Fractional‐Order Kinetics Modeling of Starch Thermal Degradation

Starch Pub Date : 2024-04-19 DOI:10.1002/star.202400024
César Roldan‐Cruz, Angeles García‐Hernandez, Heidi Andrea Fonseca‐Florido, Eduardo Jaime Vernon‐Carter, Jose Alvarez‐Ramirez
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Abstract

The thermal decomposition modeling of starch granules (rice, maize, and potato) is investigated in this work. Thermogravimetric analysis (TGA) under nitrogen conditions and different heating rates is carried out. First, a model‐free analysis is carried out to determine the variability of the activation energy with the relative conversion. The results reveal that the sequence of activation energy is rice > maize > potato. In turn, the activation energy is positively correlated (ρ = 0.98) with the relative crystallinity determined by X‐ray diffraction (XRD) analysis. Then, a fractional‐order version of the Sestak–Berggren equation is used to model the starch thermal decomposition. A least‐squares approach is used to estimate the underlying parameters by fitting non‐isothermal TGA curves. The results show that the parameters depend on the heating rate, but more strongly on the XRD relative crystallinity. Overall, the results reported in this study indicate that fractional‐order kinetics models provide an accurate description of the starch thermal degradation, without the use of the traditional TGA heuristic methods used for parameter estimation.

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淀粉热降解的分数阶动力学模型
这项工作研究了淀粉颗粒(大米、玉米和马铃薯)的热分解模型。在氮气条件和不同加热速率下进行了热重分析(TGA)。首先,进行了无模型分析,以确定活化能随相对转化率的变化情况。结果表明,活化能的顺序为水稻> 玉米> 马铃薯。而活化能与 X 射线衍射(XRD)分析确定的相对结晶度呈正相关(ρ = 0.98)。然后,使用 Sestak-Berggren 方程的分数阶版本来模拟淀粉热分解。通过拟合非等温 TGA 曲线,采用最小二乘法估算基本参数。结果表明,参数取决于加热速率,但更取决于 XRD 相对结晶度。总之,本研究报告的结果表明,分数阶动力学模型能准确描述淀粉的热降解,而无需使用用于参数估计的传统 TGA 启发式方法。
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