NiFe2O4陶瓷U型套管的注浆成型和无压烧结

doi:10.15541/jim20190359

摘要/Abstract

摘要：

采用注浆成型和无压烧结技术制备铝电解测温热电偶NiFe₂O₄陶瓷U型保护套管, 对浆料稳定性、生坯烧结行为和组装热电偶的测温性能进行了研究。结果表明: 添加10wt% NiFe₂O₄纳米粉和5wt%纳米粘结剂能有效提高浆料体系的Zeta电位, pH在10.0~11.0之间时浆料体系的稳定性较好。升温至1100 ℃以上生坯开始大量收缩, 随烧结温度的升高线收缩和线收缩速率逐渐增大, 在1300 ℃时线收缩速率达到最大值; 烧结初期活化能为295.11 kJ·mol ^-1, 受体积扩散和晶界扩散共同控制。测温结果表明组装热电偶在升降温过程中温度响应及时, 具备良好的抗熔盐腐蚀性能和抗热震性能, 满足工业铝电解测温热电偶套管的要求, 具备工业应用前景。

关键词: 注浆成型, NiFe₂O₄, 稳定性, 烧结, 腐蚀

Abstract:

Slip casting and pressureless sintering were used to produce NiFe₂O₄ ceramic U-shaped protection sleeves for thermocouple in aluminum electrolysis. The stability of slurry, sintering behavior of green body as well as the temperature measuring performances, were investigated in detail. The Zeta potential of slurry was improved effectively by adding 10wt% NiFe₂O₄ nanopowders and 5wt% nano-binder, and the slurry possessed better sedimentation stability when pH was in the range from 10.0 to 11.0. Green bodies began to shrink significantly when the sintering temperature rising to 1100 ℃. The linear shrinkage and linear shrinkage ratio increased with temperature, and the linear shrinkage ratio reached its maximum at 1300 ℃. The sintering activation energy of the initial stage was 295.11 kJ·mol ^-1, and the main transport mechanisms were volume diffusion and grain boundary diffusion. The temperature testing results showed that the assembled thermocouple with NiFe₂O₄ ceramic protection sleeves worked well with timely response to temperature variation, as well as good resistance to thermal shock and corrosion from melt salts, with the prospect of industrial temperature measurement applications in an aluminum reduction cell.

Key words: slip casting, NiFe₂O₄, stability, sintering, corrosion

中图分类号:

TQ174

张志刚,卢晓通,刘金莉. NiFe₂O₄陶瓷U型套管的注浆成型和无压烧结[J]. 无机材料学报, 2020, 35(6): 661-668.

ZHANG Zhigang,LU Xiaotong,LIU Jinli. NiFe₂O₄ Ceramic U-shaped Sleeve Prepared by Slip Casting and Pressureless Sintering[J]. Journal of Inorganic Materials, 2020, 35(6): 661-668.

图/表 12

图1 NiFe2O4纳米粉和纳米粘结剂单独添加量对浆料Zeta电位和粘度的影响

Fig. 1 Effects of NiFe2O4 nanopowder and nano-binder content on Zeta potential and viscosity, respectively

图2 浆料体系的Zeta电位随pH的变化趋势图

Fig. 2 Variation of Zeta potential as a function of pH for slurry

表1 浆料和生坯不同部位的粒度分布

Table 1 Particle size distribution in different positions for the same green body

Position	Particle size/μm
Position	D₁₀	D₅₀	D₉₀
Slurry	0.45	2.51	5.35
Top_Ⅰ	0.46	2.51	5.33
Top_Ⅱ	0.45	2.52	5.34
Middle_Ⅰ	0.46	2.52	5.36
Middle_Ⅱ	0.46	2.53	5.34
Bottom_Ⅰ	0.46	2.52	5.36
Bottom_Ⅱ	0.46	2.52	5.34

图3 烧结过程中生坯的线收缩行为和线收缩速率

Fig. 3 Variations of linear shrinkage and shrinkage rate as functions of sintering temperature for green body

图4 烧结过程中ln(ΔL/L0)T ~lnC关系曲线

Fig. 4 Curves of ln(ΔL/L0)T versus lnC at sintering

表2 不同温度ln(ΔL/L0)T ~ lnC拟合直线斜率和线性回归系数

Table 2 Values of slope and linear regression coef?cient (CR) of relationship between ln(ΔL/L0)T and lnC under different temperatures

T/℃	-1/(m+1)	C_R
1150	-0.396	0.995
1175	-0.401	0.998
1200	-0.403	0.990
1225	-0.397	0.991
1250	-0.396	0.994
Average	-0.399	—

图5 烧结过程中ln[(ΔL/L0)/T] ~ 1/T关系图

Fig. 5 Curves of ln[(ΔL/L0)/T] versus 1/T during sintering

表3 不同升温速率ln[(ΔL/L0)/T] ~ 1/T曲线拟合直线斜率a和线性回归系数CR值

Table 3 The values of slope (a) and linear regression coef?cient (CR) of relationship between ln[(ΔL/L0)/T] and 1/T at different heating rates

Heating rate/(K·min^-1)	a	C_R
5	-14049	0.990
10	-14165	0.987
20	-14279	0.985
Average	-14164	—

图6 不同温度烧结试样的SEM照片和相对密度

Fig. 6 SEM images and relative densities of samples sintered at different temperatures

图7 升降温过程中不同类型热电偶测温变化趋势

Fig. 7 Temperature changes of different thermocouples in the temperature rising and falling process

图8 测温腐蚀不同时间的NiFe2O4陶瓷表面F元素分布图和电解质中Ni含量

Fig. 8 Distribution diagrams of F element in the surfaces of NiFe2O4 ceramics and Ni contents in electrolysis after corroded different periods

图9 测温240 h后组装热电偶实物和NiFe2O4陶瓷表面微观形貌照片

Fig. 9 Picture of assembled thermocouple and SEM image of NiFe2O4 ceramic sleeve

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NiFe₂O₄陶瓷U型套管的注浆成型和无压烧结

NiFe₂O₄ Ceramic U-shaped Sleeve Prepared by Slip Casting and Pressureless Sintering

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