CN113999023A - 用于塞棒的纳米耐火材料制备方法 - Google Patents

用于塞棒的纳米耐火材料制备方法 Download PDF

Info

Publication number
CN113999023A
CN113999023A CN202111144733.9A CN202111144733A CN113999023A CN 113999023 A CN113999023 A CN 113999023A CN 202111144733 A CN202111144733 A CN 202111144733A CN 113999023 A CN113999023 A CN 113999023A
Authority
CN
China
Prior art keywords
parts
nano
stopper rod
refractory material
composite
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.)
Granted
Application number
CN202111144733.9A
Other languages
English (en)
Other versions
CN113999023B (zh
Inventor
马庆娟
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.)
Sevens New Materials Wuxi Co ltd
Original Assignee
Sevens New Materials Wuxi Co ltd
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 Sevens New Materials Wuxi Co ltd filed Critical Sevens New Materials Wuxi Co ltd
Priority to CN202111144733.9A priority Critical patent/CN113999023B/zh
Publication of CN113999023A publication Critical patent/CN113999023A/zh
Application granted granted Critical
Publication of CN113999023B publication Critical patent/CN113999023B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
    • B22D41/14—Closures
    • B22D41/16—Closures stopper-rod type, i.e. a stopper-rod being positioned downwardly through the vessel and the metal therein, for selective registry with the pouring opening
    • B22D41/18—Stopper-rods therefor
    • 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
    • C04B35/16—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 silicates other than clay
    • C04B35/18—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 silicates other than clay rich in aluminium oxide
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/6303—Inorganic additives
    • 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
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/636—Polysaccharides or derivatives thereof
    • C04B35/6365—Cellulose or derivatives thereof
    • 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
    • C04B35/71—Ceramic products containing macroscopic reinforcing agents
    • C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
    • C04B35/80—Fibres, filaments, whiskers, platelets, or the like
    • 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
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • 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
    • C04B2235/36—Glass starting materials for making ceramics, e.g. silica glass
    • C04B2235/365—Borosilicate glass
    • 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
    • C04B2235/422—Carbon
    • C04B2235/424—Carbon black
    • 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
    • C04B2235/422—Carbon
    • C04B2235/425—Graphite
    • 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
    • C04B2235/443—Nitrates or nitrites
    • 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
    • C04B2235/52—Constituents or additives characterised by their shapes
    • C04B2235/5208—Fibers
    • C04B2235/5216—Inorganic
    • C04B2235/524—Non-oxidic, e.g. borides, carbides, silicides or nitrides
    • C04B2235/5248—Carbon, e.g. graphite

Abstract

本发明涉及炼钢技术领域，尤其涉及用于塞棒的纳米耐火材料制备方法，纳米耐火材料按质量份计包括以下原料：硅酸铝85‑95份、电熔氧化铝80‑90份、石墨80‑90份、纳米碳化硅80‑90份、纳米碳纤维75‑95份、液态酚醛树脂结合剂75‑85份、炭黑45‑65份、锆莫来石45‑55份、复合高温抗氧化剂75‑135份、催化剂45‑55份、复合抗热震添加物85‑170份。本发明不仅可以提高纳米耐火材料在高温下的抗氧化性能，而且还能有效地改善纳米耐火材料的抗热震效果。

Description

用于塞棒的纳米耐火材料制备方法
技术领域
本发明涉及炼钢技术领域，尤其涉及用于塞棒的纳米耐火材料制备方法。
背景技术
塞棒是装在盛钢桶内靠升降位移控制水口开闭及钢水流量的耐火材料棒，又称陶塞杆。它由棒芯、袖砖和塞头砖组成。棒芯通常由直径为30～60mm的普碳钢圆钢加工而成，上端靠螺栓与升降机构的横臂联结，下端靠螺纹或销钉与塞头砖连接，中间套袖砖。塞棒须仔细砌筑，并经48h以上的烘烤干燥后使用，以避免耐火材料炸裂造成漏钢事故。
因此，我们提出了用于塞棒的纳米耐火材料制备方法用于解决上述问题。
发明内容
本发明的目的是为了解决现有技术中存在的缺点，而提出的用于塞棒的纳米耐火材料制备方法。
用于塞棒的纳米耐火材料，按质量份计包括以下原料：
硅酸铝85-95份、电熔氧化铝80-90份、石墨80-90份、纳米碳化硅80-90份、纳米碳纤维75-95份、液态酚醛树脂结合剂75-85份、炭黑45-65份、锆莫来石45-55份、复合高温抗氧化剂75-135份、催化剂45-55份、复合抗热震添加物85-170份。
优选的，所述催化剂为硝酸镍和硝酸钴按质量比1:1混合而成的混合物。
优选的，所述复合高温抗氧化剂由硼硅玻璃为基料，二氧化钍为复合料以及羧甲基纤维素钠溶液为结合剂经球磨混合后制备而成。
优选的，所述硼硅玻璃、二氧化钍和羧甲基纤维素钠溶液的质量比为7:5:3，羧甲基纤维素钠溶液的浓度为35%-40%。
优选的，所述复合抗热震添加物由板状刚玉粉为底料，硼熔块、二氧化硅和ThP2O7为复配添加剂以及羧甲基纤维素钠溶液为结合剂经球磨混合后制备而成。
优选的，所述板状刚玉粉、硼熔块、二氧化硅、ThP2O7以及羧甲基纤维素钠溶液的质量比为6:3:2:2:4，羧甲基纤维素钠溶液的浓度为45%-48%。
优选的，所述球磨混合的过程为：按配比称取原料放入球磨机中，再以球料比7:2加入氧化锆球磨珠，以570-600r/min的转速混磨2-5小时。
用于塞棒的纳米耐火材料制备方法，包括以下步骤：
S1、按配方称量好原料，备用；
S2、将硅酸铝、电熔氧化铝、炭黑和锆莫来石混合后通过干燥、球磨后得到复合粉体，按照顺序将复合粉体、石墨、复合抗热震添加物、液态酚醛树脂结合剂、纳米碳化硅和纳米碳纤维在混砂机中混合均匀，并干燥24小时，得混合料；
S3、利用万能压力机将混合料压制成圆柱状的塞棒，将干燥好的塞棒装在匣钵内并在埋碳条件下依次在900℃和1100℃的温度环境下分别保温2-3小时，最后取出后冷却至室温后即得纳米耐火材料；
S4、在纳米耐火材料的表面上涂抹复合高温抗氧化剂，涂抹完毕后将其置于煅烧炉内煅烧1-1.6小时，使得复合高温抗氧化剂在纳米耐火材料的表面形成一层防护膜，即得最终的纳米耐火材料。
优选的，所述万能压力机的设定压力范围在170kN-200kN之间。
相比于现有技术，本发明的有益效果是：
1、在本发明中，通过以由硼硅玻璃为基料，二氧化钍为复合料以及羧甲基纤维素钠溶液为结合剂，经混合球磨后制得复合高温抗氧化剂，使其在纳米耐火材料上形成致密的保护层，以使碳元素免于氧化，从而有效地提高了纳米耐火材料在高温下的抗氧化性能。
2、在本发明中，通过以板状刚玉粉为底料，硼熔块、二氧化硅和ThP2O7为复配添加剂以及羧甲基纤维素钠溶液为结合剂制得复合抗热震添加物，硼熔块可以制备过程中形成硼酸盐，减少耐火材料的龟裂程度，二氧化硅与ThP2O7的加入可以降低复合抗热震添加物的线膨胀系数，使其与纳米耐火材料的线膨胀系数相匹配，防止纳米耐火材料在使用过程中开裂，进而能够有效地改善纳米耐火材料的抗热震效果。
具体实施方式
下面结合具体实施例对本发明作进一步解说。
实施例1：
用于塞棒的纳米耐火材料，按质量份计包括以下原料：
硅酸铝85份、电熔氧化铝80份、石墨80份、纳米碳化硅80份、纳米碳纤维75份、液态酚醛树脂结合剂75份、炭黑45份、锆莫来石45份、复合高温抗氧化剂75份、催化剂45份、复合抗热震添加物85份。
实施例2：
用于塞棒的纳米耐火材料，按质量份计包括以下原料：
硅酸铝90份、电熔氧化铝85份、石墨85份、纳米碳化硅85份、纳米碳纤维85份、液态酚醛树脂结合剂80份、炭黑55份、锆莫来石50份、复合高温抗氧化剂105份、催化剂50份、复合抗热震添加物119份。
实施例3：
用于塞棒的纳米耐火材料，按质量份计包括以下原料：
硅酸铝95份、电熔氧化铝90份、石墨90份、纳米碳化硅90份、纳米碳纤维95份、液态酚醛树脂结合剂85份、炭黑65份、锆莫来石55份、复合高温抗氧化剂135份、催化剂55份、复合抗热震添加物170份。
上述实施例1-3中，催化剂为硝酸镍和硝酸钴按质量比1:1混合而成的混合物；
复合高温抗氧化剂由硼硅玻璃为基料，二氧化钍为复合料以及羧甲基纤维素钠溶液为结合剂经球磨混合后制备而成，其中，硼硅玻璃、二氧化钍和羧甲基纤维素钠溶液的质量比为7:5:3，羧甲基纤维素钠溶液的浓度为35%；
复合抗热震添加物由板状刚玉粉为底料，硼熔块、二氧化硅和ThP2O7为复配添加剂以及羧甲基纤维素钠溶液为结合剂经球磨混合后制备而成，其中，板状刚玉粉、硼熔块、二氧化硅、ThP2O7以及羧甲基纤维素钠溶液的质量比为6:3:2:2:4，羧甲基纤维素钠溶液的浓度为45%。
在复合高温抗氧化剂和复合抗热震添加物的原料制备过程中，球磨混合的过程如下：按配比称取原料放入球磨机中，再以球料比7:2加入氧化锆球磨珠，以570r/min的转速混磨2小时。
上述实施例1-3均通过下述过程进行制备纳米耐火材料：
用于塞棒的纳米耐火材料制备方法，包括以下步骤：
S1、按配方称量好原料，备用；
S2、将硅酸铝、电熔氧化铝、炭黑和锆莫来石混合后通过干燥、球磨后得到复合粉体，按照顺序将复合粉体、石墨、复合抗热震添加物、液态酚醛树脂结合剂、纳米碳化硅和纳米碳纤维在混砂机中混合均匀，并干燥24小时，得混合料；
S3、利用万能压力机在170kN的压力下将混合料压制成圆柱状的塞棒，将干燥好的塞棒装在匣钵内并在埋碳条件下依次在900℃和1100℃的温度环境下分别保温2小时，最后取出后冷却至室温后即得纳米耐火材料；
S4、在纳米耐火材料的表面上涂抹复合高温抗氧化剂，涂抹完毕后将其置于煅烧炉内煅烧1.5小时，使得复合高温抗氧化剂在纳米耐火材料的表面形成一层防护膜，即得最终的纳米耐火材料。
试验一：对纳米耐火材料的高温抗氧化性能测定
对比例1：与实施例1相比，除复合高温抗氧化剂的组成不同外，其余原料均一致；
对比例2：与实施例2相比，除复合高温抗氧化剂的组成不同外，其余原料均一致；
对比例3：与实施例3相比，除复合高温抗氧化剂的组成不同外，其余原料均一致；
上述对比例1-3中，复合高温抗氧化剂由硼硅玻璃为基料以及羧甲基纤维素钠溶液为结合剂经球磨混合后制备而成，其中，硼硅玻璃和羧甲基纤维素钠溶液的质量比为7:3，羧甲基纤维素钠溶液的浓度为35%；且对比例1-3中的制备过程与实施例1-3的制备过程一致。
参照例1：与实施例1相比，除不添加复合高温抗氧化剂外，其余原料均一致；
参照例2：与实施例2相比，除不添加复合高温抗氧化剂外，其余原料均一致；
参照例3：与实施例3相比，除不添加复合高温抗氧化剂外，其余原料均一致；
参照例1-3的制备过程与实施例1-3的制备过程相比，除无S4步骤外，其余步骤S1-S3均一致。
对上述实施例1-3、对比例1-3和参照例1-3中所制纳米耐火材料按GB/T 13244-91《含碳耐火材料抗氧化性试验方法》进行试验，在下表中记录纳米耐火材料在不同高温环境下的脱碳层厚度：
Figure DEST_PATH_IMAGE001
由上表试验结果可知，在1600℃以下的高温环境下，每个试验组中脱碳层厚度由大到小依次是参照例＞对比例＞实施例，由此可见，在1600℃以下的高温环境中，由硼硅玻璃、二氧化钍和羧甲基纤维素钠溶液制备而成的复合高温抗氧化剂可以显著地提高纳米耐火材料在高温环境下的抗氧化效果。
试验二：对纳米耐火材料的抗热震性能测定
对比例4：与实施例1相比，除复合抗热震添加物的组成不同外，其余原料均一致；
对比例5：与实施例2相比，除复合抗热震添加物的组成不同外，其余原料均一致；
对比例6：与实施例3相比，除复合抗热震添加物的组成不同外，其余原料均一致；
上述对比例4-6中，复合抗热震添加物由板状刚玉粉为底料，硼熔块、二氧化硅为复配添加剂以及羧甲基纤维素钠溶液为结合剂经球磨混合后制备而成，其中，板状刚玉粉、硼熔块、二氧化硅以及羧甲基纤维素钠溶液的质量比为6:3:2:4，羧甲基纤维素钠溶液的浓度为45%。
对比例7：与实施例1相比，除复合抗热震添加物的组成不同外，其余原料均一致；
对比例8：与实施例2相比，除复合抗热震添加物的组成不同外，其余原料均一致；
对比例9：与实施例3相比，除复合抗热震添加物的组成不同外，其余原料均一致；
上述对比例7-9中，复合抗热震添加物由板状刚玉粉为底料，硼熔块、ThP2O7为复配添加剂以及羧甲基纤维素钠溶液为结合剂经球磨混合后制备而成，其中，纳米板状刚玉粉、硼熔块、ThP2O7以及羧甲基纤维素钠溶液的质量比为6:3:2:4，羧甲基纤维素钠溶液的浓度为45%。
上述对比例4-9中的制备过程与实施例1-3的制备过程一致。
参照例4：与实施例1相比，除不添加复合抗热震添加物外，其余原料均一致；
参照例5：与实施例2相比，除不添加复合抗热震添加物外，其余原料均一致；
参照例6：与实施例3相比，除不添加复合抗热震添加物外，其余原料均一致；
参照例4-6的制备过程与实施例1-3的制备过程相比，除在S2步骤中不再添加复合抗热震添加物外，其余步骤均一致。
对上述实施例1-3、对比例4-9以及参照例4-6中所制纳米耐火材料按GB/T 30873-2014《耐火材料 抗热震性试验方法》中方法1（水急冷法）进行试验，并在下表记录纳米耐火材料所经历的抗热震性测试次数和受热端面的破损率（破损率取整）：
Figure 940884DEST_PATH_IMAGE002
由上表试验结果可知，每个试验组中，纳米耐火材料在进行抗热震性测试时的次数由多到少依次是实施例＞对比例＞参照例，且纳米耐火材料在测试时受热端面破损率由大到小依次为参照例＞对比例＞实施例，由此可见，无论在复合抗热震添加物中所加入的复配添加剂是二氧化硅还是ThP2O7，都可以对该纳米耐火材料起到一定的抗热震性效果，但当其二者同时添加到复合抗热震添加物中后，该抗热震性效果则会得到进一步地提升。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。

Claims (9)

1.用于塞棒的纳米耐火材料，其特征在于，按质量份计包括以下原料：
硅酸铝85-95份、电熔氧化铝80-90份、石墨80-90份、纳米碳化硅80-90份、纳米碳纤维75-95份、液态酚醛树脂结合剂75-85份、炭黑45-65份、锆莫来石45-55份、复合高温抗氧化剂75-135份、催化剂45-55份、复合抗热震添加物85-170份。
2.根据权利要求1所述的用于塞棒的纳米耐火材料，其特征在于，所述催化剂为硝酸镍和硝酸钴按质量比1:1混合而成的混合物。
3.根据权利要求1所述的用于塞棒的纳米耐火材料，其特征在于，所述复合高温抗氧化剂由硼硅玻璃为基料，二氧化钍为复合料以及羧甲基纤维素钠溶液为结合剂经球磨混合后制备而成。
4.根据权利要求3所述的用于塞棒的纳米耐火材料，其特征在于，所述硼硅玻璃、二氧化钍和羧甲基纤维素钠溶液的质量比为7:5:3，羧甲基纤维素钠溶液的浓度为35%-40%。
5.根据权利要求1所述的用于塞棒的纳米耐火材料，其特征在于，所述复合抗热震添加物由板状刚玉粉为底料，硼熔块、二氧化硅和ThP2O7为复配添加剂以及羧甲基纤维素钠溶液为结合剂经球磨混合后制备而成。
6.根据权利要求5所述的用于塞棒的纳米耐火材料，其特征在于，所述板状刚玉粉、硼熔块、二氧化硅、ThP2O7以及羧甲基纤维素钠溶液的质量比为6:3:2:2:4，羧甲基纤维素钠溶液的浓度为45%-48%。
7.根据权利要求3或5所述的用于塞棒的纳米耐火材料，其特征在于，所述球磨混合的过程为：按配比称取原料放入球磨机中，再以球料比7:2加入氧化锆球磨珠，以570-600r/min的转速混磨2-5小时。
8.用于塞棒的纳米耐火材料制备方法，其特征在于，包括以下步骤：
S1、按配方称量好原料，备用；
S2、将硅酸铝、电熔氧化铝、炭黑和锆莫来石混合后通过干燥、球磨后得到复合粉体，按照顺序将复合粉体、石墨、复合抗热震添加物、液态酚醛树脂结合剂、纳米碳化硅和纳米碳纤维在混砂机中混合均匀，并干燥24小时，得混合料；
S3、利用万能压力机将混合料压制成圆柱状的塞棒，将干燥好的塞棒装在匣钵内并在埋碳条件下依次在900℃和1100℃的温度环境下分别保温2-3小时，最后取出后冷却至室温后即得纳米耐火材料；
S4、在纳米耐火材料的表面上涂抹复合高温抗氧化剂，涂抹完毕后将其置于煅烧炉内煅烧1-1.6小时，使得复合高温抗氧化剂在纳米耐火材料的表面形成一层防护膜，即得最终的纳米耐火材料。
9.根据权利要求8所述的用于塞棒的纳米耐火材料制备方法，其特征在于，所述万能压力机的设定压力范围在170kN-200kN之间。
CN202111144733.9A 2021-09-28 2021-09-28 用于塞棒的纳米耐火材料制备方法 Active CN113999023B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111144733.9A CN113999023B (zh) 2021-09-28 2021-09-28 用于塞棒的纳米耐火材料制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111144733.9A CN113999023B (zh) 2021-09-28 2021-09-28 用于塞棒的纳米耐火材料制备方法

Publications (2)

Publication Number Publication Date
CN113999023A true CN113999023A (zh) 2022-02-01
CN113999023B CN113999023B (zh) 2022-11-25

Family

ID=79921964

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111144733.9A Active CN113999023B (zh) 2021-09-28 2021-09-28 用于塞棒的纳米耐火材料制备方法

Country Status (1)

Country Link
CN (1) CN113999023B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117383949A (zh) * 2023-11-10 2024-01-12 江苏君耀耐磨耐火材料有限公司 一种碳纳米纤维增韧耐火材料的制备方法

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5681499A (en) * 1994-06-15 1997-10-28 Vesuvius Crucible Company Method and compositions for making refractory shapes having dense, carbon free surfaces and shapes made therefrom
JPH10338569A (ja) * 1997-05-31 1998-12-22 Harima Ceramic Co Ltd タンデッシュ用ストッパーヘッド
CN1544389A (zh) * 2003-11-18 2004-11-10 北京科技大学 一种含氮化硅铁的免烘烤铁沟捣打料
CN102896309A (zh) * 2011-07-29 2013-01-30 宝山钢铁股份有限公司 一种连铸用整体塞棒及其制备方法
CN104402462A (zh) * 2014-10-13 2015-03-11 瑞泰科技股份有限公司 一种用于高炉渣生产矿棉控流的塞棒及其工艺
CN104926323A (zh) * 2015-05-18 2015-09-23 浙江长兴银兴窑业有限公司 一种含有碳化硅的耐火材料
CN105016745A (zh) * 2015-05-18 2015-11-04 浙江长兴银兴窑业有限公司 含有碳化硅的耐火材料
CN105418094A (zh) * 2015-12-01 2016-03-23 浙江铁狮高温材料有限公司 一种长寿命尖晶石材料整体塞棒
CN105967657A (zh) * 2016-05-04 2016-09-28 黄河科技学院 一种环保型耐火材料及其制备方法
CN110330319A (zh) * 2019-07-13 2019-10-15 南昌航空大学 一种低碳超低碳的铝碳烧成耐火材料及其制备方法
CN110922214A (zh) * 2019-12-06 2020-03-27 马鞍山钢铁股份有限公司 一种防止浸入式水口结瘤的涂层材料及其制备方法
CN111099901A (zh) * 2019-12-23 2020-05-05 安徽鼎特瑞网络科技有限公司 一种高抗热震性莫来石耐火砖及其生产方法
CN111348903A (zh) * 2019-07-04 2020-06-30 营口石兴耐火材料科技有限公司 一种铝碳质整体塞棒及其制备方法
CN111470851A (zh) * 2019-08-27 2020-07-31 北京利尔高温材料股份有限公司 一种整体塞棒用棒身材料

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5681499A (en) * 1994-06-15 1997-10-28 Vesuvius Crucible Company Method and compositions for making refractory shapes having dense, carbon free surfaces and shapes made therefrom
JPH10338569A (ja) * 1997-05-31 1998-12-22 Harima Ceramic Co Ltd タンデッシュ用ストッパーヘッド
CN1544389A (zh) * 2003-11-18 2004-11-10 北京科技大学 一种含氮化硅铁的免烘烤铁沟捣打料
CN102896309A (zh) * 2011-07-29 2013-01-30 宝山钢铁股份有限公司 一种连铸用整体塞棒及其制备方法
CN104402462A (zh) * 2014-10-13 2015-03-11 瑞泰科技股份有限公司 一种用于高炉渣生产矿棉控流的塞棒及其工艺
CN105016745A (zh) * 2015-05-18 2015-11-04 浙江长兴银兴窑业有限公司 含有碳化硅的耐火材料
CN104926323A (zh) * 2015-05-18 2015-09-23 浙江长兴银兴窑业有限公司 一种含有碳化硅的耐火材料
CN105418094A (zh) * 2015-12-01 2016-03-23 浙江铁狮高温材料有限公司 一种长寿命尖晶石材料整体塞棒
CN105967657A (zh) * 2016-05-04 2016-09-28 黄河科技学院 一种环保型耐火材料及其制备方法
CN111348903A (zh) * 2019-07-04 2020-06-30 营口石兴耐火材料科技有限公司 一种铝碳质整体塞棒及其制备方法
CN110330319A (zh) * 2019-07-13 2019-10-15 南昌航空大学 一种低碳超低碳的铝碳烧成耐火材料及其制备方法
CN111470851A (zh) * 2019-08-27 2020-07-31 北京利尔高温材料股份有限公司 一种整体塞棒用棒身材料
CN110922214A (zh) * 2019-12-06 2020-03-27 马鞍山钢铁股份有限公司 一种防止浸入式水口结瘤的涂层材料及其制备方法
CN111099901A (zh) * 2019-12-23 2020-05-05 安徽鼎特瑞网络科技有限公司 一种高抗热震性莫来石耐火砖及其生产方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
袁哲俊等: "《纳米科学技术及应用》", 30 September 2019, 哈尔滨工业大学出版社 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117383949A (zh) * 2023-11-10 2024-01-12 江苏君耀耐磨耐火材料有限公司 一种碳纳米纤维增韧耐火材料的制备方法
CN117383949B (zh) * 2023-11-10 2024-04-02 江苏君耀耐磨耐火材料有限公司 一种碳纳米纤维增韧耐火材料的制备方法

Also Published As

Publication number Publication date
CN113999023B (zh) 2022-11-25

Similar Documents

Publication Publication Date Title
CN110483052B (zh) 一种碳化硅耐火材料及其制备方法
JP3212600B2 (ja) シアロン基質により結合された耐火性材料及び調製方法
CN111704466B (zh) 一种碳化硅-镁铝尖晶石-铝复合耐火材料
GB2072220A (en) Composite sinter of silicon nitride/boron nitride and method for manufacturing thereof
CN109467437B (zh) 一种金属陶瓷复合耐磨材料及其制备方法
CN113716969B (zh) 一种莫来卡特抗结皮浇注料及预制件的制备方法
CN107382346B (zh) 耐火耐磨浇筑料及制备方法
CN113999023B (zh) 用于塞棒的纳米耐火材料制备方法
CN111704474A (zh) 一种超高温冶炼用莫来石质耐火浇注料
CN110483080B (zh) 一种碳化硅粉体及其制备方法
CN113968724B (zh) 一种金属改性镁砂、低碳转炉镁质滑板及它们的制备方法
WO2020013662A1 (ko) 2차 정련로용 마그네시아-카본 염기성 캐스터블
CN108101559A (zh) 镁碳砖及其制备方法
CN1003586B (zh) 赛隆-氮化硼纤维复合材料及其制造方法
CN1006886B (zh) 氮化硅/氮化硼复合材料及其制造方法
CN112358305A (zh) 一种防纵裂的电炉钢包包壁镁碳砖及其制备工艺
CN111517798A (zh) 一种碳化物基陶瓷材料、制备方法及其应用
CN109231972B (zh) 轻质电熔刚玉砖
CN110981513A (zh) 一种铬刚玉渣-高铝矾土复合无碳钢包下水口砖及其制备方法
CN113979761A (zh) 一种三元复合自修复免烧滑板砖及其制备方法
CN104987076A (zh) 一种高韧性碳化硅陶瓷及其低温烧结工艺
CN114380537A (zh) 一种碳化硅轻量型密封环及其制备方法
CN111302814B (zh) 一种铝碳化硅炭质泥浆及其制备方法
CN114644512A (zh) 特种钢连铸用抗侵蚀浸入式水口及其制备方法
CN113307625A (zh) 一种ZrO2-C纤维复合材料及其制备方法

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
GR01 Patent grant
GR01 Patent grant