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Analysis of post-condensation and thermo-oxidative degradation in cycloaliphatic polyamide through time-resolved rheology (TRR)

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Abstract

Melt post-condensation and thermal and thermo-oxidative degradation of a cycloaliphatic polyamide (Trogamid™ CX7323) were studied through time-resolved rheometry (TRR). The implemented TRR elucidates structural changes occurring during the two concurrent phenomena, namely, melt post-condensation and thermal/thermo-oxidative degradation, during the time sweep in a parallel plate rheometer. TRR measurements were conducted on neat Trogamid™ under nitrogen (inert/non-oxidative) and air (oxidative) environment at 3% strain amplitude and a range of frequencies between 0.1 and 100 rad/s for a duration of 2 h. The linear viscoelastic properties of the transparent polyamide showed an exponential increase with time at 255 ºC under both oxidative and non-oxidative environments, suggesting an increase in molecular mass. At temperatures of 260, 270, and 275 ºC, a dual-stage time-dependent growth in viscoelastic properties was observed under an oxidative environment. Thermo-oxidative degradation of the polymer melts at 270 ºC occurs from the exposed edge of the sample, continuing inwards, effectively reducing the radius of the unoxidized polymer melt by 6.4% from its initial value of 12.5 mm. In the dual-stage growth, the first exponential growth is attributed to post-condensation with continuous desorption of water, followed by logistic oxidative degradation. Furthermore, a new methodology is presented to interpret and differentiate the rheological behavior of the bulk polymer melt from the oxidized segment present within the volume of the test sample.

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Data availability

The datasets generated during and/or analysed during the current study are available in the MaterialsCloud repository (Venoor et al. 2022).

Code availability

MATLAB code to conduct data smoothing and interpolation can be obtained from the corresponding author on reasonable request. Also, a code to analyze linear viscoelastic properties using the torque recordings obtained from the parallel plate rheometer is presented in the supplementary file.

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Acknowledgements

The authors would like to thank the Department of Plastic Engineering at the University of Massachusetts Lowell and the US Army Combat Capabilities Development Command Soldier Center for the partial funding, experimental facilities, and instruments. The plots for the article were created using a modified version of MATLAB open-source code (Habib). As shown in this article, a sample code to achieve the quality of plots can be provided upon request.

Funding

This research was funded jointly by the US Army Combat Capabilities Development Command Soldier Center (DEVCOM SC) and Harnessing Emerging Research Opportunities to Empower Soldiers (HEROES) Contract #W911QY-17–2-0004, Soldier Lightweight Integrated Multifunctional Materials (SLIMM) project title MN-1 New thermoplastic materials using microcrystalline cellulose, and the UMass President’s Office Technology and Commercial Ventures Fund.

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Authors and Affiliations

  1. Department of Plastic Engineering, University of Massachusetts Lowell, Lowell, MA, USA

    Varun Venoor, David O. Kazmer & Margaret J. Sobkowicz

  2. The Combat Capabilities Development Command Soldier Center, Natick, MA, USA

    Jo Ann Ratto

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  1. Varun Venoor
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  2. Jo Ann Ratto
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  3. David O. Kazmer
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  4. Margaret J. Sobkowicz
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Contributions

All authors contributed to the study conception. Material preparation and testing and data analysis were performed by Varun Venoor. The first draft of the manuscript was written by Varun Venoor, and all authors reviewed the previous version. The final version of the manuscript was reviewed and approved by all authors.

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Correspondence to Varun Venoor or Margaret J. Sobkowicz.

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The document has been screened and approved for release by G2 and PAO at the US Army Combat Capabilities Development Command Soldier Center, Natick, MA. The assigned number is PR2021_32660.

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Venoor, V., Ratto, J.A., Kazmer, D.O. et al. Analysis of post-condensation and thermo-oxidative degradation in cycloaliphatic polyamide through time-resolved rheology (TRR). Rheol Acta 61, 319–337 (2022). https://doi.org/10.1007/s00397-022-01327-2

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