Thermal decomposition kinetics and particle evolution characteristics of nano barium titanate precursor

doi:10.16085/j.issn.1000-6613.2024-0069

Abstract

Abstract:

Barium titanate has excellent properties such as high dielectric constant and low dielectric loss, and is the main raw material for preparing multilayer ceramic capacitors and other components. The thermal decomposition and gas precipitation characteristics of nano barium titanate precursor prepared by oxalate co-precipitation method were studied using a thermogravimetric-mass spectrometry analyzer, and the mechanism of thermal decomposition reaction of nano barium titanate precursor was revealed. The kinetic calculations were carried out using kissinger-akahira-sunose (KAS) method and flynn-wall-ozawa (FWO) method. The microstructure of the thermal decomposition products was observed using scanning electron microscopy (SEM), and the evolution mechanism of particles was analyzed. The results showed that the thermal decomposition process of nano barium titanate precursor could be divided into four weight-loss stages. The first stage was the release of water, the second stage produced CO and CO₂, and the third and fourth stages produced CO₂. Based on these results, the reactions involved in each stage were derived. As the heating rate increased, the maximum weight loss rate temperature corresponding to each weight loss stage moved towards the high-temperature zone. The fourth stage had the largest displacement towards the high-temperature zone, reaching 113℃. However, this stage had the fastest weight-loss rate and the reactions had been strengthened under the condition of 30℃/min. The FWO model was more suitable for describing the thermal decomposition process of nano barium titanate precursors. The average activation energies of the four stages were 67.89 kJ/mol, 208.92 kJ/mol, 494.04 kJ/mol and 195.11 kJ/mol, respectively. The activation energy of the third stage was the highest and the reaction was difficult to occur. During the thermal decomposition process of nano barium titanate, macroscopic large particles would evolve into aggregates of microscopic small particles. A higher constant temperature would lead to an increase in particle size. Therefore, the recommended constant temperature should not exceed 900℃. This research provided a theoretical basis for the selection of thermal decomposition process parameters for nano barium titanate precursors.

Key words: barium titanate precursor, thermal decomposition, dynamics, thermogravimetric-mass spectrometry, particle evolution

摘要：

钛酸钡具有介电常数高、介电损耗低等优良性能，是制备多层陶瓷电容器等元件的基础原料。以草酸盐共沉淀法制备的纳米钛酸钡前体为原料，采用热重-质谱联用分析仪研究了其热分解特性和气体析出特性，揭示了纳米钛酸钡前体热分解反应的机理，利用kissinger-akahira-sunose（KAS）法和flynn-wall-ozawa（FWO）法进行了反应动力学计算，并采用扫描电子显微镜（SEM）观察了热分解产物的微观形貌，分析了颗粒的演化机理。结果显示：纳米钛酸钡前体热分解过程可分为4个失重阶段，第一阶段为水分析出，第二阶段的析出气体为CO和CO₂，第三和第四阶段的析出气体为CO₂，据此推导出了各阶段涉及的反应式；随着升温速率的提高，各失重阶段对应的最大失重速率温度均向高温区移动，第四阶段向高温区移动的幅度最大，达到113℃，但该阶段在30℃/min条件下的失重速率最快、反应得到强化；FWO模型更适用于描述纳米钛酸钡前体的热分解过程，四个阶段的平均反应活化能分别为67.89kJ/mol、208.92kJ/mol、494.04kJ/mol和195.11kJ/mol，第三阶段的反应活化能最高、反应较难发生；在纳米钛酸钡前体热分解过程中，宏观大颗粒会演化成微观小颗粒的聚集体，较高的恒温温度会导致颗粒粒径变大，因此恒温温度不宜超过900℃。研究结果为纳米钛酸钡前体热分解工艺参数的选择提供了理论依据。

关键词: 钛酸钡前体, 热分解, 动力学, 热重-质谱, 颗粒演化

CLC Number:

TQ174

ZHANG Hao, LU Xiaoming. Thermal decomposition kinetics and particle evolution characteristics of nano barium titanate precursor[J]. Chemical Industry and Engineering Progress, 2024, 43(7): 3987-3995.

张昊, 陆小明. 纳米钛酸钡前体热分解反应动力学及颗粒演化机理[J]. 化工进展, 2024, 43(7): 3987-3995.

Figures/Tables 11

阶段	温度/℃	失重率/%	热分解过程涉及的反应	编号
第一阶段	20~190	11	$B a T i O {(C_{2} O_{4})}_{2} \cdot 4 H_{2} O \overset{}{\to} B a T i O {(C_{2} O_{4})}_{2} + 4 H_{2} O$ ↑	式(5)
第二阶段	190~410	20	$2 B a T i O {(C_{2} O_{4})}_{2} \overset{}{\to} B a_{2} T i_{2} O_{5} C_{2} O_{5} + 4 C O ↑ + 2 C O_{2}$ ↑	式(6)
第三阶段	410~640	5	$B a_{2} T i_{2} O_{5} C_{2} O_{5} \overset{}{\to} C O_{2}$ ↑ $+ B a C O_{3} + 2 T i O_{2} + B a O$	式(7)
第四阶段	640~720	7	$B a O + T i O_{2} \overset{}{\to} B a T i O_{3}$ $B a C O_{3} + T i O_{2} \overset{}{\to} B a T i O_{3} + C O_{2} ↑$	式(8) 式(9)
第五阶段	720~1000	0	—	—

阶段	温度/℃	失重率/%	热分解过程涉及的反应	编号
第一阶段	20~190	11	$B a T i O {(C_{2} O_{4})}_{2} \cdot 4 H_{2} O \overset{}{\to} B a T i O {(C_{2} O_{4})}_{2} + 4 H_{2} O$ ↑	式(5)
第二阶段	190~410	20	$2 B a T i O {(C_{2} O_{4})}_{2} \overset{}{\to} B a_{2} T i_{2} O_{5} C_{2} O_{5} + 4 C O ↑ + 2 C O_{2}$ ↑	式(6)
第三阶段	410~640	5	$B a_{2} T i_{2} O_{5} C_{2} O_{5} \overset{}{\to} C O_{2}$ ↑ $+ B a C O_{3} + 2 T i O_{2} + B a O$	式(7)
第四阶段	640~720	7	$B a O + T i O_{2} \overset{}{\to} B a T i O_{3}$ $B a C O_{3} + T i O_{2} \overset{}{\to} B a T i O_{3} + C O_{2} ↑$	式(8) 式(9)
第五阶段	720~1000	0	—	—

阶段	升温速率 /℃·min^-1	温度/℃
阶段	升温速率 /℃·min^-1	α_10%	α_20%	α_40%	α_60%	α_80%	α_90%
第一阶段	2	44	61	74	85	106	129
	5	54	72	88	99	117	138
	10	60	81	98	111	133	156
	20	72	95	113	125	148	174
	30	73	100	121	134	156	180
第二阶段	2	288	306	326	340	358	377
	5	300	318	337	351	370	388
	10	310	327	345	360	380	398
	20	322	338	356	372	394	413
	30	327	344	362	378	402	421
第三阶段	2	436	448	471	495	522	539
	5	446	457	479	505	534	552
	10	451	461	480	506	536	555
	20	464	472	489	513	543	566
	30	470	478	494	516	544	569
第四阶段	2	608	615	623	631	646	658
	5	632	641	652	664	681	688
	10	656	668	684	696	705	709
	20	685	703	717	722	727	731
	30	705	722	730	735	740	743

阶段	转化率/%	FWO模型		KAS模型
阶段	转化率/%	E_a /kJ·mol^–1	R²	E_a /kJ·mol^–1	R²
第一阶段	10	76.86	0.985	75.29	0.982
	20	66.79	0.994	63.01	0.992
	40	62.43	0.997	59.55	0.994
	60	63.93	0.999	60.43	0.998
	80	67.03	0.99	64.41	0.986
	90	70.32	0.977	65.96	0.966
	平均	67.89	0.99	64.77	0.986
第二阶段	10	181.87	0.998	181.59	0.998
	20	201.5	0.999	206.17	0.995
	40	226.35	0.997	216.69	0.99
	60	222.68	0.996	216.3	0.99
	80	205.81	0.993	215.11	0.989
	90	215.3	0.987	215.33	0.986
	平均	208.92	0.995	208.53	0.991
第三阶段	10	327.39	0.978	332.19	0.977
	20	385.38	0.976	393.01	0.974
	40	531.34	0.962	546.17	0.963
	60	619.11	0.969	638.09	0.967
	80	615.75	0.961	634.09	0.969
	90	485.28	0.978	496.54	0.977
	平均	494.04	0.971	506.68	0.971
第四阶段	10	188.76	0.992	183.05	0.99
	20	173.01	0.992	166.29	0.99
	40	173.64	0.996	166.81	0.995
	60	183.85	0.996	177.45	0.996
	80	212.64	0.995	207.56	0.994
	90	238.78	0.998	234.91	0.998
	平均	195.11	0.995	189.35	0.994

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