ、所述原料Ⅱ和占所述原料3～4wt％的磷酸二氢铝溶液混合，混辗8～10min，得到混合料。
将所述混合料于160～180MPa条件下机压成型，在90～110℃条件下干燥20～30小时，得到干燥后的坯体。
将所述干燥后的坯体置于底部铺有鳞片石墨的氧化铝匣钵中，再用鳞片石墨填充掩埋，然后将填充鳞片石墨后的氧化铝匣钵于1420～1450℃条件下保温3～4小时，随炉冷却，制得钛铝酸钙-碳化硅复相耐火材料。
本发明所制备的钛铝酸钙-碳化硅复相耐火材料经检测：抗折强度为21～23MPa；耐压强度为121～125MPa；导热系数为1.3～1.5W·m-1·K-1(1000℃)；热震(ΔT＝1100℃，风冷10次)后强度保持率为83～85％；1300℃时抗钾、钠、氯化物、硫化物气体侵蚀性能优异。
实施例3
一种钛铝酸钙-碳化硅复相耐火材料及其制备方法。本实施例所述制备方法是：
以20～22wt％的α-Al2O3粉体、6～8wt％的硅微粉和2～2.6wt％的五氧化二钒为原料Ⅰ，以57～59wt％的钛铝酸钙颗粒、6～8wt％的碳化硅颗粒和5～5.6wt％的碳化硅细粉为原料Ⅱ，原料Ⅰ和原料Ⅱ之和为原料；先将所述原料Ⅰ球磨2～3小时，再将球磨后的原料Ⅰ、所述原料Ⅱ和占所述原料3～4wt％的磷酸二氢铝溶液混合，混辗8～10min，得到混合料。
将所述混合料于160～180MPa条件下机压成型，在90～110℃条件下干燥20～30小时，得到干燥后的坯体。
将所述干燥后的坯体置于底部铺有鳞片石墨的氧化铝匣钵中，再用鳞片石墨填充掩埋，然后将填充鳞片石墨后的氧化铝匣钵于1400～1430℃条件下保温3～4小时，随炉冷却，制得钛铝酸钙-碳化硅复相耐火材料。
本发明所制备的钛铝酸钙-碳化硅复相耐火材料经检测：抗折强度为20～23MPa；耐压强度为119～123MPa；导热系数为1.1～1.3W·m-1·K-1(1000℃)；热震(ΔT＝1100℃，风冷10次)后强度保持率为81～83％；1300℃时抗钾、钠、氯化物、硫化物气体侵蚀性能优异。
实施例4
一种钛铝酸钙-碳化硅复相耐火材料及其制备方法。本实施例所述制备方法是：
以21～23wt％的α-Al2O3粉体、5～7wt％的硅微粉和2.5～3wt％的五氧化二钒为原料Ⅰ，以58～60wt％的钛铝酸钙颗粒、5～7wt％的碳化硅颗粒和5.5～6wt％的碳化硅细粉为原料Ⅱ，原料Ⅰ和原料Ⅱ之和为原料；先将所述原料Ⅰ球磨2～3小时，再将球磨后的原料Ⅰ、所述原料Ⅱ和占所述原料3～4wt％的磷酸二氢铝溶液混合，混辗8～10min，得到混合料。
将所述混合料于160～180MPa条件下机压成型，在90～110℃条件下干燥20～30小时，得到干燥后的坯体。
将所述干燥后的坯体置于底部铺有鳞片石墨的氧化铝匣钵中，再用鳞片石墨填充掩埋，然后将填充鳞片石墨后的氧化铝匣钵于1420～1450℃条件下保温3～4小时，随炉冷却，制得钛铝酸钙-碳化硅复相耐火材料。
本发明所制备的钛铝酸钙-碳化硅复相耐火材料经检测：抗折强度为18～20MPa；耐压强度为115～119MPa；导热系数为1.2～1.4W·m-1·K-1(1000℃)；热震(ΔT＝1100℃，风冷10次)后强度保持率为80～82％；1300℃时抗钾、钠、氯化物、硫化物气体侵蚀性能优异。
本具体实施方式与现有技术相比具有以下优点：
1、本具体实施方式以钛铝酸钙为主要原料，具有资源综合利用和节能环保的特点。
2、本具体实施方式中的α-Al2O3与硅微粉在五氧化二钒作催化剂的情况下，原位反应生成莫来石。一方面，形成的莫来石相的陶瓷结合有利于提高钛铝酸钙-碳化硅复相耐火材料的抗折强度和耐压强度；另一方面，具有长径比的莫来石晶须能提高钛铝酸钙-碳化硅复相耐火材料的抗热震性能和抗折强度。
3、本具体实施方式在埋碳气氛下烧成，能有效地降低碳化硅的氧化，从而减弱钛铝酸钙中的CA6向钙长石的转变；此外，外加的硅微粉与钛铝酸钙中的游离氧化钙易形成钙硅液相，从而促进钛铝酸钙-碳化硅复相耐火材料的烧结致密化，提高钛铝酸钙-碳化硅复相耐火材料的抗碱性气体侵蚀性能。
4、本具体实施方式采用的钛铝酸钙中的CA6具有较低的导热系数、优良的抗热震性能和抗碱性气体侵蚀性能；当钛铝酸钙-碳化硅复相耐火材料遭受碱侵蚀时，一方面，钛铝酸钙中的开口气孔和CA6晶粒的间隙位置能有效地沉积碱性气体；另一方面，钛铝酸钙中的微量的钙长石与碱性气体反应后产生的钙硅钾液相能进一步阻碍碱性气体向材料内部的侵蚀，显著提高钛铝酸钙-碳化硅复相耐火材料的抗碱性气体侵蚀性能。
本具体实施方式所制备的钛铝酸钙-碳化硅复相耐火材料经检测：抗折强度为18～23MPa；耐压强度为115～125MPa；导热系数为1.1～1.6W·m-1·K-1(1000℃)；热震(ΔT＝1100℃，风冷10次)后强度保持率为80～85％；1300℃时抗钾、钠、氯化物、硫化物气体侵蚀性能优异。
因此，本具体实施方式具有资源综合利用和节能环保的特点，所制备的钛铝酸钙-碳化硅复相耐火材料抗折强度高、耐压强度大、导热系数较低、抗热震性优良和抗碱性气体侵蚀性能好。

Claims (9)

1.一种钛铝酸钙-碳化硅复相耐火材料的制备方法，其特征在于：以18～23wt％的α-Al2O3粉体、5～10wt％的硅微粉和1～3wt％的五氧化二钒为原料Ⅰ，以55～60wt％的钛铝酸钙颗粒、5～10wt％的碳化硅颗粒和4～6wt％的碳化硅细粉为原料Ⅱ，原料Ⅰ和原料Ⅱ之和为原料；先将所述原料Ⅰ球磨2～3小时，再将球磨后的原料Ⅰ、所述原料Ⅱ和占所述原料3～4wt％的磷酸二氢铝溶液混合，混辗8～10min，得到混合料；
将所述混合料于160～180MPa条件下机压成型，在90～110℃条件下干燥20～30小时，得到干燥后的坯体；
将所述干燥后的坯体置于底部铺有鳞片石墨的氧化铝匣钵中，再用鳞片石墨填充掩埋，然后将填充鳞片石墨后的氧化铝匣钵于1400～1450℃条件下保温3～4小时，随炉冷却，制得钛铝酸钙-碳化硅复相耐火材料。
2.根据权利要求1所述的钛铝酸钙-碳化硅复相耐火材料的制备方法，其特征在于所述α-Al2O3粉体的Al2O3含量≥98.7wt％；所述α-Al2O3粉体的粒度≤0.058mm。
3.根据权利要求1所述的钛铝酸钙-碳化硅复相耐火材料的制备方法，其特征在于所述硅微粉的SiO2含量≥94.8wt％；所述硅微粉的粒度≤0.058mm。
4.根据权利要求1所述的钛铝酸钙-碳化硅复相耐火材料的制备方法，其特征在于所述五氧化二钒的V2O5含量≥99.9wt％；所述五氧化二钒的粒度≤0.058mm。
5.根据权利要求1所述的钛铝酸钙-碳化硅复相耐火材料的制备方法，其特征在于所述钛铝酸钙颗粒的主要化学成分是：Al2O3≥74.18wt％，CaO≥11.69wt％，TiO2≥11.08wt％；所述钛铝酸钙颗粒的粒度≤3mm。
6.根据权利要求1所述的钛铝酸钙-碳化硅复相耐火材料的制备方法，其特征在于所述碳化硅颗粒的SiC含量≥98.8wt％；所述碳化硅颗粒的粒度≤3mm。
7.根据权利要求1所述的钛铝酸钙-碳化硅复相耐火材料的制备方法，其特征在于所述碳化硅细粉的SiC含量≥98.8wt％；所述碳化硅细粉的粒度≤0.088mm。
8.根据权利要求1所述的钛铝酸钙-碳化硅复相耐火材料的制备方法，其特征在于所述磷酸二氢铝溶液的浓度≥50wt％。
9.一种钛铝酸钙-碳化硅复相耐火材料，其特征在于所述钛铝酸钙-碳化硅复相耐火材料是根据权利要求1～8项中任一项所述的钛铝酸钙-碳化硅复相耐火材料的制备方法所制备的钛铝酸钙-碳化硅复相耐火材料。
CN201810322893.XA 2018-04-11 2018-04-11 一种钛铝酸钙-碳化硅复相耐火材料及其制备方法 Pending CN108484186A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810322893.XA CN108484186A (zh) 2018-04-11 2018-04-11 一种钛铝酸钙-碳化硅复相耐火材料及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810322893.XA CN108484186A (zh) 2018-04-11 2018-04-11 一种钛铝酸钙-碳化硅复相耐火材料及其制备方法

Publications (1)

Publication Number Publication Date
CN108484186A true CN108484186A (zh) 2018-09-04

Family

ID=63315614

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810322893.XA Pending CN108484186A (zh) 2018-04-11 2018-04-11 一种钛铝酸钙-碳化硅复相耐火材料及其制备方法

Country Status (1)

Country Link
CN (1) CN108484186A (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111362708A (zh) * 2020-03-13 2020-07-03 武汉科技大学 一种钛铝合金熔炼用耐火材料及其制备方法
CN111377728A (zh) * 2020-03-13 2020-07-07 武汉科技大学 一种高纯含钛六铝酸钙材料及其制备方法
GB2601211A (en) * 2020-03-13 2022-05-25 Univ Wuhan Science & Tech Refractory material for smelting titanium aluminium alloy and method for preparation thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107140956A (zh) * 2017-06-30 2017-09-08 武汉科技大学 一种烧成高铝质耐火砖及其制备方法
CN107266052A (zh) * 2017-07-10 2017-10-20 武汉科技大学 矾土‑钛铝酸钙‑碳化硅复相耐火材料及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107140956A (zh) * 2017-06-30 2017-09-08 武汉科技大学 一种烧成高铝质耐火砖及其制备方法
CN107266052A (zh) * 2017-07-10 2017-10-20 武汉科技大学 矾土‑钛铝酸钙‑碳化硅复相耐火材料及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JIANWEI CHEN.ETAL.: ""Effect of partial substitution of calcium alumino-titanate for bauxite on the microstructure and properties of bauxite-SiC composite refractories"，Jianwei Chen.etal. 《Ceramics International》，第44期，第2934-2940页", 《CERAMICS INTERNATIONAL》 *
刘从华: ""莫来石的低温合成与结构研究"，刘从华，《高等学校化学学报》，第4期，第698-712页", 《高等学校化学学报》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111362708A (zh) * 2020-03-13 2020-07-03 武汉科技大学 一种钛铝合金熔炼用耐火材料及其制备方法
CN111377728A (zh) * 2020-03-13 2020-07-07 武汉科技大学 一种高纯含钛六铝酸钙材料及其制备方法
WO2021179844A1 (zh) * 2020-03-13 2021-09-16 武汉科技大学 一种钛铝合金熔炼用耐火材料及其制备方法
CN111377728B (zh) * 2020-03-13 2022-04-29 武汉科技大学 一种高纯含钛六铝酸钙材料及其制备方法
CN111362708B (zh) * 2020-03-13 2022-05-24 武汉科技大学 一种钛铝合金熔炼用耐火材料及其制备方法
GB2601211A (en) * 2020-03-13 2022-05-25 Univ Wuhan Science & Tech Refractory material for smelting titanium aluminium alloy and method for preparation thereof
GB2601211B (en) * 2020-03-13 2024-01-31 Univ Wuhan Science & Tech Refractory material for smelting titanium-aluminium alloy and method of preparing same

Similar Documents

Publication Publication Date Title
US4751204A (en) Two-part gunning refractory composition
CN106167411B (zh) 一种莫来石碳化硅复相耐火材料及其制备方法
CN101857446B (zh) 脱硫搅拌器用耐火浇注料
CN101767999B (zh) 纳米Al2O3、SiC薄膜包裹碳的Al2O3-MA-SiC-C质耐火浇注料及其制备方法
WO2010047136A1 (ja) 不定形耐火物用結合剤及び不定形耐火物
CN105174980B (zh) 一种高炉出铁沟用耐火浇注料及其制备方法
CN105819875B (zh) 一种澳斯麦特炼铜炉烟道用耐火浇注料及其制备方法
CN101654370A (zh) 一种含铝灰的高炉出铁沟浇注料及其制备方法
CN104909772B (zh) 含复合添加剂的铝酸钙水泥结合刚玉质浇注料及其制备方法
CN108484186A (zh) 一种钛铝酸钙-碳化硅复相耐火材料及其制备方法
CN106587958A (zh) 一种高炉出铁用无水泥铁沟浇注料及其制备方法
CN106431436A (zh) 一种以铝铬渣为主料的电炉炉盖浇注料及其制备方法
CN107285786A (zh) 钛铝酸钙‑碳化硅‑碳复相耐火材料及其制备方法
CN100482611C (zh) 一种低成本耐用高炉主沟料
CN107140956B (zh) 一种烧成高铝质耐火砖及其制备方法
CN106966739A (zh) 一种改良的rh喷补料
CN107954710A (zh) 一种碳化硅结合钛铝酸钙复相耐火材料及其制备方法
CN108129137A (zh) 大型水泥回转窑用复合镁铝尖晶石砖及其生产方法
JP2006282486A (ja) アルミナセメント、アルミナセメント組成物及び不定形耐火物
JP2002241182A (ja) 不定形耐火組成物
CN103951444B (zh) 循环流化床锅炉风室用高抗热震性涂抹料及其生产工艺
CN112456986A (zh) 一种钙处理钢用高寿命钢包上水口砖及其制备方法
CN107151134A (zh) 一种工业窑炉用高强高铝质耐火泥浆
CN106810283B (zh) 一种莫来石-铬轻质浇注料
CN109437865A (zh) 一种含铝灰的高炉出铁沟浇注料及其制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180904

WD01 Invention patent application deemed withdrawn after publication