Multistage Thermal Decomposition Kinetics of Glycidyl Azide Polymer-Based Thermoplastic Elastomers: A Constrained Deconvolution Approach.
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| Title: | Multistage Thermal Decomposition Kinetics of Glycidyl Azide Polymer-Based Thermoplastic Elastomers: A Constrained Deconvolution Approach. |
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| Authors: | Wang, Zhu1 (AUTHOR), Yu, Haoyu2 (AUTHOR), Ding, Shanjun1,3 (AUTHOR), Liu, Wenhao1 (AUTHOR), Zhao, Shuai1,2 (AUTHOR), Luo, Yunjun1,3 (AUTHOR) yjluo@bit.edu.cn |
| Source: | Polymers (20734360). Mar2026, Vol. 18 Issue 5, p666. 25p. |
| Subjects: | Thermoplastic elastomers, Deconvolution (Mathematics), Polymers, Chemical kinetics, Activation energy, Solid propellants, Thermolysis |
| Abstract: | Glycidyl azide polymer (GAP)-based polyurethane, a kind of energetic thermoplastic elastomer (ETPE), is a promising binder for advanced solid propellants, but its thermal decomposition involves overlapping competitive reactions that conventional single-step kinetic models cannot characterize accurately, limiting its engineering applications. To address this limitation, a constrained asymmetric Gaussian deconvolution strategy with fixed peak area ratios and shape constraints was developed in this work. This strategy was applied to resolve overlapping reaction rate curves converted from derivative thermogravimetric data of GAP-based ETPEs with 50 wt% GAP content at four heating rates of 5, 10, 15 and 20 K·min−1. The complex decomposition process was successfully split into five stages, assigned to azide cleavage, polyether backbone scission, carbamate cleavage, hydrocarbon product degradation and residue decomposition, with a goodness of fit of R2 > 0.998. Apparent activation energies of the five stages were determined through cross-validation by the Friedman and Flynn–Wall–Ozawa methods without prior assumption of reaction mechanisms, following the order of residue decomposition (181.4 ± 1.0 kJ·mol−1) > hydrocarbon product degradation (159.9 ± 1.0 kJ·mol−1) ≈ azide cleavage (156.5 ± 0.6 kJ·mol−1) > backbone scission (135.1 ± 0.7 kJ·mol−1) > carbamate cleavage (111.9 ± 1.1 kJ·mol−1). Pre-exponential factors with lnA0 values ranging from 22.2 to 34.0 were derived via the kinetic compensation effect. Finally, generalized master plots were employed to compare with classic solid-state reaction models for mechanistic insight, and the Šesták–Berggren model fit three major stages excellently (R2 > 0.996) by accounting for synergistic nucleation-growth and phase boundary mechanisms, enabling high-precision kinetic equations. It should be noted that the constrained deconvolution method proposed in this work has general applicability for kinetic analysis of GAP-based ETPEs with different formulations and other complex energetic polymer systems, while the obtained kinetic parameters are composition-specific and only applicable to the corresponding ETPE formulation studied herein. [ABSTRACT FROM AUTHOR] |
| Copyright of Polymers (20734360) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
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| Header | DbId: egs DbLabel: Engineering Source An: 192641967 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Multistage Thermal Decomposition Kinetics of Glycidyl Azide Polymer-Based Thermoplastic Elastomers: A Constrained Deconvolution Approach. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Wang%2C+Zhu%22">Wang, Zhu</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Yu%2C+Haoyu%22">Yu, Haoyu</searchLink><relatesTo>2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Ding%2C+Shanjun%22">Ding, Shanjun</searchLink><relatesTo>1,3</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Liu%2C+Wenhao%22">Liu, Wenhao</searchLink><relatesTo>1</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Zhao%2C+Shuai%22">Zhao, Shuai</searchLink><relatesTo>1,2</relatesTo> (AUTHOR)<br /><searchLink fieldCode="AR" term="%22Luo%2C+Yunjun%22">Luo, Yunjun</searchLink><relatesTo>1,3</relatesTo> (AUTHOR)<i> yjluo@bit.edu.cn</i> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Polymers+%2820734360%29%22">Polymers (20734360)</searchLink>. Mar2026, Vol. 18 Issue 5, p666. 25p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Thermoplastic+elastomers%22">Thermoplastic elastomers</searchLink><br /><searchLink fieldCode="DE" term="%22Deconvolution+%28Mathematics%29%22">Deconvolution (Mathematics)</searchLink><br /><searchLink fieldCode="DE" term="%22Polymers%22">Polymers</searchLink><br /><searchLink fieldCode="DE" term="%22Chemical+kinetics%22">Chemical kinetics</searchLink><br /><searchLink fieldCode="DE" term="%22Activation+energy%22">Activation energy</searchLink><br /><searchLink fieldCode="DE" term="%22Solid+propellants%22">Solid propellants</searchLink><br /><searchLink fieldCode="DE" term="%22Thermolysis%22">Thermolysis</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Glycidyl azide polymer (GAP)-based polyurethane, a kind of energetic thermoplastic elastomer (ETPE), is a promising binder for advanced solid propellants, but its thermal decomposition involves overlapping competitive reactions that conventional single-step kinetic models cannot characterize accurately, limiting its engineering applications. To address this limitation, a constrained asymmetric Gaussian deconvolution strategy with fixed peak area ratios and shape constraints was developed in this work. This strategy was applied to resolve overlapping reaction rate curves converted from derivative thermogravimetric data of GAP-based ETPEs with 50 wt% GAP content at four heating rates of 5, 10, 15 and 20 K·min−1. The complex decomposition process was successfully split into five stages, assigned to azide cleavage, polyether backbone scission, carbamate cleavage, hydrocarbon product degradation and residue decomposition, with a goodness of fit of R2 > 0.998. Apparent activation energies of the five stages were determined through cross-validation by the Friedman and Flynn–Wall–Ozawa methods without prior assumption of reaction mechanisms, following the order of residue decomposition (181.4 ± 1.0 kJ·mol−1) > hydrocarbon product degradation (159.9 ± 1.0 kJ·mol−1) ≈ azide cleavage (156.5 ± 0.6 kJ·mol−1) > backbone scission (135.1 ± 0.7 kJ·mol−1) > carbamate cleavage (111.9 ± 1.1 kJ·mol−1). Pre-exponential factors with lnA0 values ranging from 22.2 to 34.0 were derived via the kinetic compensation effect. Finally, generalized master plots were employed to compare with classic solid-state reaction models for mechanistic insight, and the Šesták–Berggren model fit three major stages excellently (R2 > 0.996) by accounting for synergistic nucleation-growth and phase boundary mechanisms, enabling high-precision kinetic equations. It should be noted that the constrained deconvolution method proposed in this work has general applicability for kinetic analysis of GAP-based ETPEs with different formulations and other complex energetic polymer systems, while the obtained kinetic parameters are composition-specific and only applicable to the corresponding ETPE formulation studied herein. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Polymers (20734360) is the property of MDPI and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.3390/polym18050666 Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 25 StartPage: 666 Subjects: – SubjectFull: Thermoplastic elastomers Type: general – SubjectFull: Deconvolution (Mathematics) Type: general – SubjectFull: Polymers Type: general – SubjectFull: Chemical kinetics Type: general – SubjectFull: Activation energy Type: general – SubjectFull: Solid propellants Type: general – SubjectFull: Thermolysis Type: general Titles: – TitleFull: Multistage Thermal Decomposition Kinetics of Glycidyl Azide Polymer-Based Thermoplastic Elastomers: A Constrained Deconvolution Approach. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Wang, Zhu – PersonEntity: Name: NameFull: Yu, Haoyu – PersonEntity: Name: NameFull: Ding, Shanjun – PersonEntity: Name: NameFull: Liu, Wenhao – PersonEntity: Name: NameFull: Zhao, Shuai – PersonEntity: Name: NameFull: Luo, Yunjun IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 03 Text: Mar2026 Type: published Y: 2026 Identifiers: – Type: issn-print Value: 20734360 Numbering: – Type: volume Value: 18 – Type: issue Value: 5 Titles: – TitleFull: Polymers (20734360) Type: main |
| ResultId | 1 |
