CN112094125B - 一种低导热低热膨胀镁基原料及其制备方法 - Google Patents

一种低导热低热膨胀镁基原料及其制备方法 Download PDF

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CN112094125B
CN112094125B CN202011001247.7A CN202011001247A CN112094125B CN 112094125 B CN112094125 B CN 112094125B CN 202011001247 A CN202011001247 A CN 202011001247A CN 112094125 B CN112094125 B CN 112094125B
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黄奥
霍艳竹
顾华志
邹永顺
付绿平
张美杰
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Wuhan University of Science and Engineering WUSE
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Abstract

本发明涉及一种低导热低热膨胀镁基原料及其制备方法。其技术方案是首先将40～60wt％的电熔镁砂颗粒、30～40wt％的单斜氧化锆细粉、5～20wt％的氧氯化锆细粉、0.5～1.5wt％的纳米氢氧化钙粉体、0.5～1.5wt％的纳米氢氧化钙粉体和0.1～0.3wt％的马来酸，在25℃恒温条件下采用高速混碾机搅拌15min混合均匀，得到混合粉体；然后将上述混合粉体经过球磨机在25℃恒温条件下混合3min，再置于高温炉中在250～400℃条件下焙烧0.5～3h，最后冷却至室温。本发明的制备方法工艺简单、易于工业化生产，所制备的镁基耐火材料具有较低的导热系数、低热膨胀系数、分散性好和抗熔渣渗透侵蚀能力强的优点。

Description

一种低导热低热膨胀镁基原料及其制备方法
技术领域
本发明属于耐火材料技术领域，具体涉及一种低导热低热膨胀镁基原料及其制备方法。
背景技术
耐火材料直接应用于钢铁、有色、水泥、玻璃、陶瓷和化工、机械、电力等国民经济各个领域的高温工业生产过程中，是保证上述产业运行和技术发展必不可少的基础材料。镁砂具有熔点高、耐高温、抗碱性高温熔渣侵蚀性好等优点，是耐火材料中最重要的原料之一，被广泛应用于各类高温工业用耐火材料，其服役性能和使用寿命直接关系着高温工业的正常运行与产品的品质。
尽管镁砂耐火度高、抗碱性高温熔渣侵蚀性好，但镁砂的导热系数仍然偏高，而且抵御高温熔渣渗透性能和抗热震性能不佳的缺陷对其使用寿命造成了极大的限制。镁砂的抗高温熔渣渗透及抗热震性能与其显微结构有重要联系，熔渣较易通过气孔及晶界渗透进入材料内部从而产生严重的侵蚀。因此，现有镁砂制备技术多倾向于制备晶粒尺寸大且较致密的镁砂原料，即大结晶镁砂。然而，由于氧化镁热膨胀系数较大，大结晶镁砂在遭受温度剧变时，由于晶界数量少，热应力难以得到释放，抗热震性能通常不佳。此外，考虑到现有的镁砂中气孔尺寸通常较大且直接结合程度较低，微孔镁砂的开发有效降低了气孔尺寸，增加了气孔中的闭口气孔比例，能在一定程度上缓解高温熔体的渗透侵蚀，但其轻量多孔化后的隔热性和抗渣性能的平衡性仍然不够优越，有待提高。
发明内容
本发明目的是提供一种工艺简单和易于工业化生产的低导热、低热膨胀镁基原料的制备方法，具体工艺步骤如下：
将40～60wt％的电熔镁砂颗粒、30～40wt％的单斜氧化锆细粉、5～20wt％的氧氯化锆细粉、0.5～2wt％的纳米氢氧化钙粉体、0.2～0.5wt％的轻烧氧化镁细粉和0.1～0.3wt％的马来酸，在25℃恒温条件下采用高速混碾机搅拌15min混合均匀，得到混合粉体；
然后将所述混合粉体经过球磨机在25℃恒温条件下混合3min，再置于高温炉中在250～400℃条件下焙烧0.5～3h，冷却至室温形成所述镁基耐火材料。
优选地，电熔镁砂颗粒的粒径≤1mm，电熔镁砂颗粒中的MgO含量为≥96wt％。
优选地，单斜氧化锆细粉粒径≤45μm，单斜氧化锆细粉中的ZrO2含量≥98wt％。
优选地，上述氧氯化锆细粉的粒径≤45μm。
优选地，上述纳米氢氧化钙粉体的Ca(OH)2≥98wt％，粒径≤0.1μm。
优选地，上述轻烧氧化镁细粉的MgO≥95wt％，粒径≤45μm。
本发明另一方面涉及一种镁基耐火材料，其按照上述镁基耐火材料的制备方法获得。
由于采用上述技术方案，本发明与现有技术相比具有如下积极效果：
本发明采用毫米-微米-纳米颗粒复合体系和混碾及球磨工艺，结合氧氯化锆细粉和纳米氢氧化钙粉体的热解，能在镁砂晶界周围引入微纳米氧化锆和氧化钙并使其均匀分布，该镁基原料在高温使用过程中，氧化锆相变及其与氧化钙反应产生的应力能很好地促进微纳米氧化锆紧密接触镁砂晶界，其晶界杂质中的CaO会优先于SiO2与这些活性ZrO2反应在晶界生成CaZrO3；适量的纳米氧化锆ZrO2颗粒被包裹具有相似粒径的CaO以及较大的活性MgO微粉粒中，阻碍了其与镁砂晶界中CaO杂质的聚集性反应，稳定了镁砂结构，也起到缓释的作用；这些持续生成的适量晶间CaZrO3相能增强镁砂颗粒的结合力，有效降低镁砂的导热系数、热膨胀系数以及提升抗渣性能。
可见，本发明具有工艺简单和易于工业化生产的特点；所制备的低导热低热膨胀镁基原料具有导热系数较低、热膨胀系数低、分散性好和抗熔渣渗透侵蚀能力强的特点。
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：
所述电熔镁砂颗粒的粒径≤1mm，电熔镁砂颗粒中的MgO含量为≥96wt％。
所述单斜氧化锆细粉粒径≤45μm，其中的ZrO2≥98wt％，
所述氧氯化锆细粉的粒径≤45μm。
所述纳米氢氧化钙粉体的Ca(OH)2≥98wt％，粒径≤0.1μm。
所述轻烧氧化镁细粉的MgO≥95wt％，粒径≤45μm。
实施例1
将40wt％的电熔镁砂颗粒、40wt％的单斜氧化锆细粉、19wt％的氧氯化锆细粉、0.5wt％的纳米氢氧化钙粉体、0.2wt％的轻烧氧化镁细粉和0.3wt％的马来酸，在25℃恒温条件下采用高速混碾机搅拌15min混合均匀，得到混合粉体；然后将所述混合粉体经过球磨机在25℃恒温条件下混合3min，再置于高温炉中在250℃条件下焙烧3h，冷却至室温，获得本实施例的低导热低热膨胀镁基原料。
实施例2
将50wt％的电熔镁砂颗粒、35wt％的单斜氧化锆细粉、13wt％的氧氯化锆细粉、1.4wt％的纳米氢氧化钙粉体、0.5wt％的轻烧氧化镁细粉和0.1wt％的马来酸，在25℃恒温条件下采用高速混碾机搅拌15min混合均匀，得到混合粉体；然后将所述混合粉体经过球磨机在25℃恒温条件下混合3min，再置于高温炉中在400℃条件下焙烧0.5h，冷却至室温，获得本实施例的低导热低热膨胀镁基原料。
实施例3
将60wt％的电熔镁砂颗粒、33wt％的单斜氧化锆细粉、5wt％的氧氯化锆细粉、1.6wt％的纳米氢氧化钙粉体、0.2wt％的轻烧氧化镁细粉和0.2wt％的马来酸，在25℃恒温条件下采用高速混碾机搅拌15min混合均匀，得到混合粉体；然后将所述混合粉体经过球磨机在25℃恒温条件下混合3min，再置于高温炉中在300℃条件下焙烧2.5h，冷却至室温，获得本实施例的低导热低热膨胀镁基原料。
实施例4
将52wt％的电熔镁砂颗粒、40wt％的单斜氧化锆细粉、5.2wt％的氧氯化锆细粉、2wt％的纳米氢氧化钙粉体、0.5wt％的轻烧氧化镁细粉和0.3wt％的马来酸，在25℃恒温条件下采用高速混碾机搅拌15min混合均匀，得到混合粉体；然后将所述混合粉体经过球磨机在25℃恒温条件下混合3min，再置于高温炉中在350℃条件下焙烧2.5h，冷却至室温，获得本实施例的低导热低热膨胀镁基原料。
实施例5
将45wt％的电熔镁砂颗粒、37wt％的单斜氧化锆细粉、16wt％的氧氯化锆细粉、1.5wt％的纳米氢氧化钙粉体、0.3wt％的轻烧氧化镁细粉和0.2wt％的马来酸，在25℃恒温条件下采用高速混碾机搅拌15min混合均匀，得到混合粉体；然后将所述混合粉体经过球磨机在25℃恒温条件下混合3min，再置于高温炉中在400℃条件下焙烧1.5h，冷却至室温，获得本实施例的低导热低热膨胀镁基原料。
对比例1-5
对比例1-5中，电熔镁砂颗粒、单斜氧化锆细粉、氧氯化锆细粉、纳米氢氧化钙粉体、轻烧氧化镁细粉与马来酸按照表1的重量配比和工艺条件进行。
表1对比例1-5原料配比
对比例1 对比例2 对比例2 对比例2 对比例2
电熔镁砂颗粒 75 20 10 65 35
单斜氧化锆细粉 21 50 60 27 45
氧氯化锆细粉 2 24 30 3 18
纳米氢氧化钙粉体 0.2 4 0 4 0.1
轻烧氧化镁细粉 0.8 1 0 1 1.9
马来酸 1 1 0 0 0
温度(℃) 300 250 300 350 400
焙烧时间(h) 3 2.5 2 2 1.5
表2本发明实施例与对比例1-5原料性能指标对比
Figure BDA0002694391670000051
Figure BDA0002694391670000061
本发明的各实施例与传统镁基原料性能指标对比如表2所示，由上述表1和表2可以看出，采用40～60wt％的电熔镁砂颗粒、30～40wt％的单斜氧化锆细粉、5～20wt％的氧氯化锆细粉、0.5～2wt％的纳米氢氧化钙粉体、0.2～0.5wt％的轻烧氧化镁细粉和0.1～0.3wt％的马来酸的在25℃恒温条件下采用高速混碾机搅拌15min混合均匀，得到混合粉体，最后获得的原料的导热系数和热膨胀系数均远远低于传统镁基原料。其原因在于本发明采用毫米-微米-纳米颗粒复合体系和混碾及球磨工艺，结合氧氯化锆细粉和纳米氢氧化钙粉体的热解，能在镁砂晶界周围引入微纳米氧化锆和氧化钙并使其均匀分布，该镁基原料在高温使用过程中，氧化锆相变及其与氧化钙反应产生的应力能很好地促进微纳米氧化锆紧密接触镁砂晶界，其晶界杂质中的CaO会优先于SiO2与这些活性ZrO2反应在晶界生成CaZrO3；适量的纳米ZrO2颗粒被包裹具有相似粒径的CaO以及较大的活性MgO微粉粒中，阻碍了其与镁砂晶界中CaO杂质的聚集性反应，稳定了镁砂结构，也起到缓释的作用；这些持续生成的适量晶间CaZrO3相能增强镁砂颗粒的结合力，有效降低镁砂的导热系数、热膨胀系数以及提升抗渣性能。
因此，本发明具有工艺简单和易于工业化生产的特点；所制备的低导热低热膨胀镁基原料具有导热系数较低、热膨胀系数低、分散性好和抗熔渣渗透侵蚀能力强的特点。
虽然，上文中已经用一般性说明、具体实施方式，对本发明作了详尽的描述，但在本发明基础上，可以对之作一些修改或改进，这对本领域技术人员而言是显而易见的。因此，在不偏离本发明精神的基础上所做的这些修改或改进，均属于本发明要求保护的范围。

Claims (6)

1.一种低导热低热膨胀镁基原料的制备方法，其特征在于：
将40～60wt％的粒径≤1mm的电熔镁砂颗粒、30～40wt％的粒径≤45μm的单斜氧化锆细粉、5～20wt％的粒径≤45μm的氧氯化锆细粉、0.5～2wt％的粒径≤0.1μm的纳米氢氧化钙粉体、0.2～0.5wt％的粒径≤45μm的轻烧氧化镁细粉和0.1～0.3wt％的马来酸，在25℃恒温条件下采用高速混碾机搅拌15min混合均匀，得到混合粉体；
然后将所述混合粉体经过球磨机在25℃恒温条件下混合3min，再置于高温炉中在250～400℃条件下焙烧0.5～3h，冷却至室温形成所述低导热低热膨胀镁基原料。
2.根据权利要求1所述的低导热低热膨胀镁基原料的制备方法，其特征在于所述电熔镁砂颗粒中的MgO含量为≥96wt％。
3.根据权利要求1所述的低导热低热膨胀镁基原料的制备方法，其特征在于所述单斜氧化锆细粉中的ZrO2含量≥98wt％。
4.根据权利要求1所述的低导热低热膨胀镁基原料的制备方法，其特征在于所述纳米氢氧化钙粉体的Ca(OH)2≥98wt％。
5.根据权利要求1所述的低导热低热膨胀镁基原料的制备方法，其特征在于所述轻烧氧化镁细粉的MgO≥95wt％。
6.一种根据权利要求1-5项中任一项所述的低导热低热膨胀镁基原料的制备方法制得的镁基原料。
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4212679A (en) * 1978-09-12 1980-07-15 Dresser Industries, Inc. Method of making magnesite grain
JP2001122675A (ja) * 1999-10-27 2001-05-08 Natl Inst Of Advanced Industrial Science & Technology Meti ジルコン酸カルシウム／マグネシア系複合多孔体およびその製造方法
CN1837151A (zh) * 2006-04-14 2006-09-27 西安建筑科技大学 水泥窑高温带用MgO－CaO－ZrO2砖及其制造方法
CN104140278A (zh) * 2014-07-28 2014-11-12 瑞泰科技股份有限公司 一种借助原位反应制备的炉外精炼用镁钙锆砖及生产方法
CN107434404A (zh) * 2017-08-28 2017-12-05 辽宁中镁高温材料有限公司 一种锆复合高性能电熔镁钙锆砖及其制造方法
CN108821750A (zh) * 2018-07-10 2018-11-16 武汉科技大学 一种具有微-纳米复合孔结构的烧结镁砂及其制备方法

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT345716B (de) * 1974-11-29 1978-10-10 Veitscher Magnesitwerke Ag Feuerfeste trockenstampfmasse zum auskleiden von induktionstiegeloefen
JPS63162566A (ja) * 1986-12-24 1988-07-06 美濃窯業株式会社 塩基性耐火組成物
JPH0532454A (ja) * 1991-07-26 1993-02-09 Ube Ind Ltd 立方晶ジルコニア粒子分散型マグネシア焼結体及びその製造方法
JPH06107413A (ja) * 1992-09-28 1994-04-19 Shin Nippon Kagaku Kogyo Co Ltd 高純度マグネシアクリンカーの製造方法
JPH0761856A (ja) * 1993-06-30 1995-03-07 Kurosaki Refract Co Ltd セメント及び石灰焼成キルン内張り用塩基性耐火物
JPH11278918A (ja) * 1998-03-30 1999-10-12 Nippon Steel Corp 塩基性耐火物原料ならびに塩基性耐火物およびその製造方法ならびにそれを使用した金属精錬窯炉および焼成炉
JP4203157B2 (ja) * 1998-10-20 2008-12-24 黒崎播磨株式会社 マグネシア質耐火物
CN1325435C (zh) * 2004-06-30 2007-07-11 宝山钢铁股份有限公司 一种真空炉炉衬用无铬耐火材料
CN103496990B (zh) * 2013-09-13 2015-03-11 天津大学 高温抗热震性镁铝尖晶石-氧化锆复相材料及其制备方法
CN111116174A (zh) * 2019-12-24 2020-05-08 辽宁科技大学 一种高热震高致密烧结镁砂的制备方法
CN111410443A (zh) * 2020-04-30 2020-07-14 海城市军刚中档镁砂有限公司 一种MgO-CaO-ZrO2砂的制备方法
CN112094125B (zh) * 2020-09-22 2023-02-28 武汉科技大学 一种低导热低热膨胀镁基原料及其制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4212679A (en) * 1978-09-12 1980-07-15 Dresser Industries, Inc. Method of making magnesite grain
JP2001122675A (ja) * 1999-10-27 2001-05-08 Natl Inst Of Advanced Industrial Science & Technology Meti ジルコン酸カルシウム／マグネシア系複合多孔体およびその製造方法
CN1837151A (zh) * 2006-04-14 2006-09-27 西安建筑科技大学 水泥窑高温带用MgO－CaO－ZrO2砖及其制造方法
CN104140278A (zh) * 2014-07-28 2014-11-12 瑞泰科技股份有限公司 一种借助原位反应制备的炉外精炼用镁钙锆砖及生产方法
CN107434404A (zh) * 2017-08-28 2017-12-05 辽宁中镁高温材料有限公司 一种锆复合高性能电熔镁钙锆砖及其制造方法
CN108821750A (zh) * 2018-07-10 2018-11-16 武汉科技大学 一种具有微-纳米复合孔结构的烧结镁砂及其制备方法

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
Fabrication and properties of in situ intergranular CaZrO3 modified microporous magnesia aggregates;Yong shunZou 等;《Ceramics International》;20200406;第46卷(第10期);16956-16965 *
Formation Mechanism of In Situ Intergranular CaZrO3 Phases in Sintered Magnesia Refractories;Zou Yongshun等;《Metallurgical and Materials Transactions A》;20200727;第51卷(第10期);1-11 *
MgO—CaO—ZrO2耐火材料的性能,制备与应用;王领航 等;《耐火材料》;20040531;第38卷(第5期);350-352 *
MgO-CaZrO3-ZrO2系含MgO复合陶瓷的结构与烧结性能，;张广宇 等;《人工晶体学报》;20190228;第48卷(第2期);219-225 *
MgO-ZrO2复合材料的烧结和热震稳定性;姬莹莹 等;《中国陶瓷工业》;20140630;第21卷(第6期);20-25 *

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