Electrospinning of Aqueous Solutions of Atactic Poly(N-isopropylacrylamide) with Physical Gelation
Abstract
:1. Introduction
2. Results and Discussion
2.1. Determination of Binodal Temperature and Entanglement Concentration
2.2. Determination of Gel Point (Tgel)
2.3. Proposed Mechanism of the Formation of a Gel Junction (Coupled Pearls)
2.4. Electrospinning of a-PNIPAM/H2O Solutions at 10 °C
2.4.1. Concentration Effect
2.4.2. Flow Rate Effect
2.5. Electrospinning of a-PNIPAM/H2O Solution at Different Temperatures
3. Conclusions
4. Materials and Methods
4.1. Solution Preparation and Properties
4.2. Electrospinning and Fiber Morphology
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Acknowledgments
Conflicts of Interest
References
- Reneker, D.H.; Fong, H. (Eds.) Polymeric Nanofibers; ACS Symposium Series 918; American Chemical Society: Washington, DC, USA, 2006. [Google Scholar]
- Greiner, A.; Wendorff, J.H. Electrospinning: A fascinating method for the preparation of ultrathin fibres. Angew. Chem. Int. Ed. 2007, 46, 5670–5703. [Google Scholar] [CrossRef] [PubMed]
- Xue, J.; Wu, T.; Dai, Y.; Xia, Y. Electrospinning and Electrospun Nanofibers: Methods, Materials, and Applications. Chem. Rev. 2019, 119, 5298–5415. [Google Scholar] [CrossRef] [PubMed]
- Reneker, D.H.; Yarin, A.L.; Fong, H.; Koombhongse, S. Bending instability of electrically charged liquid jets of polymer solutions in electrospinning. J. Appl. Phys. 2000, 87, 4531–4547. [Google Scholar] [CrossRef] [Green Version]
- McKee, M.G.; Wilkes, G.L.; Colby, R.H.; Long, T.E. Correlations of solution rheology with electrospun fiber formation of linear and branched polyesters. Macromolecules 2004, 37, 1760–1767. [Google Scholar] [CrossRef]
- Wang, C.; Hsu, C.-H.; Lin, J.-H.; Wang, I.-C. Scaling laws in electrospinning of polystyrene solutions. Macromolecules 2006, 39, 7662–7672. [Google Scholar] [CrossRef]
- Rockwood, N.; Chase, D.B.; Akins, R.E., Jr.; Rabolt, J.F. Characterization of electrospun poly(N-isopropyl acrylamdie) fibers. Polymer 2008, 49, 4025–4032. [Google Scholar] [CrossRef]
- Schoolaert, E.; Ryckx, P.; Geltmeyer, J.; Maji, S.; Van Steenberge, P.H.M.; D’hooge, D.R.; Hoogenboom, R.; De Clerck, K. Waterbone electrospinning of poly(N-isopropylacrylamide) by control of environmental parameters. ACS Appl. Mater. Interfaces 2017, 9, 24100–24110. [Google Scholar] [CrossRef] [Green Version]
- Koombhongse, S.; Liu, W.; Reneker, D.H. Flat polymer ribbons and other shapes by electrospinning. J. Polym. Sci. Polym. Phys. Ed. 2001, 39, 2598–2606. [Google Scholar] [CrossRef]
- Wang, C.; Hashimoto, T.; Wang, Y.; Lai, H.-Y.; Kuo, C.-H. Formation of dissipative structures in the straight segment of electrospinning jets. Macromolecules 2020, 53, 7876–7886. [Google Scholar] [CrossRef]
- Yoshida, R.; Sakai, K.; Okano, T.; Sakurai, Y. Pulsatile drug delivery systems using hydrogels. Adv. Drug Deliv. Rev. 1993, 11, 85–108. [Google Scholar] [CrossRef]
- Yamato, M.; Akiyama, Y.; Kobayashi, J.; Yang, J.; Kikuchi1, A.; Okano, T. Temperature-responsive cell culture surfaces for regenerative medicine with cell sheet engineering. Prog. Polym. Sci. 2007, 32, 1123–1133. [Google Scholar] [CrossRef]
- Heskins, M.; Guillet, J.E. Solution properties of poly(N-isopropylacrylamide). J. Macromol. Sci. Chem. 1968, 2, 1441–1455. [Google Scholar] [CrossRef]
- Halperin, A.; Kröger, M.; Winnik, F.M. Poly(N-isopropylacrylamide) phase diagrams: Fifty years of research. Angew. Chem. Int. Ed. 2015, 54, 15342–15367. [Google Scholar] [CrossRef] [PubMed]
- Schild, H.G. Poly(N-isopropylacrylamide): Experiment, theory and application. Prog. Polym. Sci. 1992, 17, 163–249. [Google Scholar] [CrossRef]
- Okada, Y.; Tanaka, F. Cooperative hydration, chain collapse, and flat LCST behavior in aqueous poly(N-isopropylacrylamide) solutions. Macromolecules 2005, 38, 4465–4471. [Google Scholar] [CrossRef]
- Tong, Z.; Zeng, F.; Zheng, X.; Sato, T. Inverse molecular weight dependence of cloud points for aqueous poly(N-isopropylacrylamide) solutions. Macromolecules 1999, 32, 4488–4490. [Google Scholar] [CrossRef]
- Gomes de Azevedo, R.; Rebelo, L.P.N.; Ramos, A.M.; Szydlowski, J.; de Sousa, H.C.; Klein, J. Phase behavior of (polyacrylamides + water) solutions: Concentration, pressure and isotope effects. Fluids Phase Equilib. 2001, 185, 189–198. [Google Scholar] [CrossRef] [Green Version]
- Shibayama, M.; Suetoh, Y.; Nomura, S. Structure relaxation of hydrophobically aggregated poly(N-isopropylacrylamide) in water. Macromolecules 1996, 29, 6966–6968. [Google Scholar] [CrossRef]
- Hamamura, K.; Watanabe, K.; Sanada, Y.; Tanaka, F.; Kastsumoto, Y. Relationship between the phase diagram and hysteresis in demixing and remixing for atactic and meso-rich poly(N-isopropylacrylamide)s in water. Polymer 2019, 161, 92–100. [Google Scholar] [CrossRef]
- Kogo, T.; Shundo, A.; Wang, C.; Tanaka, K. Spatial heterogeneity accompanying gel formation of poly(N-isopropylacrylamide) aqueous solution at a temperature below cloud point. Macromolecules 2020, 53, 10964–10971. [Google Scholar] [CrossRef]
- Han, J.; Takahashi, R.; Kuang, C.; Sato, T. Phase separation behavior of aqueous poly(N-isopropylacrylamide) solutions studied by scattering experiments. Langmuir 2022, 38, 5089–5097. [Google Scholar] [CrossRef] [PubMed]
- Ishihara, H.; Ikemoto, R.; Yamamoto, M.; Sanada, Y.; Watanabe, K.; Katsumoto, Y. Phase-separated nanodroplets formed below the cloud point for the aqueous solution of stereo-controlled poly(N-isopropylacrylamide). Langmuir 2022, 38, 12300–12306. [Google Scholar] [CrossRef] [PubMed]
- Niebuur, B.-J.; Chiappisi, L.; Jung, F.; Zhang, X.; Schulte, A.; Papadakis, C.M. Kinetics of mesoglobule formation and growth in aqueous poly(N-isopropylacrylamide) solutions: Pressure jumps at low and at high pressure. Macromolecules 2019, 52, 6416–6427. [Google Scholar] [CrossRef] [Green Version]
- Ko, C.-H.; Claude, K.-L.; Niebuur, B.-J.; Jung, F.A.; Kang, J.-J.; Schanzenbach, D.; Frielinghaus, H.; Barnsley, L.C.; Wu, B.; Pipich, V.; et al. Temperature-dependent phase behavior of the thermoresponsive polmer poly(N-isopropylmethacrylamide) in an aqueous solution. Macromolecules 2020, 53, 6816–6827. [Google Scholar] [CrossRef]
- Ono, Y.; Shikata, T. Hydration and dynamic behavior of poly(N-isopropylacrylamide)s in aqueous solution: A sharp phase transition at the lower critical solution temperature. J. Am. Chem. Soc. 2006, 128, 10030–10031. [Google Scholar] [CrossRef]
- Kubota, K.; Fujishige, S.; Ando, I. Solution properties of poly(N-isopropylacrylamide) in water. Polym. J. 1990, 22, 15–20. [Google Scholar] [CrossRef] [Green Version]
- Inomata, H.; Yagi, Y.; Otake, K.; Konno, M.; Saito, S. Spinodal decomposition of an aqueous solution of poly(N-isopropylacrylamide). Macromolecules 1989, 22, 3494–3495. [Google Scholar] [CrossRef]
- Shibayama, M.; Tanaka, T.; Han, C.C. Small angle neutron scattering study on poly(N-isopropyl acrylamide) gels near their volume-phase transition temperature. J. Chem. Phys. 1992, 97, 6829–6841. [Google Scholar] [CrossRef]
- Kujawa, P.; Winnik, F.M. Volumetric studies of aqueous polymer solutions using pressure perturbation calorimetry: A new look at the temperature-induced phase transition of poly(N-isopropylacrylamide) in water and D2O. Macromolecules 2001, 34, 4130–4135. [Google Scholar] [CrossRef]
- Yanase, K.; Buchner, R.; Sato, T. Microglobule formation and a microscopic order parameter monitoring the phase transition of aqueous poly(N-isopropylacrylamide) solution. Phys. Rev. Mater. 2018, 2, 085601. [Google Scholar] [CrossRef]
- Osváth, Z.; Iván, B. The dependence of the cloud point, clearing point, and hysteresis of poly(N-isopropylacrylamide) on experimental conditions: The need for standardization of thermoresponsive transition determinations. Macromol. Chem. Phys. 2017, 218, 1600407. [Google Scholar] [CrossRef] [Green Version]
- Zheng, X.; Tong, Z.; Xie, X.; Zeng, F. Phase separation in poly(N-isopropyl acrylamide)/water solutions I. cloud point curves and microgelation. Polym. J. 1998, 30, 284–288. [Google Scholar] [CrossRef] [Green Version]
- Nakao, S.; Ogiso, T.; Kita, R.; Shinyashiki, N.; Yagihara, S.; Yoneyama, M.; Katsumoto, Y. Thermoreversible gelation of isotactic-rich poly(N-isopropylacrylamide) in water. J. Chem. Phys. 2011, 135, 114903. [Google Scholar] [CrossRef] [PubMed]
- Choi, J.H.; Ko, S.-W.; Kim, B.C.; Blackwell, J.; Lyoo, W.S. Phase behavior and physical gelation of high molecular weight syndiotactic poly(vinyl alcohol) solution. Macromolecules 2001, 34, 2964–2972. [Google Scholar] [CrossRef]
- Winter, H.H.; Mours, M. Rheology of polymers near liquid-solid transitions. Adv. Polym. Sci. 1997, 34, 165–234. [Google Scholar]
- Ajji, A.; Choplin, L. Rheology and dynamics near phase separation in a polymer blend: Model and scaling analysis. Macromolecules 1991, 24, 5221–5223. [Google Scholar] [CrossRef]
- Wang, C.; Hashimoto, T.; Chuang, Y.-C.; Tanaka, K.; Chang, Y.-P.; Yang, T.-W.; Huang, M.-T. Physical gelation of aqueous solutions of atactic poly(N-isopropylacrylamide). Macromolecules 2022, 55, 9152–9167. [Google Scholar] [CrossRef]
- Wang, C.; Hashimoto, T. A scenario of a fiber formation mechanism in electrospinning: Jet evolves assemblies of phase-separated strings that eventually split into as-spun fibers observed on the grounded collector. Macromolecules 2020, 53, 9584–9600. [Google Scholar] [CrossRef]
- Wang, C.; Hashimoto, T.; Wang, Y. Extension rate and bending instability of electrospinning jet: The role of electric field. Macromolecules 2021, 54, 7193–7209. [Google Scholar] [CrossRef]
- Wang, C.; Cheng, Y.-W.; Hsu, C.-H.; Chien, H.-S.; Tsou, S.-Y. How to manipulate the electrospinning jet with controlled properties to obtain uniform fibers with the smallest diameter?—A brief discussion of solution electrospinning process. J. Polym. Res. 2011, 18, 111–123. [Google Scholar] [CrossRef]
- Winter, H.H.; Chambon, F. Analysis of linear viscoelasticity of a crosslinking polymer at the gel point. J. Rheol. 1986, 30, 367–382. [Google Scholar] [CrossRef]
- Mours, M.; Winter, H.H. Relaxation patterns of nearly critical gels. Macromolecules 1996, 29, 7221–7229. [Google Scholar] [CrossRef] [Green Version]
- Venkataraman, S.K.; Winter, H.H. Finite shear strain behavior of a crosslinking polydimethylsiloxane near its gel point. Rheol. Acta 1990, 29, 423–432. [Google Scholar] [CrossRef]
- Joshi, N.; Suman, K.; Joshi, Y.M. Rheological behavior of aqueous poly(vinyl alcohol) solution during a free-thaw gelation process. Macromolecules 2020, 53, 3452–3463. [Google Scholar] [CrossRef]
- Kujawa, P.; Watanabe, H.; Tanaka, F.; Winnik, F.M. Amphiphilic telechelic poly(N-isopropylacrylamide) in water: From micelles to gels. Eur. Phy. J. E 2005, 17, 129–137. [Google Scholar] [CrossRef]
- Grosskopf, A.K.; Mann, J.L.; Baillet, J.; Hernandez, H.L.; Autzen, A.A.A.; Yu, A.C.; Appel, E.A. Extreme extensibility in physically cross-linked nanocomposite hyfdrogels leveraging dynamic polymer-nanparticle interactions. Macromolecules 2022, 55, 7498–7511. [Google Scholar] [CrossRef]
- Ahmed, Z.; Gooding, E.A.; Pimenov, K.V.; Wang, L.; Asher, S.A. UV resonance Raman determination of molecular mechanism of poly(N-isopropylacrylamide) volume phase transition. J. Phys. Chem. B 2009, 113, 4248–4256. [Google Scholar] [CrossRef]
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Chuang, Y.-C.; Chang, Y.-C.; Tsai, M.-T.; Yang, T.-W.; Huang, M.-T.; Wu, S.-H.; Wang, C. Electrospinning of Aqueous Solutions of Atactic Poly(N-isopropylacrylamide) with Physical Gelation. Gels 2022, 8, 716. https://doi.org/10.3390/gels8110716
Chuang Y-C, Chang Y-C, Tsai M-T, Yang T-W, Huang M-T, Wu S-H, Wang C. Electrospinning of Aqueous Solutions of Atactic Poly(N-isopropylacrylamide) with Physical Gelation. Gels. 2022; 8(11):716. https://doi.org/10.3390/gels8110716
Chicago/Turabian StyleChuang, Ya-Chen, Yu-Chia Chang, Meng-Tzu Tsai, Ting-Wei Yang, Meng-Tse Huang, Shao-Hua Wu, and Chi Wang. 2022. "Electrospinning of Aqueous Solutions of Atactic Poly(N-isopropylacrylamide) with Physical Gelation" Gels 8, no. 11: 716. https://doi.org/10.3390/gels8110716