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Keywords = polyurethane/CNC nanocomposites

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17 pages, 6635 KB  
Article
In Situ Synthesis of Environmentally Friendly Waterborne Polyurethane Extended with Regenerated Cellulose Nanoparticles for Enhanced Mechanical Performances
by Soon Mo Choi, Soo Young Lee, Sunhee Lee, Sung Soo Han and Eun Joo Shin
Polymers 2023, 15(6), 1541; https://doi.org/10.3390/polym15061541 - 20 Mar 2023
Cited by 6 | Viewed by 2743
Abstract
The development of waterborne polyurethane (WPU) has been stimulated as an alternative to solvent-based polyurethanes due to low-VOC alternatives and reduced exposure to solvents. However, their relatively low mechanical performance and degradation have presented challenges in their wide application. Here, we developed environmentally-friendly [...] Read more.
The development of waterborne polyurethane (WPU) has been stimulated as an alternative to solvent-based polyurethanes due to low-VOC alternatives and reduced exposure to solvents. However, their relatively low mechanical performance and degradation have presented challenges in their wide application. Here, we developed environmentally-friendly bio polyol-based WPU nanocomposite dispersions and films, and presented the optimal process conditions for their manufacture. Additionally, the condition was established without using harmful catalysts or ethyl methyl ketone (MEK) during the polymerization. Moreover, regenerated cellulose nanoparticles (RCNs) were employed as natural chain-extenders in order to improve the biodegradability and mechanical performances of the nanocomposite films. The RCNs have a lower crystallinity compared to cellulose nanocrystals (CNCs), allowing them to possess high toughness without interfering with the elastomeric properties of polyurethane. The prepared CWPU/RCNs nanocomposite films exhibited high toughness of 58.8 ± 3 kgf∙mm and elongation at break of 240 ± 20%. In addition, depending on the molar ratio of NCO/OH, the polyurethane particle size is variously controlled from 70 to 230 nm, enabling to fabricate their dispersions with various transmittances. We believe that our findings not only open a meaningful path toward green elastomers with biodegradability but provides the design concept for bio-elastomers in order to develop industrial elastomers with mechanical and thermal properties. Full article
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15 pages, 51753 KB  
Article
Fabrication of Silane-Grafted Cellulose Nanocrystals and Their Effects on the Structural, Thermal, Mechanical, and Hysteretic Behavior of Thermoplastic Polyurethane
by Xuenan Sun, Xinze Yang, Jiajing Zhang, Bin Shang, Pei Lyu, Chunhua Zhang, Xin Liu and Liangjun Xia
Int. J. Mol. Sci. 2023, 24(5), 5036; https://doi.org/10.3390/ijms24055036 - 6 Mar 2023
Cited by 11 | Viewed by 3104
Abstract
Reinforcement of polymer nanocomposites can be achieved by the selection of the appropriate fabrication method, surface modification, and orientation of the filler. Herein, we present a nonsolvent-induced phase separation method with ternary solvents to prepare thermoplastic polyurethane (TPU) composite films with excellent mechanical [...] Read more.
Reinforcement of polymer nanocomposites can be achieved by the selection of the appropriate fabrication method, surface modification, and orientation of the filler. Herein, we present a nonsolvent-induced phase separation method with ternary solvents to prepare thermoplastic polyurethane (TPU) composite films with excellent mechanical properties using 3-Glycidyloxypropyltrimethoxysilane-modified cellulose nanocrystals (GLCNCs). ATR-IR and SEM analyses of the GLCNCs confirmed that GL was successfully coated on the surface of the nanocrystals. The incorporation of GLCNCs in TPU resulted in the enhancement of the tensile strain and toughness of pure TPU owing to the enhanced interfacial interactions between them. The GLCNC–TPU composite film had tensile strain and toughness values of 1740.42% and 90.01 MJ/m3, respectively. Additionally, GLCNC–TPU exhibited a good elastic recovery rate. CNCs were readily aligned along the fiber axis after the spinning and drawing of the composites into fibers, which further improved the mechanical properties of the composites. The stress, strain, and toughness of the GLCNC–TPU composite fiber increased by 72.60%, 10.25%, and 103.61%, respectively, compared to those of the pure TPU film. This study demonstrates a facile and effective strategy for fabricating mechanically enhanced TPU composites. Full article
(This article belongs to the Special Issue Recent Advances in Cellulose Chemistry)
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15 pages, 3876 KB  
Article
Novel Cellulose Nanocrystals-Based Polyurethane: Synthesis, Characterization and Antibacterial Activity
by Maolan Zhang, Xiujuan Lu, Guiping Zhang, Xiaoling Liao, Jiale Wang, Na Zhang, Chunyi Yu and Guoming Zeng
Polymers 2022, 14(11), 2197; https://doi.org/10.3390/polym14112197 - 28 May 2022
Cited by 5 | Viewed by 2654
Abstract
As a new type of polymer, water-driven polyurethane (PU) has attracted increasing attention of researchers; however, with the popularization of its application, the following infection problems limit their applications, especially in the biomedical field. Herein, a series of novel cellulose nanocrystals (CNCs)-based PUs [...] Read more.
As a new type of polymer, water-driven polyurethane (PU) has attracted increasing attention of researchers; however, with the popularization of its application, the following infection problems limit their applications, especially in the biomedical field. Herein, a series of novel cellulose nanocrystals (CNCs)-based PUs were first synthesized by chemical cross-linking CNCs with triblock copolymer polylactide–poly (ethylene glycol)–polylactide (CNC-PU). After covalent binding with tannic acid (TA-CNC-PU), the silver nanoparticles (Ag NPs) were further introduced into the material by a reduction reaction (Ag/TA-CNC-PU). Finally, the prepared serial CNCs-based PU nanocomposites were fully characterized, including the microstructure, water contact angle, water uptake, thermal properties as well as antibacterial activity. Compared with CNC-PU, the obtained TA-CNC-PU and Ag/TA-CNC-PU were capable of lower glass transition temperatures and improved thermal stability. In addition, we found that the introduction of tannic acid and Ag NPs clearly increased the material hydrophobicity and antibacterial activity. In particular, the Ag/TA-CNC-PU had a better antibacterial effect on E. coli, while TA-CNC-PU had better inhibitory effect on S. aureus over a 24 h time period. Therefore, these novel CNCs-based PUs may be more beneficial for thermal processing and could potentially be developed into a new class of smart biomaterial material with good antibacterial properties by adjusting the ratio of TA or Ag NPs in their structures. Full article
(This article belongs to the Section Polymer Composites and Nanocomposites)
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16 pages, 2491 KB  
Article
High-Performance Polyurethane Nanocomposite Membranes Containing Cellulose Nanocrystals for Protein Separation
by Víctor-Hugo Antolín-Cerón, Francisco-Jesús González-López, Pablo Daniel Astudillo-Sánchez, Karla-Alejandra Barrera-Rivera and Antonio Martínez-Richa
Polymers 2022, 14(4), 831; https://doi.org/10.3390/polym14040831 - 21 Feb 2022
Cited by 21 | Viewed by 3454
Abstract
With the aim of exploring new materials and properties, we report the synthesis of a thermoplastic chain extended polyurethane membrane, with superior strength and toughness, obtained by incorporating two different concentrations of reactive cellulose nanocrystals (CNC) for potential use in kidney dialysis. Membrane [...] Read more.
With the aim of exploring new materials and properties, we report the synthesis of a thermoplastic chain extended polyurethane membrane, with superior strength and toughness, obtained by incorporating two different concentrations of reactive cellulose nanocrystals (CNC) for potential use in kidney dialysis. Membrane nanocomposites were prepared by the phase inversion method and their structure and properties were determined. These materials were prepared from a polyurethane (PU) yielded from poly(1,4 butylene adipate) as a soft segment diol, isophorone diisocyanate (IPDI) and hexamethylenediamine (HMDA) as isocyanate and chain extender, respectively (hard segment), filled with 1 or 2% w/w CNC. Membrane preparation was made by the phase inversion method using N,N-dimethylformamide as solvent and water as nonsolvent, and subjected to dead-end microfiltration. Membranes were evaluated by their pure water flux, water content, hydraulic resistance and protein rejection. Polymers and nanocomposites were characterized by scanning electronic and optical microscopy, differential scanning calorimetry, infrared spectroscopy, strain stress testing and 13C solid state nuclear magnetic resonance. The most remarkable effects observed by the addition of CNCs are (i) a substantial increment in Young’s modulus to twenty-two times compared with the neat PU and (ii) a marked increase in pure water flux up to sixty times, for sample containing 1% (w/w) of CNC. We found that nanofiller has a strong affinity to soft segment diol, which crystallizes in the presence of CNCs, developing both superior mechanical and pure water flow properties, compared to neat PU. The presence of nanofiller also modifies PU intermolecular interactions and consequently the nature of membrane pores. Full article
(This article belongs to the Special Issue High Performance Polymer Membranes)
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13 pages, 53941 KB  
Article
Electrospinning of Cellulose Nanocrystal-Reinforced Polyurethane Fibrous Mats
by Alexandre Redondo, Daseul Jang, LaShanda T. J. Korley, Ilja Gunkel and Ullrich Steiner
Polymers 2020, 12(5), 1021; https://doi.org/10.3390/polym12051021 - 1 May 2020
Cited by 19 | Viewed by 5416
Abstract
We report the electrospinning of mechanically-tunable, cellulose nanocrystal (CNC)-reinforced polyurethanes (PUs). Using high-aspect ratio CNCs from tunicates, the stiffness and strength of electrospun PU/CNC mats are shown to generally increase. Furthermore, by tuning the electrospinning conditions, fibrous PU/CNC mats were created with either [...] Read more.
We report the electrospinning of mechanically-tunable, cellulose nanocrystal (CNC)-reinforced polyurethanes (PUs). Using high-aspect ratio CNCs from tunicates, the stiffness and strength of electrospun PU/CNC mats are shown to generally increase. Furthermore, by tuning the electrospinning conditions, fibrous PU/CNC mats were created with either aligned or non-aligned fibers, as confirmed by scanning electron microscopy. PU/CNC mats having fibers aligned in the strain direction were stiffer and stronger compared to mats containing non-aligned fibers. Interestingly, fiber alignment was accompanied by an anisotropic orientation of the CNCs, as confirmed by wide-angle X-ray scattering, implying their alignment additionally benefits both stiffness and strength of fibrous PU/CNC nanocomposite mats. These findings suggest that CNC alignment could serve as an additional reinforcement mechanism in the design of stronger fibrous nanocomposite mats. Full article
(This article belongs to the Special Issue Electrospinning of Biopolymer Nanofibers)
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17 pages, 4721 KB  
Article
Melt-Spun Nanocomposite Fibers Reinforced with Aligned Tunicate Nanocrystals
by Alexandre Redondo, Sourav Chatterjee, Pierre Brodard, LaShanda T. J. Korley, Christoph Weder, Ilja Gunkel and Ullrich Steiner
Polymers 2019, 11(12), 1912; https://doi.org/10.3390/polym11121912 - 20 Nov 2019
Cited by 19 | Viewed by 6261
Abstract
The fabrication of nanocomposite films and fibers based on cellulose nanocrystals (P-tCNCs) and a thermoplastic polyurethane (PU) elastomer is reported. High-aspect-ratio P-tCNCs were isolated from tunicates using phosphoric acid hydrolysis, which is a process that affords nanocrystals displaying high thermal stability. Nanocomposites were [...] Read more.
The fabrication of nanocomposite films and fibers based on cellulose nanocrystals (P-tCNCs) and a thermoplastic polyurethane (PU) elastomer is reported. High-aspect-ratio P-tCNCs were isolated from tunicates using phosphoric acid hydrolysis, which is a process that affords nanocrystals displaying high thermal stability. Nanocomposites were produced by solvent casting (films) or melt-mixing in a twin-screw extruder and subsequent melt-spinning (fibers). The processing protocols were found to affect the orientation of both PU hard segments and the P-tCNCs within the PU matrix and therefore the mechanical properties. While the films were isotropic, both the polymer matrix and the P-tCNCs proved to be aligned along the fiber direction in the fibers, as shown using SAXS/WAXS, angle-dependent Raman spectroscopy, and birefringence analysis. Tensile tests reveal that fibers and films, at similar P-tCNC contents, display Young’s moduli and strain-at-break that are within the same order of magnitude, but the stress-at-break was found to be ten-times higher for fibers, conferring them a superior toughness over films. Full article
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