Two decoupling methods for non-isothermal DSC results of AIBN decomposition

Zhang, Cai-xing; Gui-Bin, LU; Chen, Liping; Chen, Wanghua; Peng, Minjun; Lv, Jiayu

doi:10.1016/j.jhazmat.2014.11.022

Cited by 34 publications

(12 citation statements)

References 15 publications

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“…Compared with the activation energy of AIBM calculated in Reference , the activation energy of this study is slightly higher due to the difference in calculation method, experimental condition, and experimental instrument.…”

Section: Resultscontrasting

confidence: 60%

“…In theory, the NN structure readily breaks and releases nitrogen at elevated temperatures. A substantial number of accidents have occurred in the manufacturing or storage processes of chemical agents because of improper coping approaches . 2,2′‐azobis(2‐methylpropionitrile) (AIBN) and 1,1′‐azobis(cyclohexanecarbonitrile) (ABCN) are common azo compounds, which are used as initiators in polymerization because they are easily cleaved and form groups with high activation energy.…”

Section: Introductionmentioning

confidence: 99%

“…Notably, some of these compounds can slowly decompose, even at room temperature, causing fire and explosions as typical autocatalytic reactions. In previous studies, scholars mostly focused on theoretical research of AIBN and ABCN, including some kinetic calculations . However, no one has so far associated its thermal risk with the actual situation.…”

Section: Introductionmentioning

confidence: 99%

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Solid thermal explosion of autocatalytic material based on nonisothermal experiments: Multistage evaluations for 2,2′‐azobis(2‐methylpropionitrile) and 1,1′‐azobis(cyclohexanecarbonitrile)

Cao

Pan

et al. 2019

Process Safety Progress

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To achieve the thermal stability characteristics of azo compounds, a method for characterizing the kinetics of the reaction and decomposition for azo compounds based on nonisothermal calorimetric data was explored. Differential scanning calorimetry (DSC) was employed to analyze the thermal decomposition of two azo compounds, 2,2 0 -azobis(2-methylpropionitrile) and 1,1 0 -azobis(cyclohexanecarbonitrile). DSC experiments were performed to acquire the exothermic peak temperature (T p ), exothermic final temperature (T f ), and heat of decomposition (4H d ). Corresponding thermokinetics were calculated using Flynn-Wall-Ozawa method. Moreover, data determined through DSC experiments were utilized to predict the self-accelerating decomposition temperature, control temperature, and emergency temperature. A nonisothermal experiment was performed to investigate the runaway characteristics of azo compounds, the melting behavior that occurred in the decomposition process interfered with thermal analysis. Through dividing the reaction into several stages, multistage evaluations were carried out in the process of our study. During the thermal explosion simulation, the actual packing parameter of 25.0 kg was applied to ensure that the simulation results were more practical. Thermal safety parameters acquired from the simulation results can provide information on loss prevention and facilitated the establishment of an emergency relief system. Highlights• The decomposition process was divided into several stages and considered melting behavior.• A green method contributes to intrinsic safety design.• Solid thermal explosion was simulated. K E Y W O R D Sazo compound, loss prevention, multistage evaluation, self-accelerating decomposition temperature, thermal analysis

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Section: Resultscontrasting

confidence: 60%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Solid thermal explosion of autocatalytic material based on nonisothermal experiments: Multistage evaluations for 2,2′‐azobis(2‐methylpropionitrile) and 1,1′‐azobis(cyclohexanecarbonitrile)

Cao

Pan

et al. 2019

Process Safety Progress

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“…The overlap of endothermic peak and exothermic peak in DSC curves also makes it difficult to establish suitable kinetic model. Cai-Xing Zhang et al [20] called this phenomenon "a coupling phenomenon of heat absorption and generation", and proposed a solvent method and a mathematical decoupling method to separate the "pure" exothermic DSC curve. This paper aims to establish a multistep kinetic model considering the influence of melting to separate the endothermic peak and exothermic peak.…”

Section: Introductionmentioning

confidence: 99%

Kinetic Modeling of Liquid Phase RDX Thermal Decomposition Process and its Application in the Slow Cook‐Off Test Prediction

Zhao

et al. 2021

Propellants Explo Pyrotec

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RDX is an important and commonly used energetic material. The understanding thermal decomposition process of RDX is of great significance for the safety of its production, storage, and use. However, due to the coupling of phase transition and thermal decomposition process, a multi-step kinetic model including melting and decomposition process has not been established so far, which is not helpful to the prediction of its thermal behavior in different conditions. In this paper, Differential Scanning Calorimetry was used to measure the decomposition characteristics of RDX at different heating rates. A four-step consecutive reaction model A!A liq !B!C!D was established to depict the melting and decomposition process. Then quench and reheat experiments were performed to determine the types of each step, where the reaction types are autocatalytic except that the step of B!C is an N-order reaction. The model was used to predict the result of slow cook-off test. It was found that the predicted time of thermal explosion is 0.2 h earlier than the experiment and the onset temperature is 0.6°C smaller than experiment, which verifies the rationality of the kinetic model.

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“…At present, thermal analysis kinetics software (AKTS) and MATLAB software are reported to separate the overlapping parts of the thermal analysis process [18][19][20]. The principle of both of them is to use suitable mathematical functions for curve fitting to find the best matching function model and parameters.…”

Section: Introductionmentioning

confidence: 99%

An analytical method for overlapping of the melting and decomposition of 2-oximemalononitrile

Zhu

An²,

Chang³

et al. 2020

J Therm Anal Calorim

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In the thermal analysis of many energetic compounds, there is a phenomenon of melting before decomposition, and the melting endothermic process is masked by the subsequent rapid exothermic decomposition, which has affected the research of separation in melting and thermal decomposition processes. 2-oximemalononitrile, an energetic intermediate whose melting and decomposition processes had the overlapping, was used as the research object in this paper, and the complete melting and decomposition processes were acquired by MATLAB software, separately. In addition, the kinetics and mechanism of thermal decomposition of 2-oximemalononitrile were investigated by Málek method, which was used as guidance for the safe application in handling, processing, and storage.

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Two decoupling methods for non-isothermal DSC results of AIBN decomposition

Cited by 34 publications

References 15 publications

Solid thermal explosion of autocatalytic material based on nonisothermal experiments: Multistage evaluations for 2,2′‐azobis(2‐methylpropionitrile) and 1,1′‐azobis(cyclohexanecarbonitrile)

Solid thermal explosion of autocatalytic material based on nonisothermal experiments: Multistage evaluations for 2,2′‐azobis(2‐methylpropionitrile) and 1,1′‐azobis(cyclohexanecarbonitrile)

Kinetic Modeling of Liquid Phase RDX Thermal Decomposition Process and its Application in the Slow Cook‐Off Test Prediction

An analytical method for overlapping of the melting and decomposition of 2-oximemalononitrile

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