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浙江大学学报(工学版)
浙江大学学报(工学版)  2021, Vol. 55 Issue (11): 2100-2107    DOI: 10.3785/j.issn.1008-973X.2021.11.010
机械工程     
基于扫描升温模式的差示功率补偿绝热量热方法
原明阳(),许启跃,丁炯,叶树亮*()
中国计量大学 工业与商贸计量技术研究所，浙江 杭州 310018
Differential power compensation’s adiabatic calorimetry method based on scanning heating mode
Ming-yang YUAN(),Qi-yue XU,Jiong DING,Shu-liang YE*()
Institute of Industry and Trade Measurement Technology, China Jiliang University, Hangzhou 310018, China
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摘要：

为了解决传统绝热加速量热仪反应检测效率低、反应判断灵敏度不高、绝热性能受限的问题，提出差示功率补偿绝热扫描量热方法. 在实验样品分解反应的激发阶段，用扫描模式匀速升温，并采用基于扫描基线的两通道补偿功率差、温差和样品温升速率3种动态反应检测方法并行进行检测，以适应复杂工况的反应环境，提高反应检测效率和灵敏度；当判断发生反应后，结合差示功率补偿控制和基于恒温基线的动态绝热追踪，使样品实现接近理想的绝热反应过程. 以过氧化二叔丁基（DTBP）为实验对象进行实验验证，结果表明，与传统绝热加速量热方法相比，差示功率补偿绝热扫描量热方法在0.3~0.7 ℃/min的扫描速率范围内，能明显提高反应检测效率和灵敏度，并可以得到更准确的热分解特性参数和动力学参数.
关键词： 差示绝热扫描量热;  动态绝热追踪;  功率补偿;  热惰性;  反应检测    
Abstract:

A differential power compensation adiabatic scanning calorimetry method was proposed, in order to solve the problems of low reaction detection efficiency, low reaction judgment sensitivity, and limited adiabatic performance of traditional adiabatic accelerating calorimeter. During the excitation stage of sample decomposition reaction, scanning mode is used to heat up the entire two-channel reaction system at a constant rate, and in order to adapt to the reaction environment of complex working condition, three dynamic reaction detection methods based on scanning baseline, i.e., two-channel heating power difference, two-channel sample temperature difference, and sample temperature rise rate, are used at the same time to improve the reaction detection efficiency and sensitivity. When the reaction happens, the differential power compensation control method and the dynamic adiabatic tracking method based on the constant temperature baseline are combined, making the sample achieve close to ideal adiabatic reaction process. The experimental verification with di-tert-butyl peroxide (DTBP) as the experimental object shows that the differential power compensation adiabatic scanning calorimetry method can significantly improve the reaction detection efficiency and sensitivity, and obtain more accurate thermal decomposition characteristics and kinetic parameters within the scan rate range of 0.3 ℃/min to 0.7 ℃/min compared with traditional adiabatic accelerating calorimetry method.
Key words: differential adiabatic scanning calorimetry    dynamic adiabatic tracking    power compensation    thermalinertia    reaction detection
收稿日期: 2020-12-11 出版日期: 2021-11-05
CLC:  TQ 013.2  
基金资助: 国家自然科学基金资助项目（22003059，21927815）；浙江省基础公益研究计划资助项目（LGF18B030001）
通讯作者: 叶树亮     E-mail: ethan_yuan@qq.com;itmt_paper@126.com
作者简介: 原明阳（1995—），男，硕士生，从事量热技术与仪器研究. orcid.org/0000-0002-7150-528X. E-mail: ethan_yuan@qq.com
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原明阳
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引用本文:

原明阳,许启跃,丁炯,叶树亮. 基于扫描升温模式的差示功率补偿绝热量热方法[J]. 浙江大学学报(工学版), 2021, 55(11): 2100-2107.

Ming-yang YUAN,Qi-yue XU,Jiong DING,Shu-liang YE. Differential power compensation’s adiabatic calorimetry method based on scanning heating mode. Journal of ZheJiang University (Engineering Science), 2021, 55(11): 2100-2107.

链接本文:

https://www.zjujournals.com/eng/CN/10.3785/j.issn.1008-973X.2021.11.010    或    https://www.zjujournals.com/eng/CN/Y2021/V55/I11/2100

图 1  双通道炉体结构图
图 2  差示绝热扫描量热控温流程
图 3  差示功率补偿绝热扫描量热过程样品预期温度曲线
图 4  匀速扫描基线控温曲线
图 5  扫描基线扫描升温阶段获得的3种基线曲线
图 6  台阶恒温基线控温曲线
图 7  恒温基线恒温阶段获得的2种基线曲线
图 8  差示绝热量热实验平台
图 9  3种量热模式实验曲线
量热模式 θ′ 0/℃ vmax/（℃·min?1） Δθ′/℃ L/min
差示功率补偿绝热
扫描量热方法 		120~130 16~35 86~98 300~410
低热惰性扫描量热方法 135~140 7~20 60~70 160~260
差示绝热量热方法 112~127 6~18 80~94 500-600
表 1  不同量热模式实验热分解特性分析
Rs/（℃·min?1） θ′ 0/℃ vmax/（℃·min?1） Δθ′/℃
0.3 124~126 13~24 86~94
0.5 120~125 16~27 91~98
0.7 124~129 17~32 89~96
表 2  不同扫描速率量热实验热分解特性分析
图 10  3种扫描速率下的时间-温度实验曲线
w/% θ′ 0/℃ vmax/（℃·min?1） Δθ′/℃
10 128~135 0.9~1.7 42~49
15 120~130 16.0~35.0 85~94
20 115~123 38.0~50.0 104~114
表 3  不同DTBP溶液质量分数下的热分解特性分析
Rs/（℃·min?1） n A/(1015 s?1) E/（105 kJ·mol?1）
0.3 1 3.75~34.10 1.56~1.63
0.5 1 6.48~9.95 1.58~1.59
0.7 1 3.66~6.56 1.55~1.58
表 4  不同扫描速率的热降解动力学分析
w/% n A/s?1 E/（105 kJ·mol?1）
10 1 2.53×1019~4.03×1020 1.87~1.96
15 1 3.66×1015~3.41×1016 1.55~1.60
20 1 2.46×1015~4.53×1015 1.54~1.57
表 5  不同DTBP溶液质量分数的热降解动力学分析
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