纳米增韧NiFe2O4陶瓷惰性阳极烧结行为与性能的研究

doi:10.15541/jim20150602

摘要/Abstract

摘要：

采用粉末冶金法制备NiFe₂O₄纳米粉增韧NiFe₂O₄陶瓷铝电解惰性阳极, 研究了NiFe₂O₄纳米粉添加量对NiFe₂O₄陶瓷惰性阳极烧结行为和材料性能的影响。通过线收缩和SEM对NiFe₂O₄陶瓷的烧结性能和显微结果进行分析。研究结果表明: 随着NiFe₂O₄纳米粉添加量的增加, 烧结收缩程度逐渐增大, 烧结致密化开始温度和烧结初期活化能逐渐降低, 添加量为40%时试样从900℃开始大幅度收缩, 烧结初期表观活化能下降到291.43 kJ/mol。NiFe₂O₄陶瓷惰性阳极的体积密度、抗弯强度和断裂韧性随NiFe₂O₄纳米粉添加量的增加均呈现先上升后下降的变化趋势, 气孔率和静态腐蚀率呈先下降后上升的趋势, 均在30%达到极值, 断裂韧性达到最大值3.12 MPa•m^1/2, 是未添加纳米粉试样的2.14倍。NiFe₂O₄纳米粉的添加能够明显增强晶界结合强度, 降低陶瓷材料气孔率, 从而提高断裂表面能实现增韧作用。

关键词: NiFe2O4, 线收缩, 活化能, 断裂表面能, 增韧

Abstract:

NiFe₂O₄ ceramic inert anode for aluminum electrolysis, strengthened by adding NiFe₂O₄nanopowder, was prepared via powder metallurgy method. The effects of NiFe₂O₄ nanopowder content on sintering behavior and properties of NiFe₂O₄ ceramic inert anode were studied. Linear shrinkage and scanning electron microscope (SEM) were employed to characterize the sintering property and microstructure. The results show that the sintering shrinkage degree increases gradually as increase of NiFe₂O₄ nanopowder content, while the sintering temperature and apparent activation energy of initial stage of sintering decrease. When nanopowder content is 40%, the sharp sintering shrinkage begins from 900℃ and the apparent activation energy of initial stage of sintering drops to 291.43 kJ/mol. Volume density, bending strength and fracture toughness are enhanced firstly and then decreased with the increase of nanopowder content, while the porosity and static corrosion rate display opposite tendency. The maximum value of fracture toughness is 3.12 MPa•m^1/2 with nanopowder content of 30%, which is 2.14 times that of without adding nanopowder. The toughening effect is realized by the elevated fracture surface energy, which is attributed to the enhanced grain boundary cohesive bond and the reduced porosity with addition of NiFe₂O₄ nanopowder.

Key words: NiFe2O4, linear shrinkage, activation energy, fracture surface energy, toughening

中图分类号:

TQ174

张志刚, 姚广春, 罗洪杰, 张啸, 马俊飞, 徐建荣. 纳米增韧NiFe₂O₄陶瓷惰性阳极烧结行为与性能的研究[J]. 无机材料学报, 2016, 31(7): 761-768.

ZHANG Zhi-Gang, YAO Guang-Chun, LUO Hong-Jie, ZHANG Xiao, MA Jun-Fei, XU Jian-Rong. Sintering Behavior and Properties of NiFe₂O₄ Ceramic Inert Anode Toughened by Adding NiFe₂O₄ Nanopowder[J]. Journal of Inorganic Materials, 2016, 31(7): 761-768.

图/表 13

表1 粒度级配设计表

Table 1 Design of particle gradation

Main granule (500-355 μm)	Filler granule (105-74 μm)	Fine granule (<74 μm)	Nanopowder (30-65 nm)
42wt%	18wt%	40wt%	0
		30wt%	10wt%
		20wt%	20wt%
		10wt%	30wt%
		0	40wt%

图1 低温固相反应制备得到NiFe2O4纳米粉的XRD图谱(a)和TEM照片(b)

Fig. 1 XRD pattern (a) and TEM image (b) of NiFe2O4 nanopowders prepared by low temperature solid-state reaction

图2 纳米粉添加量对阳极试样线收缩的影响

Fig. 2 Effect of nanopowder content on linear shrinkage of inert anodes as a function of temperature

表2 不同纳米粉添加量试样1300℃时的线收缩

Table 2 Linear shrinkage of samples prepared by adding different amount of nanopowders at 1300℃

Nanopowder content/wt %	0	10	20	30	40
Linear shrinkage/ %	-5.23	-6.09	-6.93	-9.41	-10.41

图3 纳米粉添加量对阳极试样密度与气孔率的影响

Fig. 3 Effect of nanopowder content on density and porosity

图4 不添加NiFe2O4纳米粉试样的ln(△L/L0)T ~lnC关系图

Fig. 4 ln(△L/L0)T versus lnC for samples without nanopowders

表3 不添加NiFe2O4纳米粉试样在不同温度下的ln(△L/L0)T ~lnC拟合直线斜率和线性回归系数

Table 3 Values of slope and linear regression coefﬁcient (R) of relationship between ln(△L/L0)T and lnC for samples without nanopowders under different temperatures

T/℃	1150	1175	1200	1225	1250	Average
-1/(m+1)	-0.352	-0.338	-0.362	-0.373	-0.365	-0.358
R	0.991	0.994	0.985	0.987	0.992	-

图5 不添加NiFe2O4纳米粉试样ln[(△L/L0)/T] ~ 1/T关系图

Fig. 5 ln[(△L/L0)/T] versus 1/T relation graph for sample without nanopowders

表4 不添加NiFe2O4纳米粉试样不同升温速率ln[(△L/L0)/T] ~ 1/T曲线拟合直线斜率a和线性回归系数R值

Table 4 Values of slope (a) and linear regression coefﬁcient (R) of relationship between ln[(△L/L0)/T] and 1/T for samples without nanopowders under different heating rates

Heating rate/(K·min^-1)	5	10	20	Average
a	-16731	-17165	-15889	-16595
R	0.978	0.985	0.981	-

表5 不同NiFe2O4纳米粉试样烧结初期的指数m和表观活化能Q值

Table 5 Values of exponent and apparent activation energy for samples with various contents of NiFe2O4 nanopowders at the early-stage sintering

Nanopowder content /wt%	0	10	20	30	40
Exponent m	1.793	1.648	1.564	1.486	1.453
Apparent activation energy, Q/(kJ·mol^-1)	385.35	349.52	324.27	302.69	291.43

图6 纳米粉添加量对抗弯强度和断裂韧性的影响

Fig. 6 Effect of nanopowder content on bending strength and fracture toughness

图7 不同纳米粉添加量试样的断口SEM照片

Fig. 7 SEM images of fracture surfaces of NiFe2O4 ceramic inert anodes with various contents of nanopowder

图8 纳米粉添加量对阳极试样静态腐蚀率的影响

Fig. 8 Effect of nanopowder content on the static corrosion rate of inert anodes

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纳米增韧NiFe₂O₄陶瓷惰性阳极烧结行为与性能的研究

Sintering Behavior and Properties of NiFe₂O₄ Ceramic Inert Anode Toughened by Adding NiFe₂O₄ Nanopowder

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