CN115353382A - 一种连铸用高强、增韧氧化锆定径水口及其制造方法 - Google Patents
一种连铸用高强、增韧氧化锆定径水口及其制造方法 Download PDFInfo
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000009749 continuous casting Methods 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000000498 ball milling Methods 0.000 claims description 20
- 235000015895 biscuits Nutrition 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052582 BN Inorganic materials 0.000 claims description 13
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 13
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 13
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 13
- 239000001095 magnesium carbonate Substances 0.000 claims description 13
- 239000000395 magnesium oxide Substances 0.000 claims description 13
- 239000002135 nanosheet Substances 0.000 claims description 13
- 238000000227 grinding Methods 0.000 claims description 12
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- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 11
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 11
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 11
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000748 compression moulding Methods 0.000 claims description 4
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims 2
- 230000035939 shock Effects 0.000 abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 abstract description 9
- 239000007791 liquid phase Substances 0.000 abstract description 7
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Abstract
本发明涉及耐火材料技术领域,尤其为一种连铸用高强、增韧氧化锆定径水口及其制造方法,其原料组份质量百分比为:氧化钇为1.8~2.4%,碱式碳酸镁为2.5~4%,氮化硼纳米片为0.08~0.1%,纳米氧化镁为0.3~0.5%,纳米氧化铝为0.5~0.8%,PVA胶水为8~9%,余量为氧化锆,本发明通过设计采用纳米级原料使其纳米特性烧制后仍部分存在,添加剂组分生成的晶体大小、含量及液相区分布对锆制品的高强、增韧、超微孔结构效应影响很大,控制共混、造粒、烧制等使纳米晶粒生成、扩散在适当的液相区范围内,可有效增强锆制品的抗冲刷、抗热震性能,且能有效避免结瘤的生成,同时设计了一套完善的、切实可行的纳米原料掺杂的锆制品制备方案,提高液相区的稳定性、抗冲刷性。
Description
技术领域
本发明涉及耐火材料技术领域,具体为一种连铸用高强、增韧氧化锆定径水口及其制造方法。
背景技术
氧化锆定径水口是一类十分关键的连铸工艺用功能性耐火材料制品,在使用过程中起到控流作用,控制中间包中的钢水连续、稳定的流向结晶器,稳定结晶器内的钢水液面高度,进而保持拉坯速度并提高连铸工作效率和产品质量,延长连铸浇铸炉数的同时提高中间包的使用寿命。
氧化锆定径水口在使用过程中,承受着严重的机械冲刷、化学侵蚀和应力剥落。其性能的评价常采用第二抗热应力断裂因子R'来评价,其理论核心为氧化锆定径水口材质的气孔率越低,晶粒尺寸越小,材料的强度越大,性能越好。同时需要具有良好的热震性能,减缓钢水对定径水口接触面的瞬间热冲击和冲刷,避免造成接触面微裂纹的生成,以及在使用过程中微裂纹的扩大甚至局部脱落。因此,具有高强度、低气孔率、小晶粒、高韧性是显著提高氧化锆定径水口使用寿命的关键。
综上所述,本发明通过设计一种连铸用高强、增韧氧化锆定径水口及其制造方法来解决存在的问题。
发明内容
本发明的目的在于提供一种连铸用高强、增韧氧化锆定径水口及其制造方法,以解决上述背景技术中提出的问题。
为实现上述目的,本发明提供如下技术方案:
一种连铸用高强、增韧氧化锆定径水口,其原料组份质量百分比为:氧化钇为1.8~2.4%,碱式碳酸镁为2.5~4%,氮化硼纳米片为0.08~0.1%,纳米氧化镁为0.3~0.5%,纳米氧化铝为0.5~0.8%,PVA胶水为8~9%,余量为氧化锆。
作为本发明优选的方案,所述的定径水口原料组份中,氧化钇为2.1%,碱式碳酸镁为3.1%,氮化硼纳米片为0.09%,纳米氧化镁为0.4%,纳米氧化铝为0.61%,PVA胶水为8.7%,余量为氧化锆。
作为本发明优选的方案,所述的氧化钇为工业级;碱式碳酸镁为工业级;氮化硼纳米片片径为0.1~0.4μm,BN含量为98wt%;纳米氧化镁平均粒径为20nm,近球形,比表面积>42m2/g,MgO含量为98wt%;纳米氧化铝平均粒径为10~15nm,γ相,比表面积>120m2/g,Al2O3含量为99.9wt%;PVA胶水中干基PVA的浓度为5wt%。
一种连铸用高强、增韧氧化锆定径水口的制造方法,其具体步骤如下:
步骤1,依重量百分比称取氧化钇、碱式碳酸镁、氧化锆作为球磨物料,装入聚氨酯球磨罐,加入氧化锆质磨球,在转速为160±10r/min的条件下磨至325~400目,形成预混料A,预混料A的混合均匀度变异系数小于2.5%;
步骤2,将预混料A进行焙烧,焙烧温度为1470±25℃,焙烧时间为8±0.5h,冷却后再次球磨至325~400目,形成预混料B;
步骤3,依重量百分比称取45%的预混料B与无水乙醇进行湿法研磨后干燥,粒度磨至8000~10000目,形成预混料C;
步骤4,依重量百分比称取氮化硼纳米片、纳米氧化镁、纳米氧化铝、PVA胶水,混合后先进行低速搅拌,搅拌速度为1000r/min,搅拌时间为15min,之后进行高速搅拌,搅拌速度为3500r/min,搅拌时间为45min,形成预混料D;
步骤5,将余下的预混料B、预混料C、预混料D进行充分混合后造粒,然后装入模具中,采用150t液压机压制成型,形成定径水口素坯;
步骤6,将素坯自然干燥24小时后,置于110℃烘箱中干燥20±2h,再放入1725±5℃的电炉中烧结7h,制成定径水口;
步骤7,降温后,进行局部打磨、测试、包装,入库,进行销售。
作为本发明优选的方案,所述步骤5中在混合的同时进行超声波振动。
与现有技术相比,本发明的有益效果是:
1、本发明中,通过采用纳米级原料使其纳米特性烧制后仍部分存在,添加剂组分生成的晶体大小、含量及液相区分布对锆制品的高强、增韧、超微孔结构效应影响很大,控制共混、造粒、烧制等使纳米晶粒生成、扩散在适当的液相区范围内,可有效增强锆制品的抗冲刷、抗热震性能,且能有效避免结瘤的生成。
2、本发明中,通过设计了一套完善的、切实可行的纳米原料掺杂的锆制品制备方案,可有效地对制品结构和液相区结构形态进行受控设计,解决了锆制品强度与抗热震性难以同时提升的难题,提高液相区的稳定性、抗冲刷性,从而具有高强、增韧的特性,具有良好的热震性能,可显著延长水口的使用寿命。
附图说明
图1为本发明氧化锆中液相区及纳米晶粒分别结构示意图。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例,基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
为了便于理解本发明,下面将参照相关附图对本发明进行更全面的描述,给出了本发明的若干实施例,但是,本发明可以以许多不同的形式来实现,并不限于本文所描述的实施例,相反地,提供这些实施例的目的是使对本发明的公开内容更加透彻全面。
需要说明的是,当元件被称为“固设于”另一个元件,它可以直接在另一个元件上或者也可以存在居中的元件,当一个元件被认为是“连接”另一个元件,它可以是直接连接到另一个元件或者可能同时存在居中元件,本文所使用的术语“垂直的”、“水平的”、“左”、“右”以及类似的表述只是为了说明的目的。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同,本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的,不是旨在于限制本发明,本文所使用的术语“及/或”包括一个或多个相关的所列项目的任意的和所有的组合。
实施例,请参阅图1,本发明提供一种技术方案:
一种连铸用高强、增韧氧化锆定径水口,其原料组份质量百分比为:氧化钇为1.8~2.4%,碱式碳酸镁为2.5~4%,氮化硼纳米片为0.08~0.1%,纳米氧化镁为0.3~0.5%,纳米氧化铝为0.5~0.8%,PVA胶水为8~9%,余量为氧化锆。
所述的定径水口原料组份中,氧化钇为2.1%,碱式碳酸镁为3.1%,氮化硼纳米片为0.09%,纳米氧化镁为0.4%,纳米氧化铝为0.61%,PVA胶水为8.7%,余量为氧化锆。
所述的氧化钇为工业级;碱式碳酸镁为工业级;氮化硼纳米片片径为0.1~0.4μm,BN含量为98wt%;纳米氧化镁平均粒径为20nm,近球形,比表面积>42m2/g,MgO含量为98wt%;纳米氧化铝平均粒径为10~15nm,γ相,比表面积>120m2/g,Al2O3含量为99.9wt%;PVA胶水中干基PVA的浓度为5wt%。
一种连铸用高强、增韧氧化锆定径水口的制造方法,步骤为:
(1)依重量百分比称取氧化钇、碱式碳酸镁、氧化锆作为球磨物料,装入聚氨酯球磨罐,加入氧化锆质磨球,在转速为160±10r/min的条件下磨至325~400目,形成预混料A,预混料A的混合均匀度变异系数小于2.5%;
(2)将预混料A进行焙烧,焙烧温度为1470±25℃,焙烧时间为8±0.5h,冷却后再次球磨至325~400目,形成预混料B;
(3)依重量百分比称取45%的预混料B与无水乙醇进行湿法研磨后干燥,粒度磨至8000~10000目,形成预混料C;
(4)依重量百分比称取氮化硼纳米片、纳米氧化镁、纳米氧化铝、PVA胶水,混合后先进行低速搅拌,搅拌速度为1000r/min,搅拌时间为15min,之后进行高速搅拌,搅拌速度为3500r/min,搅拌时间为45min,形成预混料D;
(5)将余下的预混料B、预混料C、预混料D进行充分混合后造粒,然后装入模具中,采用150t液压机压制成型,形成定径水口素坯;
(6)将素坯自然干燥24小时后,置于110℃烘箱中干燥20±2h,再放入1725±5℃的电炉中烧结7h,制成定径水口;
(7)降温后,进行局部打磨、测试、包装,入库,进行销售。
所述定径水口的制备方法,步骤(5)中,在混合的同时进行超声波振动。
本发明的氧化锆定径水口,合格产品检测指标范围为:耐压强度≥400MPa;热震次数≥20次,使用寿命≥15h;
具体实施案例:
请参见附图1,实施例1~6和对比例1~4的一种连铸用高强、增韧氧化锆定径水口,其原料组份质量分数见表1。
表1实施例1~6和对比例1~4的原料组成,wt%
一种连铸用高强、增韧氧化锆定径水口的制造方法,步骤为:
(1)依重量百分比称取氧化钇、碱式碳酸镁、氧化锆作为球磨物料,装入聚氨酯球磨罐,加入氧化锆质磨球,在转速为160±10r/min的条件下磨至325~400目,形成预混料A,预混料A的混合均匀度变异系数小于2.5%;
(2)将预混料A进行焙烧,焙烧温度为1470±25℃,焙烧时间为8±0.5h,冷却后再次球磨至325~400目,形成预混料B;
(3)依重量百分比称取45%的预混料B与无水乙醇进行湿法研磨后干燥,粒度磨至8000~10000目,形成预混料C;
(4)依重量百分比称取氮化硼纳米片、纳米氧化镁、纳米氧化铝、PVA胶水,混合后先进行低速搅拌,搅拌速度为1000r/min,搅拌时间为15min,之后进行高速搅拌,搅拌速度为3500r/min,搅拌时间为45min,形成预混料D;
(5)将余下的预混料B、预混料C、预混料D进行充分混合后造粒,然后装入模具中,采用150t液压机压制成型,形成定径水口素坯;
(6)将素坯自然干燥24小时后,置于110℃烘箱中干燥20±2h,再放入1725±5℃的电炉中烧结7h,制成定径水口;
(7)降温后,进行局部打磨、测试、包装,入库,进行销售。
所述定径水口的制备方法,步骤(5)中,在混合的同时进行超声波振动。
本发明的氧化锆定径水口,合格产品检测指标范围为:耐压强度≥400MPa;热震次数≥20次,使用寿命≥15h。
将实施例1~6和对比例1~4的一种连铸用高强、增韧氧化锆定径水口,体积密度、显气孔率按照GB/T2997-2000用排水法进行测试,耐压强度按照GB/T 5072-2008耐火材料常温耐压强度试验方法进行测试,热震性按照YB/T376.3-2004耐火制品热震性试验检测方法进行测试,使用寿命在生产现场使用时获得。测试结果列于表2中。
表2实施例1~6和对比例1~4的测试结果
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (5)
1.一种连铸用高强、增韧氧化锆定径水口,其特征在于,其原料组份质量百分比为:氧化钇为1.8~2.4%,碱式碳酸镁为2.5~4%,氮化硼纳米片为0.08~0.1%,纳米氧化镁为0.3~0.5%,纳米氧化铝为0.5~0.8%,PVA胶水为8~9%,余量为氧化锆。
2.根据权利要求1所述的一种连铸用高强、增韧氧化锆定径水口,其特征在于,所述的定径水口原料组份中,氧化钇为2.1%,碱式碳酸镁为3.1%,氮化硼纳米片为0.09%,纳米氧化镁为0.4%,纳米氧化铝为0.61%,PVA胶水为8.7%,余量为氧化锆。
3.根据权利要求1所述的一种连铸用高强、增韧氧化锆定径水口,其特征在于,所述的氧化钇为工业级;碱式碳酸镁为工业级;氮化硼纳米片片径为0.1~0.4μm,BN含量为98wt%;纳米氧化镁平均粒径为20nm,近球形,比表面积>42m2/g,MgO含量为98wt%;纳米氧化铝平均粒径为10~15nm,γ相,比表面积>120m2/g,Al2O3含量为99.9wt%;PVA胶水中干基PVA的浓度为5wt%。
4.根据权利要求1所述的一种连铸用高强、增韧氧化锆定径水口的制造方法,其具体步骤如下:
步骤1,依重量百分比称取氧化钇、碱式碳酸镁、氧化锆作为球磨物料,装入聚氨酯球磨罐,加入氧化锆质磨球,在转速为160±10r/min的条件下磨至325~400目,形成预混料A,预混料A的混合均匀度变异系数小于2.5%;
步骤2,将预混料A进行焙烧,焙烧温度为1470±25℃,焙烧时间为8±0.5h,冷却后再次球磨至325~400目,形成预混料B;
步骤3,依重量百分比称取45%的预混料B与无水乙醇进行湿法研磨后干燥,粒度磨至8000~10000目,形成预混料C;
步骤4,依重量百分比称取氮化硼纳米片、纳米氧化镁、纳米氧化铝、PVA胶水,混合后先进行低速搅拌,搅拌速度为1000r/min,搅拌时间为15min,之后进行高速搅拌,搅拌速度为3500r/min,搅拌时间为45min,形成预混料D;
步骤5,将余下的预混料B、预混料C、预混料D进行充分混合后造粒,然后装入模具中,采用150t液压机压制成型,形成定径水口素坯;
步骤6,将素坯自然干燥24小时后,置于110℃烘箱中干燥20±2h,再放入1725±5℃的电炉中烧结7h,制成定径水口;
步骤7,降温后,进行局部打磨、测试、包装,入库,进行销售。
5.根据权利要求4所述的一种连铸用高强、增韧氧化锆定径水口的制造方法,其特征在于:所述步骤5中在混合的同时进行超声波振动。
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