In-Out Surface Modification of Halloysite Nanotubes (HNTs) for <i>Excellent</i> Cure of Epoxy: Chemistry and Kinetics Modeling
In-out surface modification of halloysite nanotubes (HNTs) has been successfully performed by taking advantage of 8-hydroxyquinolines in the lumen of HNTs and precisely synthesized aniline oligomers (AO) of different lengths (tri- and pentamer) anchored on the external surface of the HNTs. Several a...
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| Format: | Article |
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MDPI AG
2021-11-01
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| Series: | Nanomaterials |
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| Online Access: | https://www.mdpi.com/2079-4991/11/11/3078 |
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| author | Shahab Moghari Seyed Hassan Jafari Mohsen Khodadadi Yazdi Maryam Jouyandeh Aleksander Hejna Payam Zarrintaj Mohammad Reza Saeb |
| author_facet | Shahab Moghari Seyed Hassan Jafari Mohsen Khodadadi Yazdi Maryam Jouyandeh Aleksander Hejna Payam Zarrintaj Mohammad Reza Saeb |
| author_sort | Shahab Moghari |
| collection | DOAJ |
| description | In-out surface modification of halloysite nanotubes (HNTs) has been successfully performed by taking advantage of 8-hydroxyquinolines in the lumen of HNTs and precisely synthesized aniline oligomers (AO) of different lengths (tri- and pentamer) anchored on the external surface of the HNTs. Several analyses, including FTIR, H-NMR, TGA, UV-visible spectroscopy, and SEM, were used to establish the nature of the HNTs’ surface engineering. Nanoparticles were incorporated into epoxy resin at 0.1 wt.% loading for investigation of the contribution of surface chemistry to epoxy cure behavior and kinetics. Nonisothermal differential scanning calorimetry (DSC) data were fed into home-written MATLAB codes, and isoconversional approaches were used to determine the apparent activation energy (<i>E<sub>α</sub></i>) as a function of the extent of cure reaction (α). Compared to pristine HNTs, AO-HNTs facilitated the densification of an epoxy network. Pentamer AO-HNTs with longer arms promoted an <i>Excellent</i> cure; with an <i>E<sub>α</sub></i> value that was 14% lower in the presence of this additive than for neat epoxy, demonstrating an enhanced cross-linking. The model also predicted a triplet of cure (<i>m</i>, <i>n</i>, and ln <i>A</i>) for autocatalytic reaction order, non-catalytic reaction order, and pre-exponential factor, respectively, by the Arrhenius equation. The enhanced autocatalytic reaction in AO-HNTs/epoxy was reflected in a significant rise in the value of <i>m,</i> from 0.11 to 0.28. Kinetic models reliably predict the cure footprint suggested by DSC measurements. |
| first_indexed | 2024-03-10T05:13:01Z |
| format | Article |
| id | doaj.art-8dc61182416640d9a20778a62f8c73bc |
| institution | Directory Open Access Journal |
| issn | 2079-4991 |
| language | English |
| last_indexed | 2024-03-10T05:13:01Z |
| publishDate | 2021-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Nanomaterials |
| spelling | doaj.art-8dc61182416640d9a20778a62f8c73bc2023-11-23T00:42:51ZengMDPI AGNanomaterials2079-49912021-11-011111307810.3390/nano11113078In-Out Surface Modification of Halloysite Nanotubes (HNTs) for <i>Excellent</i> Cure of Epoxy: Chemistry and Kinetics ModelingShahab Moghari0Seyed Hassan Jafari1Mohsen Khodadadi Yazdi2Maryam Jouyandeh3Aleksander Hejna4Payam Zarrintaj5Mohammad Reza Saeb6School of Chemical Engineering, College of Engineering, University of Tehran, Tehran 11155-4563, IranSchool of Chemical Engineering, College of Engineering, University of Tehran, Tehran 11155-4563, IranCenter of Excellence in Electrochemistry, School of Chemistry, College of Science, University of Tehran, Tehran 141746-6191, IranCenter of Excellence in Electrochemistry, School of Chemistry, College of Science, University of Tehran, Tehran 141746-6191, IranDepartment of Polymer Technology, Gdańsk University of Technology, Narutowicza, 11/12, 80-233 Gdańsk, PolandSchool of Chemical Engineering, Oklahoma State University, 420 Engineering North, Stillwater, OK 74078, USADepartment of Polymer Technology, Gdańsk University of Technology, Narutowicza, 11/12, 80-233 Gdańsk, PolandIn-out surface modification of halloysite nanotubes (HNTs) has been successfully performed by taking advantage of 8-hydroxyquinolines in the lumen of HNTs and precisely synthesized aniline oligomers (AO) of different lengths (tri- and pentamer) anchored on the external surface of the HNTs. Several analyses, including FTIR, H-NMR, TGA, UV-visible spectroscopy, and SEM, were used to establish the nature of the HNTs’ surface engineering. Nanoparticles were incorporated into epoxy resin at 0.1 wt.% loading for investigation of the contribution of surface chemistry to epoxy cure behavior and kinetics. Nonisothermal differential scanning calorimetry (DSC) data were fed into home-written MATLAB codes, and isoconversional approaches were used to determine the apparent activation energy (<i>E<sub>α</sub></i>) as a function of the extent of cure reaction (α). Compared to pristine HNTs, AO-HNTs facilitated the densification of an epoxy network. Pentamer AO-HNTs with longer arms promoted an <i>Excellent</i> cure; with an <i>E<sub>α</sub></i> value that was 14% lower in the presence of this additive than for neat epoxy, demonstrating an enhanced cross-linking. The model also predicted a triplet of cure (<i>m</i>, <i>n</i>, and ln <i>A</i>) for autocatalytic reaction order, non-catalytic reaction order, and pre-exponential factor, respectively, by the Arrhenius equation. The enhanced autocatalytic reaction in AO-HNTs/epoxy was reflected in a significant rise in the value of <i>m,</i> from 0.11 to 0.28. Kinetic models reliably predict the cure footprint suggested by DSC measurements.https://www.mdpi.com/2079-4991/11/11/3078epoxy nanocompositecure kineticsanilineisoconversional methodsHNT |
| spellingShingle | Shahab Moghari Seyed Hassan Jafari Mohsen Khodadadi Yazdi Maryam Jouyandeh Aleksander Hejna Payam Zarrintaj Mohammad Reza Saeb In-Out Surface Modification of Halloysite Nanotubes (HNTs) for <i>Excellent</i> Cure of Epoxy: Chemistry and Kinetics Modeling Nanomaterials epoxy nanocomposite cure kinetics aniline isoconversional methods HNT |
| title | In-Out Surface Modification of Halloysite Nanotubes (HNTs) for <i>Excellent</i> Cure of Epoxy: Chemistry and Kinetics Modeling |
| title_full | In-Out Surface Modification of Halloysite Nanotubes (HNTs) for <i>Excellent</i> Cure of Epoxy: Chemistry and Kinetics Modeling |
| title_fullStr | In-Out Surface Modification of Halloysite Nanotubes (HNTs) for <i>Excellent</i> Cure of Epoxy: Chemistry and Kinetics Modeling |
| title_full_unstemmed | In-Out Surface Modification of Halloysite Nanotubes (HNTs) for <i>Excellent</i> Cure of Epoxy: Chemistry and Kinetics Modeling |
| title_short | In-Out Surface Modification of Halloysite Nanotubes (HNTs) for <i>Excellent</i> Cure of Epoxy: Chemistry and Kinetics Modeling |
| title_sort | in out surface modification of halloysite nanotubes hnts for i excellent i cure of epoxy chemistry and kinetics modeling |
| topic | epoxy nanocomposite cure kinetics aniline isoconversional methods HNT |
| url | https://www.mdpi.com/2079-4991/11/11/3078 |
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