Quiescent and flow-induced crystallization in polyamide 12/cellulose nanocrystal composites
[Display omitted] •Cellulose nanocrystals are efficient nucleating agents for PA12.•Fast scanning calorimetry of a sheared nanocomposite was evaluated.•Nanofiller nucleation dominates flow-induced nucleation.•AFM was used to characterize CNC dispersion and crystal microstructure.•Wide angle XRD was...
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| Published in | Thermochimica acta Vol. 677; pp. 99 - 108 |
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| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
Elsevier B.V
01.07.2019
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| Subjects | |
| Online Access | Get full text |
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| Abstract | [Display omitted]
•Cellulose nanocrystals are efficient nucleating agents for PA12.•Fast scanning calorimetry of a sheared nanocomposite was evaluated.•Nanofiller nucleation dominates flow-induced nucleation.•AFM was used to characterize CNC dispersion and crystal microstructure.•Wide angle XRD was used to characterize crystal polymorph.
Understanding the crystallization kinetics and microstructure that result after an imposed shear flow in an additive-containing polymeric system is imperative for the development of robust polymer composites suitable for advanced engineering applications. Both nucleating agents and flow accelerate the crystallization kinetics as well as alter the ultimate polymer microstructure. During melt processing, polymers are subject to shear flow prior to the solidification of the melt. As an unsheared baseline in this study, the addition of 5 wt % cellulose nanocrystals (CNC) into quiescent polyamide 12 (PA 12) revealed that CNCs act as a natural nucleating agent to the quiescent PA 12 during slow cooling and at high temperatures, as measured by standard differential scanning calorimetry. To evaluate the role of shear work in promoting flow-induced crystallization, both neat and PA 12/CNC composite were subjected to known amounts of shear work. Then fast scanning calorimetry was used to differentiate the nucleation activity from both flow-induced precursors and CNC particles during isothermal crystallization across a wide temperature range. It was found that the addition of the CNC accelerated crystallization in the heterogeneous nucleation regime (T > 100 °C) in the quiescent material. With the addition of shear, the neat system displayed a reduced crystallization peak time with increasing shear history. In the nanocomposite system, the CNCs are an extremely efficient nucleating agent, achieving a saturating limit for nucleation of crystallization, such that shear was only a factor at low supercooling, specifically at temperatures greater than 140 °C. |
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| AbstractList | Understanding the crystallization kinetics and microstructure that result after an imposed shear flow in an additive-containing polymeric system is imperative for the development of robust polymer composites suitable for advanced engineering applications. Both nucleating agents and flow accelerate the crystallization kinetics as well as alter the ultimate polymer microstructure. During melt processing, polymers are subject to shear flow prior to the solidification of the melt. As an unsheared baseline in this study, the addition of 5 wt % cellulose nanocrystals (CNC) into quiescent polyamide 12 (PA 12) revealed that CNCs act as a natural nucleating agent to the quiescent PA 12 during slow cooling and at high temperatures, as measured by standard differential scanning calorimetry. To evaluate the role of shear work in promoting flow-induced crystallization, both neat and PA 12/CNC composite were subjected to known amounts of shear work. Then fast scanning calorimetry was used to differentiate the nucleation activity from both flow-induced precursors and CNC particles during isothermal crystallization across a wide temperature range. It was found that the addition of the CNC accelerated crystallization in the heterogeneous nucleation regime (T > 100 °C) in the quiescent material. With the addition of shear, the neat system displayed a reduced crystallization peak time with increasing shear history. In the nanocomposite system, the CNCs are an extremely efficient nucleating agent, achieving a saturating limit for nucleation of crystallization, such that shear was only a factor at low supercooling, specifically at temperatures greater than 140 °C. [Display omitted] •Cellulose nanocrystals are efficient nucleating agents for PA12.•Fast scanning calorimetry of a sheared nanocomposite was evaluated.•Nanofiller nucleation dominates flow-induced nucleation.•AFM was used to characterize CNC dispersion and crystal microstructure.•Wide angle XRD was used to characterize crystal polymorph. Understanding the crystallization kinetics and microstructure that result after an imposed shear flow in an additive-containing polymeric system is imperative for the development of robust polymer composites suitable for advanced engineering applications. Both nucleating agents and flow accelerate the crystallization kinetics as well as alter the ultimate polymer microstructure. During melt processing, polymers are subject to shear flow prior to the solidification of the melt. As an unsheared baseline in this study, the addition of 5 wt % cellulose nanocrystals (CNC) into quiescent polyamide 12 (PA 12) revealed that CNCs act as a natural nucleating agent to the quiescent PA 12 during slow cooling and at high temperatures, as measured by standard differential scanning calorimetry. To evaluate the role of shear work in promoting flow-induced crystallization, both neat and PA 12/CNC composite were subjected to known amounts of shear work. Then fast scanning calorimetry was used to differentiate the nucleation activity from both flow-induced precursors and CNC particles during isothermal crystallization across a wide temperature range. It was found that the addition of the CNC accelerated crystallization in the heterogeneous nucleation regime (T > 100 °C) in the quiescent material. With the addition of shear, the neat system displayed a reduced crystallization peak time with increasing shear history. In the nanocomposite system, the CNCs are an extremely efficient nucleating agent, achieving a saturating limit for nucleation of crystallization, such that shear was only a factor at low supercooling, specifically at temperatures greater than 140 °C. |
| Author | Seo, Jiho Ferris, Trapper Venkatraman, Priya Foster, E. Johan Gohn, Anne M. Rhoades, Alicyn M. |
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•Cellulose nanocrystals are efficient nucleating agents for PA12.•Fast scanning calorimetry of a sheared nanocomposite was... Understanding the crystallization kinetics and microstructure that result after an imposed shear flow in an additive-containing polymeric system is imperative... |
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| SubjectTerms | cellulose Cellulose nanocrystal cooling Crystallization differential scanning calorimetry engineering Fast scanning chip calorimetry melting microstructure nanocomposites nanocrystals Polyamide 12 polyamides solidification supercooling temperature |
| Title | Quiescent and flow-induced crystallization in polyamide 12/cellulose nanocrystal composites |
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