Experimental and modeling studies of IPDI-based polyurea elastomers – The role of hard segment fraction

Demetrios A. Tzelepis; Jorge Suzuki; Yi Feng Su; Yiyu Wang; Yong Chae Lim; Mohsen Zayernouri; Valeriy V. Ginzburg

doi:10.1002/app.53592

Experimental and modeling studies of IPDI-based polyurea elastomers – The role of hard segment fraction

Demetrios A. Tzelepis, Jorge Suzuki, Yi Feng Su, Yiyu Wang, Yong Chae Lim, Mohsen Zayernouri, Valeriy V. Ginzburg

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

Segmented polyureas (PUa) are industrially important class of polymers widely used in coatings, sealant, and adhesive applications. Here, we report synthesis, characterization, and modeling of Isophorone Diisocyanate-Diethyl-Toluene-Diamine-Polyether amine (IPDI-DETDA-PO PUa) with varied hard segment contents of 20, 30, and 40 weight percent. For each of the three materials, we study its structure and phase behavior using FTIR, DSC, and TEM, and clearly show the presence of microphase separation between the hard and soft nanodomains. We then measure the linear viscoelastic response of the PUa-s using DMA (frequency sweeps at multiple temperatures). The DMA data are shown to obey the time-temperature superposition. Finally, we develop a new micromechanical model describing the DMA results; the model describes a phase-separated PUa as two “Fractional-order Maxwell gels” branches, connected in parallel, with the first FMG branch representing the “percolated hard phase" and the second one modeling the “filled soft phase". In agreement with the earlier thermodynamic theories, the volume-fraction of the percolated hard phase is related to the hard segment weight-fraction (HSWF), defined as the combined mass of IPDI and DETDA normalized to the total mass of the polymer. The data and model are found to be in a good qualitative and quantitative agreement.

Original language	English
Article number	e53592
Journal	Journal of Applied Polymer Science
Volume	140
Issue number	10
DOIs	https://doi.org/10.1002/app.53592
State	Published - Mar 10 2023

Funding

JLS was partially supported by the NSF award (DMS-1923201) and MZ's startup fund, moreover, MZ was supported jointly by the US ARO YIP award (W911NF-19-1-0444) and the US NSF award (DMS-1923201). Experimental work was partially supported by PPG Industries Inc. under Collaboration Agreement Number 201825-140909 and US-Army Ground Vehicle System Center under an In-house Laboratory Independent Research Grant. The authors would like to Acknowledge Dr. Mahmoodul Haq for his experimental support at Composite Vehicle Research Center. JLS was partially supported by the NSF award (DMS‐1923201) and MZ's startup fund, moreover, MZ was supported jointly by the US ARO YIP award (W911NF‐19‐1‐0444) and the US NSF award (DMS‐1923201). Experimental work was partially supported by PPG Industries Inc. under Collaboration Agreement Number 201825‐140909 and US‐Army Ground Vehicle System Center under an In‐house Laboratory Independent Research Grant.

Funders	Funder number
US ARO	W911NF‐19‐1‐0444
National Science Foundation	DMS‐1923201
U.S. Army
PPG Industries	201825‐140909
CCDC Ground Vehicle Systems Center

Keywords

adhesive
dynamic mechanical analysis
fractional calculus
hard domains
polyurea
time temperature superposition

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title = "Experimental and modeling studies of IPDI-based polyurea elastomers – The role of hard segment fraction",

abstract = "Segmented polyureas (PUa) are industrially important class of polymers widely used in coatings, sealant, and adhesive applications. Here, we report synthesis, characterization, and modeling of Isophorone Diisocyanate-Diethyl-Toluene-Diamine-Polyether amine (IPDI-DETDA-PO PUa) with varied hard segment contents of 20, 30, and 40 weight percent. For each of the three materials, we study its structure and phase behavior using FTIR, DSC, and TEM, and clearly show the presence of microphase separation between the hard and soft nanodomains. We then measure the linear viscoelastic response of the PUa-s using DMA (frequency sweeps at multiple temperatures). The DMA data are shown to obey the time-temperature superposition. Finally, we develop a new micromechanical model describing the DMA results; the model describes a phase-separated PUa as two “Fractional-order Maxwell gels” branches, connected in parallel, with the first FMG branch representing the “percolated hard phase{"} and the second one modeling the “filled soft phase{"}. In agreement with the earlier thermodynamic theories, the volume-fraction of the percolated hard phase is related to the hard segment weight-fraction (HSWF), defined as the combined mass of IPDI and DETDA normalized to the total mass of the polymer. The data and model are found to be in a good qualitative and quantitative agreement.",

keywords = "adhesive, dynamic mechanical analysis, fractional calculus, hard domains, polyurea, time temperature superposition",

author = "Tzelepis, {Demetrios A.} and Jorge Suzuki and Su, {Yi Feng} and Yiyu Wang and Lim, {Yong Chae} and Mohsen Zayernouri and Ginzburg, {Valeriy V.}",

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AU - Wang, Yiyu

AU - Lim, Yong Chae

AU - Zayernouri, Mohsen

AU - Ginzburg, Valeriy V.

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AB - Segmented polyureas (PUa) are industrially important class of polymers widely used in coatings, sealant, and adhesive applications. Here, we report synthesis, characterization, and modeling of Isophorone Diisocyanate-Diethyl-Toluene-Diamine-Polyether amine (IPDI-DETDA-PO PUa) with varied hard segment contents of 20, 30, and 40 weight percent. For each of the three materials, we study its structure and phase behavior using FTIR, DSC, and TEM, and clearly show the presence of microphase separation between the hard and soft nanodomains. We then measure the linear viscoelastic response of the PUa-s using DMA (frequency sweeps at multiple temperatures). The DMA data are shown to obey the time-temperature superposition. Finally, we develop a new micromechanical model describing the DMA results; the model describes a phase-separated PUa as two “Fractional-order Maxwell gels” branches, connected in parallel, with the first FMG branch representing the “percolated hard phase" and the second one modeling the “filled soft phase". In agreement with the earlier thermodynamic theories, the volume-fraction of the percolated hard phase is related to the hard segment weight-fraction (HSWF), defined as the combined mass of IPDI and DETDA normalized to the total mass of the polymer. The data and model are found to be in a good qualitative and quantitative agreement.

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Experimental and modeling studies of IPDI-based polyurea elastomers – The role of hard segment fraction

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