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基于苦味酸热分解模型动力学分析的保质期预测

Shelf Life Prediction of Picric Acid via Model-Based Kinetic Analysis of Its Thermal Decomposition.

作者信息

Sanchirico Roberto, Santonocito Marco Luca, Di Sarli Valeria, Lisi Luciana

机构信息

Istituto di Scienze e Tecnologie per l'Energia e la Mobilità Sostenibili (STEMS), Consiglio Nazionale delle Ricerche (CNR), via Guglielmo Marconi 4, 80125 Napoli, Italy.

Segretariato Generale della Difesa e Direzione Nazionale degli Armamenti, Direzione degli Armamenti Terrestri, Ufficio Tecnico Territoriale Armamenti Terrestri, Piazzale degli Eroi 1, 00048 Nettuno, Italy.

出版信息

Materials (Basel). 2022 Dec 13;15(24):8899. doi: 10.3390/ma15248899.

DOI:10.3390/ma15248899
PMID:36556705
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9785429/
Abstract

A priori knowledge of the shelf life of energetic materials (EMs) is relevant due to its direct association with safety and functionality. This paper proposes a quick and reliable approach to predicting the shelf life of EMs whose thermal decomposition is an autocatalytic process once their failure threshold has been defined as a function of the limiting extent of conversion. This approach is based on the assumption of a kinetic law consistent with the autocatalytic behavior and on the subsequent extraction, via a suitable procedure of parameter identification, of the kinetics of thermal decomposition from differential scanning calorimetry (DSC) data gathered under dynamic conditions at three different heating rates. Its reliability is proven for picric acid (PA) through the comparison of kinetic predictions with evaluations of conversion obtained by using high performance liquid chromatography (HPLC) analysis for samples subjected to isothermal and non-isothermal accelerated aging tests, as well as for a sample of naturally aged material, i.e., PA, stored at room temperature for more than 10 years.

摘要

由于其与安全性和功能性直接相关，含能材料（EMs）保质期的先验知识具有重要意义。本文提出了一种快速且可靠的方法来预测EMs的保质期，这些EMs的热分解是一个自催化过程，一旦将其失效阈值定义为转化率极限程度的函数。该方法基于与自催化行为一致的动力学定律假设，并通过合适的参数识别程序，从在三种不同加热速率的动态条件下收集的差示扫描量热法（DSC）数据中提取热分解动力学。通过将动力学预测结果与使用高效液相色谱（HPLC）分析对经历等温及非等温加速老化试验的样品以及在室温下储存超过10年的天然老化材料（即苦味酸（PA））样品所获得的转化率评估结果进行比较，证明了该方法对苦味酸（PA）的可靠性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/692d251b91f4/materials-15-08899-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/948e09712325/materials-15-08899-g001.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/2bd9bd02b0a1/materials-15-08899-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/75ae51c49edb/materials-15-08899-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/e640429e1452/materials-15-08899-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/b7b152e39450/materials-15-08899-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/b248ea61b8e9/materials-15-08899-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/692d251b91f4/materials-15-08899-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/948e09712325/materials-15-08899-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/e320a32e02e1/materials-15-08899-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/7bc42680b5de/materials-15-08899-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/2bd9bd02b0a1/materials-15-08899-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/75ae51c49edb/materials-15-08899-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/e640429e1452/materials-15-08899-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/b7b152e39450/materials-15-08899-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/b248ea61b8e9/materials-15-08899-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/dd87/9785429/692d251b91f4/materials-15-08899-g009.jpg

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