CN106336232A - 一种抗氧化彩色锆英石耐火砖的制备方法 - Google Patents
一种抗氧化彩色锆英石耐火砖的制备方法 Download PDFInfo
- Publication number
- CN106336232A CN106336232A CN201610750245.5A CN201610750245A CN106336232A CN 106336232 A CN106336232 A CN 106336232A CN 201610750245 A CN201610750245 A CN 201610750245A CN 106336232 A CN106336232 A CN 106336232A
- Authority
- CN
- China
- Prior art keywords
- antioxidation
- refractory brick
- colour
- zircon
- zircon refractory
- 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
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
- C04B35/01—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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/482—Refractories from grain sized mixtures
-
- 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
-
- 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
- C04B35/634—Polymers
- C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
-
- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5029—Magnesia
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5031—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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- 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
- C04B2235/3225—Yttrium oxide or oxide-forming salts 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
- 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
- C04B2235/3234—Titanates, not containing zirconia
-
- 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
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B2235/3248—Zirconates or hafnates, e.g. zircon
-
- 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
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
-
- 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
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
-
- 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
- C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
- C04B2235/661—Multi-step sintering
-
- 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
- C04B2235/963—Surface properties, e.g. surface roughness
-
- 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
- C04B2235/9684—Oxidation resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Furnace Housings, Linings, Walls, And Ceilings (AREA)
Abstract
本发明公开了一种抗氧化彩色锆英石耐火砖的制备方法,抗氧化彩色锆英石耐火砖由混合料、结合剂和抗氧化剂烧结而成,步骤如下:1)混合料准备;2)混合浆准备;3)待烧砖;4)彩色锆英石耐火砖;5)整理砖;6)抗氧化砖坯;7)抗氧化彩色锆英石耐火砖。本发明所制备的抗氧化彩色锆英石耐火砖实现了对锆英石耐火砖的着色,是对无彩色锆英石耐火砖的一个重要补充,且具有耐久性的抗氧化、耐高温、抗侵蚀、耐磨损、低导热和优良的热震稳定性能等特点。
Description
技术领域
本发明属于耐火材料领域,尤其是涉及一种抗氧化彩色锆英石耐火砖的制备方法。
背景技术
锆英石耐火砖是一种酸性耐火材料,是以天然锆英石砂(ZrSiO2)为原料制得的制品。锆英石耐火砖不同于硅铝系列耐火砖和含碳系列耐火砖,其抗渣性好,热膨胀率较小,热导率随温度的升高而降低,荷重软化温度高,耐磨强度大,抗热震性好,现已成为各个工业领域中的重要材料。随着冶金工业中连铸和真空脱气技术的发展,锆英石耐火砖的应用越来越广泛。
在炼钢过程中,采用出钢脱气法,而锆英石质耐火材料对熔渣,钢水的耐侵蚀性和抗热震性良好,且适于在减压下工作,它在冶金工业中广泛用于砌筑脱气用盛钢桶内衬,也用作不锈钢盛钢桶内衬,连铸盛钢桶内衬、铸口砖、塞头砖、袖砖以及高温感应电炉炉衬等。锆英石质耐火砖对酸性渣和玻璃具有高的抵抗性,因而还广泛用于熔炼最活泼玻璃的玻璃窑的严重损坏部位。锆英石质耐火材料还具有不为金属铝、铝的氧化物及其熔渣侵透的性质,因而在炼铝的炉底上也获得了良好的效果。
目前对于锆英石耐火砖的制作与使用上强调高导热耐火材料的制备,也从其用途上进行设计。将高导热、中等导热材料相结合的炉衬设计思想从炉底扩展到炉缸、炉腰、炉腹和炉身部分,使高炉炉缸、炉底等部分得到了一个特定的等温线分布,保证了冶炼正常进行。如果采用单一温度等级的高温耐火作为炉衬,既浪费了材料,又由于高温耐火砖的售价往往较高,也导致企业使用成本上升,减少了市场竞争力。然而,目前所制备的锆英石耐火砖多为灰土色,在高炉炉缸的施工过程中,往往辨识度不足,易造成施工误操作而影响冶炼正常进行,也浪费资源。因此,如何提高锆英石砖的辨识度,提高施工效率,降低耐火砖的使用成本,保证冶炼正常进行具有重要的意义。
此外,锆英石耐火砖是一种多晶氧化锆耐火材料,晶体组成一般为四方和/或立方相氧化锆。由于氧化锆本身的具有2715℃的高熔点、不易被氧化和高温优良特点,可以成为一种可以在氧化、中性和还原性环境中使用,在1600℃以上的超高温下长期稳定使用,最高温度可达2200℃,导热系统最小,耐酸碱腐蚀能力强于氧化硅和氧化铝,然而,多晶氧化锆也有物理特性上的不足。氧化锆常温以单斜相出现,升温至1100℃左右转变为四方相,这种相变是可逆的。相变也会带来体积的变化,单斜相向四方相转变的时候会产生较大的体积收缩,从而使多晶氧化锆砖破裂的发生频率大幅提高。碳素具有热膨胀率低的特点,将碳素作为填料在熔融体系中分散,使与碳结合的基体部分形成柔性结构化、韧性化,从而使该耐火材料的宏观特性被改善,抑制耐火材料破裂的产生。然而,另一个问题随之出现,即碳素容易受到氧化侵蚀,反而使耐火材料的结构遭受破坏。因此,提供一种锆英石耐火砖的抗氧化方法是非常重要的研究方向。
对于提高耐火材料的抗氧化性能主要是通过在制备过程中加入抗氧化剂的方式实现。专利CN102295464B公开了一种碳复合耐火材料及其制备方法,先将石墨烯、氧化物微粉和抗氧化剂共磨,得到预制混合粉,再进行烧结成型。然而采用共混的方法加入抗氧化剂难以使耐火材料表层免受氧化作用侵袭,空气中的氧化组分的逐层侵入会大大减少耐火材料的使用寿命。
发明内容
为克服锆英石耐火砖辨识度不足及抗氧化能力差的问题,本发明提供一种抗氧化彩色锆英石耐火砖的制备方法。
本发明是通过以下技术实现的:
1. 一种抗氧化彩色锆英石耐火砖的制备方法,所述抗氧化彩色锆英石耐火砖由混合料、结合剂和抗氧化剂烧结而成,所述混合料由锆英石、斜锆石、钛锆钍矿、磷钇矿、钛铁矿以及着色物质组成,所述结合剂为聚乙烯醇水溶液、羧甲基纤维素水溶液、海藻酸钠水溶液和聚甲基丙烯酸甲酯水溶液中的一种或几种,所述着色物质为三氧化二铁、氧化亚铁、氧化亚铜、五氧化二钒和三氧化二铬中的一种或几种,步骤如下:
1)混合料准备:按质量配比称取锆英石、斜锆石、钛锆钍矿、磷钇矿、钛铁矿以及着色物质,并在800~1000℃下保温1~3小时,保温完毕,碾碎至50~150目得到混合料;
2)混合浆准备:取混合料与结合剂混合,并加水搅拌均匀后陈化1~2天得到混合浆;
3)待烧砖:利用制砖模具对混合浆进行制砖,于80~85℃下烘焙5~6小时得到待烧砖;
4)彩色锆英石耐火砖:将待烧砖分段保温烧结成型得到彩色锆英石耐火砖;
5)整理砖:将彩色锆英石耐火砖浸没于抗氧化整理液中,时间为10~60分钟,得到整理砖;
6)抗氧化砖坯:将整理砖在60~80℃温度下烘焙6~8小时得到抗氧化砖坯;
7)抗氧化彩色锆英石耐火砖:将抗氧化砖坯于300~500℃条件下保温2~4小时后,以升温速度为30~50℃/分升温至1600~1700℃,保温1~3小时得到抗氧化彩色锆英石耐火砖。
本发明所制备的是一种可在超高温下长期稳定使用的锆英石耐火砖,成分中含锆量达50%以上,具有优良抗侵蚀性能、抗渗透性、抗剥落性能和优良的热震稳定性能,使用温度为1900~2100℃。本说明书中,在原料配比上并未直接加入碳素材料,然而结合剂多为有机化合物,该有机化合物的加入正是为碳素的形成提供原料,在彩色锆英石耐火砖的高温烧结过程中,有机化合物受到高温的作用而碳化形成碳素。氧化锆常温以单斜相出现,升温至1100℃左右转变为四方相,这种相变是可逆的。相变也会带来体积的变化,单斜相向四方相转变的时候会产生较大的体积收缩。碳素的形成正可起到缓冲多晶氧化锆砖在高温使用条件下的体积收缩现象,与碳结合的基体部分形成柔性结构化、韧性化,使该耐火材料的宏观特性被改善,抑制导致耐火材料破裂的产生,甚至可以减少裂纹的产生。
在本说明书中,为克服锆英石耐火砖辨识度的不足,发明人采用对锆英石耐火砖进行染色,所使用的着色物质多为价格低廉、健康环保的金属氧化物。
在原料中加入着色物质实现对锆英石耐火砖的着色是本发明的发明点之一。经本发明人实践表明,无着色物质的加入,所制备的锆英石耐火砖呈现的是一种浅灰色,而加入2%~5%的着色物质,制得的锆英石耐火砖则表现出了着色物质的本色。其中三氧化二铁、五氧化二钒的加入可获黄色锆英石耐火砖,氧化亚铜可得红色锆英石耐火砖,氧化亚铁、三氧化二铬可得绿色锆英石耐火砖。本发明首次对锆英石耐火砖进行着色,这对于传统意义上无彩色的锆英石耐火砖是一个重要的补充。
对所制得的彩色锆英石耐火砖进行抗氧化整理方法是本发明的另一个重要发明点。本发明首先配备抗氧化整理液,以水镁石和铝土矿为抗氧化剂。水镁石的主体成分为氢氧化镁,氢氧化镁在350℃下熔融并分解成氧化镁和水,1800℃时会完全脱水。铝土矿的主体成分氢氧化铝,氢氧化铝在300℃下熔融并分解成氧化铝和水。1600℃时会完全脱水。将400~600目抗氧化剂在分散剂的作用下与水形成具有一定粘度的悬浮体系,即为抗氧化整理液。将彩色锆英石耐火砖浸入抗氧化整理液中,抗氧化剂粘附至耐火砖的表面。将表面粘附有抗氧化剂的耐火砖(即为整理砖)于60~80℃温度下烘焙6~8小时,其目的是去除耐火砖所吸附的水分。发明人经反复实验表明,在去除水分过程的温度不宜过高,较低的温度利于抗氧化剂在耐火砖表面的均匀分布。将烘焙完毕所得的抗氧化砖坯于300~500℃条件下保温,可使抗氧化剂在耐火砖的表面熔融、均匀扩散。随着将保温温度迅速提升至1600~1800℃,使均匀扩散的抗氧化剂发生完全脱水,形成氧化镁或氧化铝物质层,氧化镁或氧化铝的熔点较高,分别为2800℃和2054℃,可知,在彩色锆英石耐火砖表面形成抗氧化层并不会影响耐火砖的使用温度,且该抗氧化层可以起到将耐火砖中的碳素与空气中氧化组分相隔离的作用,以避免碳素受到氧化作用以影响耐火砖的使用寿命。此外,经测试,抗氧化彩色锆英石耐火砖表面的抗氧化层厚度为1~2微米,不会对耐火砖的表面色产生明显影响。
优选地,所述混合料的质量配比为锆英石45%~55%,斜锆石石10%~20%,钛锆钍矿15%~25%,磷钇矿5%~10%,钛铁矿5%~15%,着色物质2%~5%,总量为100%。
优选地,所述混合浆中,混合料的含量为80wt%~90wt%,结合剂的含量为5wt%~10wt%,水的含量为5wt%~10wt%,总量为100wt%。
优选地,所述抗氧化整理液中,抗氧化剂的含量为20wt%~30wt%,分散剂的含量为5wt%~10wt%,水的含量为60wt%~75wt%,总量为100wt%。
优选地,所述抗氧化剂为水镁石粉末和铝土矿粉末中的一种或两种,粒径为400~600目。
优选地,所述聚乙烯醇水溶液的浓度为3wt%~5 wt%,所述羧甲基纤维素水溶液的浓度为2wt%~8wt%,所述海藻酸钠水溶液的浓度为4wt%~7wt%,所述聚甲基丙烯酸甲酯水溶液的浓度为2wt%~5wt%。
优选地,分段保温烧结成型是在工业氮气的气氛中完成。
优选地,分段保温烧结成型是在1100~1300℃条件下保温6~12小时,然而以升温速度1~10℃/分升温至1500~1700℃并保温6~12小时。
优选地,所述抗氧化彩色锆英石耐火砖的颜色为红色、绿色、黄色中的一种。
优选地,所述分散剂为水玻璃、三聚磷酸钠、六偏磷酸钠和焦磷酸钠中的一种或几种。
本发明的有益效果在于:(1)对锆英石耐火砖进行着色,是对无彩色锆英石耐火砖的一个重要补充;(2)通过表面涂层的方法实现抗氧化彩色锆英石耐火砖的制备,将耐火砖中的碳素与空气中氧化组分相隔离,具有耐久的抗氧化效果;(3)通过锆英石、斜锆石、钛锆钍矿、磷钇矿、钛铁矿以及着色物质配制而成的锆英石耐火砖,具有良好的耐高温、抗侵蚀、耐磨损、低导热性能以及优良的热震稳定性能。
具体实施方式
实施例1
称取锆英石46.7wt%、斜锆石16.3wt%、钛锆钍矿20.5wt%、磷钇矿6.3wt%、钛铁矿7.2wt%以及氧化亚铜3.0wt%,碾碎至50目,800℃下保温1小时得到混合料。保温完毕,称取混合料85wt%,羧甲基纤维素水溶液(浓度为5%)10wt%,水5wt%,搅拌混合均匀并陈化1天得到混合浆。利用制砖模具对混合浆进行制砖,并于80℃下烘焙5小时得到待烧砖。将待烧砖在工业氮气氛围下,于1100℃条件下保温6小时后,以3℃/分升温速度升温至1500℃并保温6小时得到彩色锆英石耐火砖。称取水镁石粉末(400目)25wt%,水玻璃8wt%和水67wt%,混合并搅拌得到抗氧化整理液。将彩色锆英石耐火砖浸入抗氧化整理液中,15分钟后取出并置于65℃温度下烘焙6小时得到抗氧化砖坯。将抗氧化砖坯于350℃条件下保温3小时后,以升温速度为50℃/分升温至1800℃,保温2小时后即得抗氧化彩色锆英石耐火砖。
利用Datacolor SF600X测色仪对锆英石耐火砖进行测色,其色度指标为L * 31.2,a * 33.5,b * 7.2,由色度指标可知,本实施例所得抗氧化彩色锆英石耐火砖的颜色为红色。
实施例2
称取锆英石51.3wt%、斜锆石13.2wt%、钛锆钍矿16.4wt%、磷钇矿8.3wt%、钛铁矿6.3wt%以及氧化亚铁4.5wt%,碾碎至100目,850℃下保温2小时得到混合料。保温完毕,称取混合料90wt%,聚乙烯醇水溶液(浓度为4%)5wt%,水5wt%,搅拌混合均匀并陈化1.5天得到混合浆。利用制砖模具对混合浆进行制砖,并于85℃下烘焙6小时得到待烧砖。将待烧砖在工业氮气氛围下,于1200℃条件下保温9小时后,以5℃/分升温速度升温至1600℃并保温8小时得到彩色锆英石耐火砖。称取铝土矿粉末(500目)30wt%,三聚磷酸钠10wt%和水60wt%,混合并搅拌得到抗氧化整理液。将彩色锆英石耐火砖浸入抗氧化整理液中,30分钟后取出并置于80℃温度下烘焙7小时得到抗氧化砖坯。将抗氧化砖坯于300℃条件下保温4小时后,以升温速度为30℃/分升温至1600℃,保温3小时后即得抗氧化彩色锆英石耐火砖。
利用Datacolor SF600X测色仪对锆英石耐火砖进行测色,其色度指标为L * 59.1,a * -33.1,b * 6.1,由色度指标可知,本实施例所得抗氧化彩色锆英石耐火砖的颜色为绿色。
Claims (10)
1.一种抗氧化彩色锆英石耐火砖的制备方法,其特征是,所述抗氧化彩色锆英石耐火砖由混合料、结合剂和抗氧化剂烧结而成,所述混合料由锆英石、斜锆石、钛锆钍矿、磷钇矿、钛铁矿以及着色物质组成,所述结合剂为聚乙烯醇水溶液、羧甲基纤维素水溶液、海藻酸钠水溶液和聚甲基丙烯酸甲酯水溶液中的一种或几种,所述着色物质为三氧化二铁、氧化亚铁、氧化亚铜、五氧化二钒和三氧化二铬中的一种或几种,步骤如下:
1)混合料准备:按质量配比称取锆英石、斜锆石、钛锆钍矿、磷钇矿、钛铁矿以及着色物质,并在800~1000℃下保温1~3小时,保温完毕,碾碎至50~150目得到混合料;
2)混合浆准备:取混合料与结合剂混合,并加水搅拌均匀后陈化1~2天得到混合浆;
3)待烧砖:利用制砖模具对混合浆进行制砖,于80~85℃下烘焙5~6小时得到待烧砖;
4)彩色锆英石耐火砖:将待烧砖分段保温烧结成型得到彩色锆英石耐火砖;
5)整理砖:将彩色锆英石耐火砖浸没于抗氧化整理液中,时间为10~60分钟,得到整理砖;
6)抗氧化砖坯:将整理砖在60~80℃温度下烘焙6~8小时得到抗氧化砖坯;
7)抗氧化彩色锆英石耐火砖:将抗氧化砖坯于300~500℃条件下保温2~4小时后,以升温速度为30~50℃/分升温至1600~1800℃,保温1~3小时得到抗氧化彩色锆英石耐火砖。
2.根据权利要求1所述的一种抗氧化彩色锆英石耐火砖的制备方法,其特征是,所述混合料的质量配比为锆英石45%~55%,斜锆石10%~20%,钛锆钍矿15%~25%,磷钇矿5%~10%,钛铁矿5%~15%,着色物质2%~5%,总量为100%。
3.根据权利要求1所述的一种抗氧化彩色锆英石耐火砖的制备方法,其特征是,所述混合浆中,混合料的含量为80wt%~90wt%,结合剂的含量为5wt%~10wt%,水的含量为5wt%~10wt%,总量为100wt%。
4.根据权利要求1所述的一种抗氧化彩色锆英石耐火砖的制备方法,其特征是,所述抗氧化整理液中,抗氧化剂的含量为20wt%~30wt%,分散剂的含量为5wt%~10wt%,水的含量为60wt%~75wt%,总量为100wt%。
5.根据权利要求1或4所述的一种抗氧化彩色锆英石耐火砖的制备方法,其特征是,所述抗氧化剂为水镁石粉末和铝土矿粉末中的一种或两种,粒径为400~600目。
6.根据权利要求1所述的一种抗氧化彩色锆英石耐火砖的制备方法,其特征是,所述聚乙烯醇水溶液的浓度为3wt%~5 wt%,所述羧甲基纤维素水溶液的浓度为2wt%~8wt%,所述海藻酸钠水溶液的浓度为4wt%~7wt%,所述聚甲基丙烯酸甲酯水溶液的浓度为2wt%~5wt%。
7.根据权利要求1所述的一种抗氧化彩色锆英石耐火砖的制备方法,其特征是,分段保温烧结成型是在工业氮气的气氛中完成。
8.根据权利要求1所述的一种抗氧化彩色锆英石耐火砖的制备方法,其特征是,分段保温烧结成型是在1100~1300℃条件下保温6~12小时,然而以升温速度1~10℃/分升温至1500~1700℃并保温6~12小时。
9.根据权利要求1所述的一种抗氧化彩色锆英石耐火砖的制备方法,其特征是,所述抗氧化彩色锆英石耐火砖的颜色为红色、绿色和黄色中的一种。
10.根据权利要求4所述的一种抗氧化彩色锆英石耐火砖的制备方法,其特征是,所述分散剂为水玻璃、三聚磷酸钠、六偏磷酸钠和焦磷酸钠中的一种或几种。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610750245.5A CN106336232A (zh) | 2016-08-30 | 2016-08-30 | 一种抗氧化彩色锆英石耐火砖的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610750245.5A CN106336232A (zh) | 2016-08-30 | 2016-08-30 | 一种抗氧化彩色锆英石耐火砖的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN106336232A true CN106336232A (zh) | 2017-01-18 |
Family
ID=57823166
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610750245.5A Pending CN106336232A (zh) | 2016-08-30 | 2016-08-30 | 一种抗氧化彩色锆英石耐火砖的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN106336232A (zh) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101842325A (zh) * | 2007-10-26 | 2010-09-22 | 康宁股份有限公司 | 包含纳米添加剂的低蠕变锆石及其制备方法 |
CN102108025A (zh) * | 2009-12-29 | 2011-06-29 | 宋永刚 | 一种装饰用耐火制品 |
CN105218121A (zh) * | 2015-10-30 | 2016-01-06 | 淄博工陶耐火材料有限公司 | 低蠕变、锆英石不分解的溢流砖及其制备方法 |
CN105541411A (zh) * | 2015-12-30 | 2016-05-04 | 唐伟 | 锆英石基耐火制品 |
-
2016
- 2016-08-30 CN CN201610750245.5A patent/CN106336232A/zh active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101842325A (zh) * | 2007-10-26 | 2010-09-22 | 康宁股份有限公司 | 包含纳米添加剂的低蠕变锆石及其制备方法 |
CN102108025A (zh) * | 2009-12-29 | 2011-06-29 | 宋永刚 | 一种装饰用耐火制品 |
CN105218121A (zh) * | 2015-10-30 | 2016-01-06 | 淄博工陶耐火材料有限公司 | 低蠕变、锆英石不分解的溢流砖及其制备方法 |
CN105541411A (zh) * | 2015-12-30 | 2016-05-04 | 唐伟 | 锆英石基耐火制品 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102030548B (zh) | 一种金属陶瓷结合免烧低碳滑板砖及其制备方法 | |
CN101693791B (zh) | 连铸板坯高温防氧化涂料及其制备工艺 | |
CN103382116B (zh) | 含锆高强耐磨浇注料 | |
CN100584799C (zh) | 一种低成本耐火浇注料及其制备方法 | |
CN102584293B (zh) | 一种镁锆碳质滑动水口的制备方法 | |
CN103086728B (zh) | 一种钢包工作层防爆浇注料 | |
CN102329137B (zh) | 一种无碳铝镁质不烧砖、配制方法及应用 | |
CN103588492B (zh) | 一种精炼钢包衬用优质无碳铝镁尖晶石砖及其制备方法 | |
CN102838360B (zh) | 一种复合耐火材料及其制备方法 | |
CN104591752A (zh) | 一种用于rh精炼炉浸渍管和环流管的烧成镁尖晶石砖及其制备方法 | |
CN107162604B (zh) | 一种中高温烧成免浸渍滑板砖及其制备方法 | |
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 | |
CN112409002B (zh) | 一种碳含量大于40%的超高碳镁碳砖及其制备方法 | |
CN103787678A (zh) | 一种铝镁碳钢包耐火砖的制备方法 | |
CN102838361A (zh) | 一种MgCa-SiC-C耐火材料及其制备方法 | |
CN103332940A (zh) | 铜熔炼炉用半再结合镁铬砖及其制备方法 | |
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 | |
CN108585797B (zh) | 一种添加氮化硼的自润滑镁质挡渣滑板砖及其制备方法 | |
CN108558416A (zh) | 一种陶瓷烧成窑具及制备方法 | |
CN105272314A (zh) | 一种环保无铬透气砖 | |
CN103183516B (zh) | 一种钢包用机压无碳衬砖 | |
CN106396613A (zh) | 一种彩色烧结铝硅质耐火砖的制备方法 | |
CN112811888A (zh) | 一种中频感应炉炉底抗渗浇注料 | |
CN101733371B (zh) | 长圆形无锥度钢锭功能保护材料 | |
CN110627484A (zh) | 一种耐火砖及其制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
RJ01 | Rejection of invention patent application after publication | ||
RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170118 |