电熔MgAl2O4对Al2O3-MgAl2O4复合耐火材料高温蠕变性能的影响

李人骏; 张玲; 郑培毓

doi:10.13801/j.cnki.fhclxb.20210310.003

电熔MgAl₂O₄对Al₂O₃-MgAl₂O₄复合耐火材料高温蠕变性能的影响

doi: 10.13801/j.cnki.fhclxb.20210310.003

辽宁科技大学　材料与冶金学院，鞍山 114051

基金项目: 国家自然基金联合基金项目(U20A20239)

详细信息

通讯作者:
张玲，博士，教授，研究方向为耐火材料　E-mail：452433876@qq.com

中图分类号: TQ175
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- 被引次数: 0
出版历程
- 收稿日期: 2021-01-22
- 修回日期: 2021-02-09
- 录用日期: 2021-02-21
- 网络出版日期: 2021-03-10
- 刊出日期: 2022-01-15

Effect of fused MgAl₂O₄ on high temperature creep properties of Al₂O₃-MgAl₂O₄ refractory

School of Materials and Metallurgy, University of Science and Technology Liaoning, Anshan 114051, China

摘要

摘要: 以烧结板状刚玉和电熔镁铝尖晶石为原料、磷酸为结合剂，在1680℃下制备了刚玉-镁铝尖晶石复合耐火材料样品。在1500℃、0. 2 MPa的条件下保温50 h测试试样高温蠕变性能，采用 XRD、SEM和EDS分析蠕变前后试样的物相组成及显微结构，分析镁铝尖晶石添加量对刚玉-镁铝尖晶石复合耐火材料高温蠕变性能的影响。结果表明：刚玉-镁铝尖晶石复相材料较纯刚玉材料有着更好的抗蠕变性。镁铝尖晶石骨料在蠕变过程中会与氧化铝基质之间发生固溶反应而在尖晶石颗粒周围形成二次尖晶石层，有效连接了基质与骨料，提高了试样的抗蠕变性。在二次尖晶石层形成的过程中由于Mg²⁺有着更高的迁移速率和在反应界面两侧较高的厚度比，会诱发柯肯达尔效应，导致界面处空位大量积累和孔隙的产生。
- 高温蠕变 /
- 板状刚玉 /
- 镁铝尖晶石 /
- 固溶体 /
- 复合耐火材料
Abstract: The Al₂O₃ bonded MgAl₂O₄ fire-resistant composites were prepared with tabular alumina and fused magnesia-alumina spinel as raw materials, and phosphoric acid as binder and then sintered at 1680℃. The creep resistance test was conducted at 1500℃ under 0.2 MPa with insulation for 50 h, The specimens after creep resistance test were characterized and analyzed by XRD, SEM and EDS to investigate the effect of adding amount of MgAl₂O₄ on high temperature creep resistance of Al₂O₃ bonded MgAl₂O₄ fire-resistant composites as well as its mechanism. The results show that Al₂O₃ bonded MgAl₂O₄ fire-resistant composites has better creep resistance than Al₂O₃ composite. During the creep test, magnesium-aluminum spinel aggregate will react with alumina matrix to form secondary spinel layer around the spinel particles, which effectively connects the matrix and aggregate and improves the creep resistance of the specimens. During the formation of the secondary spinel layer, due to the higher migration rate of Mg²⁺ and the higher thickness ratio on both sides of the reaction interface, the Kirkendall effect will be induced, resulting in a large number of vacancies and pores at the interface.
- high temperature creep /
- tabular alumina /
- magnesia-alumina spinel /
- solid solution /
- fire-resistant composites

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图 1 蠕变实验前后Al₂O₃-MgAl₂O₄复合耐火材料样品的XRD图谱

Figure 1. XRD patterns of Al₂O₃-MgAl₂O₄ refractory samples before and after creep test

X—0wt%, 8wt%, 12wt%, 20wt%

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图 2 图1中镁铝尖晶石物相特征峰(311)的XRD图谱

Figure 2. XRD pattern of phase characteristic peak (311) of spinel in Fig. 1

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图 3 Al₂O₃-MgAl₂O₄复合耐火材料1500℃保温50 h蠕变曲线

Figure 3. Creep rate curves of Al₂O₃-MgAl₂O₄ refractory at 1500℃ for 50 h

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图 4 Al₂O₃-MgAl₂O₄复合耐火材料1500℃保温0~25 h的蠕变拟合曲线

Figure 4. Creep fitting curves of Al₂O₃-MgAl₂O₄ refractory at 1500℃ for 0-25 h

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图 5 Al₂O₃-MgAl₂O₄复合耐火材料1500℃保温25~50 h的蠕变拟合曲线

Figure 5. Creep fitting curves of Al₂O₃-MgAl₂O₄ refractory at 1500℃ for 25-50 h

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图 6 Al₂O₃-8wt%MgAl₂O₄、Al₂O₃-12wt%MgAl₂O₄和Al₂O₃-20wt%MgAl₂O₄试样蠕变实验前后的SEM图像

Figure 6. SEM images of Al₂O₃-8wt%MgAl₂O₄ Al₂O₃-12wt%MgAl₂O₄ and Al₂O₃-20wt%MgAl₂O₄ specimens before and after creep test

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图 7 蠕变实验后试样Al₂O₃-12wt%MgAl₂O₄和Al₂O₃-20wt%MgAl₂O₄中层带状结构SEM图像

Figure 7. SEM images of layer banded structure in specimens Al₂O₃-12wt%MgAl₂O₄ and Al₂O₃-20wt%MgAl₂O₄ after creep test

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图 8 镁铝尖晶石和刚玉形成镁铝尖晶石固溶体的示意图^[19]

Figure 8. Diagram of magnesia-aluminum spinel and corundum forming a magnesia-aluminum spinel solid solution^[19]

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图 9 镁铝尖晶石与刚玉之间形成层带状结构的二次尖晶石层示意图

Figure 9. Diagram of secondary spinel layer with a band-like structure formed between magnesium aluminum spinel and corundum

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表 1 原料化学组成

Table 1. Chemical composition of raw materials wt%

	Al₂O₃	MgO	SiO₂	Fe₂O₃	Na₂O
Tabular corundum	99.55	—	0.04	0.03	0.3
Fused MA	71.4	27.8	0.19	0.33	0.28
Note: MA—Magnesia alumina spinel.

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表 2 Al₂O₃-MgAl₂O₄复合耐火材料样品配比

Table 2. Proportion of Al₂O₃-MgAl₂O₄ refractory samples

Raw material/wt%	Grain size/mm	Al₂O₃	Al₂O₃-8wt%MgAl₂O₄	Al₂O₃-12wt%MgAl₂O₄	Al₂O₃-20wt%MgAl₂O₄
Tabular corundum	5-3	7	7	7	7
Tabular corundum	3-1	38	30	26	18
Fused MA	3-1	0	8	12	20
Tabular corundum	1-0	22	22	22	22
Tabular corundum	<0.088	33	33	33	33

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表 3 Al₂O₃-MgAl₂O₄复合耐火材料样品的物理性能指标

Table 3. Physical properties of Al₂O₃-MgAl₂O₄ refractory samples

Sample	Apparent porosity/%	Bulk density/(g·cm^–3)	Cold crushing/strength/MPa
Al₂O₃	14.5	3.23	73
Al₂O₃-8wt%MgAl₂O₄	17.3	3.13	62
Al₂O₃-12wt%MgAl₂O₄	16.5	2.96	58
Al₂O₃-20wt%MgAl₂O₄	16.1	3.02	66

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表 4 Al₂O₃-MgAl₂O₄复合耐火材料1500℃保温50 h蠕变曲线拟合方程

Table 4. Fitting equation of creep curve of Al₂O₃-MgAl₂O₄ refractory at 1500℃ for 50 h

Time/h	Sample	Equation	R²
0-25	Al₂O₃	Y=0.517exp(−t/2.012)+1.488exp(−t/24.646)−2	0.999
	Al₂O₃-8wt%MgAl₂O₄	Y=0.192exp(−t/1.569)+0.618exp(−t/22.462)−0.81	0.999
	Al₂O₃-12wt%MgAl₂O₄	Y=0.137exp(−t/0.113)+0.23exp(−t/8.088)−0.367	0.999
	Al₂O₃-20wt%MgAl₂O₄	Y=0.235exp(−t/2.22)+0.618exp(−t/239.243)−1.57	0.999
25-30	Al₂O₃	Y=−0.017t−1.056	0.994
	Al₂O₃-8wt%MgAl₂O₄	Y=−0.009t−0.373	0.994
	Al₂O₃-12wt%MgAl₂O₄	Y=−0.0007t−0.34	0.879
	Al₂O₃-20wt%MgAl₂O₄	Y=−0.002t−0.33	0.824
Notes: Y—Creep rate; t—Time.

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表 5 图7中所选微区的EDS结果

Table 5. EDS results of areas marked in Fig. 7

Specimen	Marked area	Atom fraction/at%
Specimen	Marked area	Mg	Al	O
Al₂O₃-12wt%MgAl₂O₄	1	10.25	31.8	57.95
	2	9.31	32.55	58.14
	3	9.19	32.65	58.16
	4	8.76	33.00	58.25
	5	5.01	35.99	59.00
	6	—	40	60
Al₂O₃-20wt%MgAl₂O₄	7	9.61	32.31	58.08
	8	9.47	32.43	58.11
	9	9.61	32.31	58.08
	10	5.29	35.77	58.94
	11	—	40	60

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