TiO2促进CaAl4O7材料烧结规律及其机理

doi:10.16085/j.issn.1000-6613.2020-0335

摘要/Abstract

摘要：

为了适应材料轻量化、经济化以及功能化的发展需要，以Al₂O₃和CaCO₃粉末为主要原料，TiO₂为添加剂，采用固相烧结法，经1200℃预烧2h-1600℃烧结1h后，制备了CA₂材料,并考察了TiO₂促进该材料烧结规律及其机理。结果表明，添加TiO₂中的Ti⁴⁺离子在烧结过程中通过取代Al³⁺离子固溶入了CA₂相中，有效地促进了CA₂相的晶格畸变，增加了Al³⁺离子空位，提高了CA₂相的活性，加速了离子混淆与扩散，从而有效地促进了CA₂相的烧结，同时超过固溶极限过量的TiO₂与脱溶的Al₂O₃反应生成Al₂TiO₅新相，填塞气孔，进一步促进了烧结致密化。综上因素，CA₂材料的致密化被有效促进。当TiO₂的添加量为1%时，显气孔率已由未添加时的12.7%下降到4.7%，体积密度已由未添加时的2.51g/cm³上升到2.65g/cm³，可制得显微结构交织分布的致密CA₂材料。

关键词: 二铝酸钙, 轻量化, TiO₂添加, 合成, 烧结, 活化, 化学过程

Abstract:

In order to adapt the demands for the lightweight, economic and functional materials, CA₂ material was prepared by two steps reaction and sintering of mixture powders method after the mixture powders of Al₂O₃ and CaCO₃ was pre-sintering at 1200℃ for 2h and sintering at 1600℃ for 1h by addition of TiO₂ micro powder, and the promoting law and mechanism of TiO₂ addition on sintering of this_{refractory was discussed.The results showed that the added Ti⁴⁺ dissolves to CA₂ by substituting Al³⁺, which effectively promotes the lattice distortion of CA₂ and increases the Al³⁺ vacancies, and then effectively improves the sintering activity of CA₂, accelerates intercrystalline mixing and diffusion in the sintering process, thus the sintering of CA₂ is effectively promoted. At the same time, the excess TiO₂ reacts with the exsolution of Al₂O₃ to form the Al₂TiO₅ further fills the pores and promots the sintering densification of CA₂. Based on the above factors, the sintering densification behavior of CA₂ material is synergistically promoted. As a result, the dense microstructure is obtained, with the apparent porosity decreases from 12.7% to 4.7% and the bulk density increases from 2.51g/cm³ to 2.65g/cm³ after firing at 1600℃ for 1h by addition of 2%TiO₂, and a texture microstructure of CA₂ phases is prepared.}

Key words: CA₂, lightweight, TiO₂ addition, synthesis, sintering, activation, chemical processes

中图分类号:

TB335

尹雪亮, 马贺利, 宫长伟, 杜成武, 韩廷全. TiO₂促进CaAl₄O₇材料烧结规律及其机理[J]. 化工进展, 2020, 39(S1): 200-205.

Xueliang YIN, Heli MA, Changwei GONG, Chengwu DU, Tingquan HAN. Promoting law and mechanism of TiO₂ addition on sintering of CaAl₄O₇ refractory[J]. Chemical Industry and Engineering Progress, 2020, 39(S1): 200-205.

图/表 8

表1 实验原料及其质量分数

编号	$w A l 2 O 3$ /%	（ $w C a C O 3 / w 折算 C a O)$ /%	$w T i O 2$ /%
Ti0	78.5	38.4/21.5	0
Ti0.5	78.5	38.4/21.5	0.5
Ti1	78.5	38.4/21.5	1
Ti1.5	78.5	38.4/21.5	1.5

表1 实验原料及其质量分数

编号	$w A l 2 O 3$ /%	（ $w C a C O 3 / w 折算 C a O)$ /%	$w T i O 2$ /%
Ti0	78.5	38.4/21.5	0
Ti0.5	78.5	38.4/21.5	0.5
Ti1	78.5	38.4/21.5	1
Ti1.5	78.5	38.4/21.5	1.5

图1 1600℃、1h烧结后不同TiO2添加试样的XRD图谱

表2 1600℃保温1h烧成后CA2相的晶格常数变化

编号	a/?	（Δa/a）/%	b/?	（Δb/b）/%	c/?	(Δc/c)/%
Ti0	12.8342	—	8.8607	—	5.4302	—
Ti0.5	12.8881	0.42	8.8829	0.25	5.4405	0.19
Ti1	12.9382	0.81	8.9032	0.48	5.4503	0.37
Ti1.5	12.9420	0.84	8.9068	0.52	5.4525	0.41

图2 体积密度和气孔率随TiO2添加的变化关系

图3 1600℃、1h烧结后试样SEM图

图4 1600℃、1h烧结后1% TiO2添加试样微区元素面分布图

图5 1600℃、1h烧结后添加1% TiO2试样的EDS图

表3 添加1% TiO2的CA2试样的EDS分析结果

组分	质量分数/%
CaO	21.29
Al₂O₃	77.72
TiO₂	0.99
总量	100

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TiO₂促进CaAl₄O₇材料烧结规律及其机理

Promoting law and mechanism of TiO₂ addition on sintering of CaAl₄O₇ refractory

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