通过等转化动力学分析评估二元和三元生物可降解聚合物混合物的热稳定性

IF 3.1 2区 化学 Q2 CHEMISTRY, ANALYTICAL
Tibor Dubaj , Stefano Vecchio Ciprioti , Jacopo Tirillò , Fabrizio Sarasini
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引用次数: 0

摘要

在此,我们报告了聚合物共混物热降解的动力学分析,该分析基于增量等转换法,以及基于 Fraser-Suzuki 峰值函数的热重曲线数学解卷积。测得的动力学包络线被分解成与聚合物混合物各成分降解大致对应的部分。等转化分析得出的动力学参数被进一步用于估算混合物对各成分热稳定性的影响。与常规使用的降解起始温度或 DTG 峰值温度等参数相比,解卷积分析可以确定混合物中所有成分的稳定性,而无需考虑其相对含量。在这里,我们还展示了可以直接对积分 α(T) 曲线进行解卷积分析,从而绕过了使用差分数据 dα/dt 的工作。通过对去卷积 α(T)曲线进行等转换分析,可以计算出各种参数,以评估对热降解的潜在加速或抑制作用,例如通过分解半衰期 t0.5。利用 t0.5(混合物)/t0.5(纯聚合物)等稳定性相对标准,可以使结果更加可靠。利用这种方法,证实了 PHBV 和 PBAT 在 300 °C 以上对聚乳酸热稳定性的不利影响。另一方面,与纯聚合物相比,PHBV 在二元和三元混合物中的稳定性都有所提高。
本文章由计算机程序翻译,如有差异,请以英文原文为准。

Thermal stability of binary and ternary biodegradable polymer blends assessed by isoconversional kinetic analysis

Thermal stability of binary and ternary biodegradable polymer blends assessed by isoconversional kinetic analysis

Here we report on kinetic analysis of thermal degradation of polymer blends based on incremental isoconversional method coupled with mathematical deconvolution of thermogravimetric curves based on Fraser–Suzuki peak function. The measured kinetic envelope was decomposed into contributions approximately corresponding to degradation of each constituent of a polymer blend. Kinetic parameters from isoconversional analysis were further used for estimating the effect of blending on thermal stability of the constituents. Compared to routinely used parameters such as degradation onset temperature or DTG-peak temperature, the deconvolution analysis allows to determine stability of all components in a mixture regardless of their relative content. Here we also show that deconvolution analysis can be carried out directly on integral α(T) curves, thus bypassing the work with differential data /dt. Isoconversional analysis of deconvoluted α(T) curves allows to calculate various parameters for assessing the potentially accelerating or inhibiting effect on thermal degradation, for example, by means of decomposition half-time t0.5. The results can be made more robust by utilizing relative criteria for stability such as t0.5(blend)/t0.5(neat polymer). Using this approach, detrimental effect of PHBV and PBAT on thermal stability of PLA above 300 °C was confirmed. On the other hand, stability of PHBV in both binary and ternary mixtures was improved compared to neat polymer.

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来源期刊
Thermochimica Acta
Thermochimica Acta 化学-分析化学
CiteScore
6.50
自引率
8.60%
发文量
210
审稿时长
40 days
期刊介绍: Thermochimica Acta publishes original research contributions covering all aspects of thermoanalytical and calorimetric methods and their application to experimental chemistry, physics, biology and engineering. The journal aims to span the whole range from fundamental research to practical application. The journal focuses on the research that advances physical and analytical science of thermal phenomena. Therefore, the manuscripts are expected to provide important insights into the thermal phenomena studied or to propose significant improvements of analytical or computational techniques employed in thermal studies. Manuscripts that report the results of routine thermal measurements are not suitable for publication in Thermochimica Acta. The journal particularly welcomes papers from newly emerging areas as well as from the traditional strength areas: - New and improved instrumentation and methods - Thermal properties and behavior of materials - Kinetics of thermally stimulated processes
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