Flexible and biocompatible poly (vinyl alcohol)/multi-walled carbon nanotubes hydrogels with epsilon-near-zero properties

doi:10.1016/j.jmst.2022.05.019

Abstract

Abstract:

Epsilon-near-zero (ENZ) material has been a research hotspot in recent years due to unique physical properties such as inverse Doppler effect and negative refractive index, showing great potentials in the fields of flexible electronics, wearable devices, sensors, etc. The ENZ materials are mostly reported at visible, infrared and terahertz wavelengths, while the report about ENZ materials at radio frequency is rare. In this work, flexible and biocompatible poly (vinyl alcohol)/multi-walled carbon nanotubes (PVA/MWCNTs) hydrogels, which were successfully fabricated by an environmentally friendly method, were used as ENZ materials at radio frequency for the first time. Cytotoxicity experiments proved that the experimental process and products are green, environmentally friendly and biocompatible. The microstructure, crystalline structure, chemical composition and dielectric properties were investigated. Two different water states, which were free water molecules and bound water molecules, coexisted in these PVA/MWCNTs hydrogels and accounted for about 37.5 wt% and 15.9 wt% respectively by analyzing the thermogravimetric analysis curves. When the MWCNTs content reached 12 wt% and 15 wt%, the continuous conductive MWCNTs network was formed in the hydrogel, and ENZ phenomenon was observed at about 760 kHz and 580 kHz respectively, which was attributed to the interband transition. Considering the flexibility and non-toxicity of PVA/MWCNTs hydrogels, the ENZ properties of this structure at the radio frequency can be well used in wearable invisibility cloak, flexible electronics, skin sensors and other wearable devices.

Key words: Epsilon-near-zero, Hydrogels, Biocompatibility, Negative permittivity

Jiahong Tian, Runhua Fan, Zheng Zhang, Yang Li, Haikun Wu, Pengtao Yang, Peitao Xie, Wenxin Duan, Chun-Sing Lee. Flexible and biocompatible poly (vinyl alcohol)/multi-walled carbon nanotubes hydrogels with epsilon-near-zero properties[J]. J. Mater. Sci. Technol., 2022, 131: 91-99.

Figures/Tables 10

Fig. 1. Process of fabricating PVA/MWCNTs hydrogels.

Fig. 2. (a) Photograph of PVA/MWCNTs hydrogel with MWCNTs content of 15 wt%. The SEM images of pure PVA hydrogel (b) and PVA/MWCNTs hydrogels with MWCNTs content of 3 wt% (c), 6 wt% (d, e), 9 wt% (f), 12 wt% (g, h) and 15 wt% (i).

Fig. 3. XRD patterns (a) and TGA curves (b) of pure PVA hydrogel and PVA/MWCNTs hydrogels with different content of MWCNTs.

Fig. 4. C 1 s high resolution peaks of (a) pure PVA hydrogel and (b) PVA/MWCNTs hydrogel with 15 wt% content of MWCNTs.

Fig. 5. (a(f) Growth status of mouse pre-osteoblast MC3T3-E1 incubated in media containing hydrogels with different MWCNTs content from 0 to 15 wt% for 72 h, respectively. (g) Cell viability in media containing hydrogels with different MWCNTs content.

Fig. 6. Real permittivity (?′) spectra for the PVA/MWCNTs hydrogels with different content of MWCNTs from 0 wt% to 9 (a) and from 12 wt% to 15 wt% (b).

Fig. 7. Contribution of interband transition to the real permittivity as a function of frequency.

Table. 1. Transition frequency of permittivity from positive to negative.

Composite	Filler	Filler content	Transition frequency	Ref.
La_1-_xSr_xMnO₃	Sr²⁺	x = 0.5	∼ 15 MHz	[52]
BaTiO₃/Cu	Cu	6.9 vol.%	∼ 50 MHz	[53]
PDMS/carbon coated iron	carbon coated iron	20 wt%	∼ 10 MHz	[54]
BiFeO₃/Bi₂Fe₄O₉	BiFeO₃	52.5 mol%	∼ 900 MHz	[55]
BaTiO₃/Y₃Fe₅O₁₂	Y₃Fe₅O₁₂	15 mol%	∼ 750 MHz	[56]
BaTiO₃/Ni	Ni	6.98 vol.%	∼ 900 MHz	[57]
PVA/MWCNTs	MWCNTs	12 wt%	∼ 760 kHz	This work

Fig. 8. (a) Alternating current conductivity (σac) spectra of PVA/MWCNTs hydrogels with different content of MWCNTs. (b) Dependence of electrical conductivity on MWCNTs content.

Fig. 9. Dependence of impedance on frequency for PVA/MWCNTs hydrogels. Impedance spectra of PVA/MWCNTs hydrogels below (a) and above (b) the percolation threshold, respectively.

References 62

[1]	D. Smith, W. Padilla, D. Vier, S. Nasser, S. Schultz, Phys. Rev. Lett. 84 (20 0 0) 4184-4187. DOI URL
[2]	N. Yu, F. Aieta, P. Genevet, M. Kats, Z. Gaburro, F. Capasso, Nano Lett. 12 (2012) 6328-6333. DOI URL
[3]	I. Liberal, N. Engheta, Science 358 (2017) 1540-1541. DOI PMID
[4]	X. Huang, Y. Lai, Z. Hang, H. Zheng, C. Chan, Nat. Mater. 10 (2011) 582-586. DOI URL
[5]	A. Poddubny, I. Iorsh, P. Belov, V. Kivshar, Nat. Photonics 7 (2013) 948-957. DOI URL
[6]	E. Cubukcu, S. Zhang, Y. Park, G. Bartal, X. Zhang, Appl. Phys. Lett. 95 (2009) 043113.
[7]	H. Bai, Z. Zhang, Y. Huo, Y. Shen, M. Qin, W. Feng, J. Mater. Sci. Technol. 98 (2022) 167-176.
[8]	J. Tong, F. Suo, J. Ma, L. Tobing, L. Qian, D. Zhang, Opto Electron. Adv. 2 (2019) 180026.
[9]	H. Yu, Y. Feng, C. Chen, Z. Zhang, Y. Cai, M. Qin, W. Feng, Carbon 179 (2021) 348-357 N Y. DOI URL
[10]	R. Maas, J. Parsons, N. Engheta, A. Polman, Nat. Photonics 7 (2013) 907-912. DOI URL
[11]	P. Dyachenko, S. Molesky, A. Petrov, M. Stormer, T. Krekeler, S. Lang, M. Ritter, Z. Jacob, M. Eich, Nat. Commun. 7 (2016) 1-8.
[12]	P. Yu, L. Besteiro, Y. Huang, Adv. Opt. Mater. 7 (2019) 1800995.
[13]	V. Caligiuri, M. Palei, G. Biffi, S. Artyukhin, R. Krahne, Nano Lett. 19 (2019) 3151-3160. DOI PMID
[14]	X. Niu, X. Hu, S. Chu, Q. Gong, Adv. Opt. Mater. 6 (2018) 1701292.
[15]	W. Lewandowski, M. Fruhnert, J. Mieczkowski, C. Rockstuhl, E. Gorecka, Nat. Commun. 6 (2015) 1-9.
[16]	A. Alu, M. Silveirinha, A. Salandrino, N. Engheta, Phys. Rev. B 75 (2007) 155410.
[17]	D. George, A. Chandroth, C. Ng, P. Young, J. Phys. D 51 (2018) 135102.
[18]	Y. Li, C. Argyropoulos, Phys. Rev. B 99 (2019) 075413.
[19]	G. Lio, A. Ferraro, M. Giocondo, R. Caputo, A. Luca, Adv. Opt. Mater. 8 (2020) 2000487.
[20]	C. Cheng, R. Fan, Y. Ren, T. Ding, L. Qian, J. Guo, X. Li, L. An, Y. Lei, Y. Yin, Z. Guo, Nanoscale 9 (2017) 5779-5787. DOI URL
[21]	F. Jamshaid, R. Khan, A. Islam, A. Ahmad, M. Adrees, R. Dilshad, Iran. Polym. J. 29 (2020) 875-889. DOI URL
[22]	H. Khosravi, R. Eslami-Farsani, Polym. Compos. 39 (2018) 677-686.
[23]	M. Islam, M. Rahman, T. Mieno, Adv. Compos. Hybrid Mater. 3 (2020) 285-293. DOI URL
[24]	S. Mirabootalebi, Adv. Compos. Hybrid Mater. 3 (2020) 336-343. DOI URL
[25]	M. Hisham, M. Abdeen, Adv. Compos. Hybrid Mater. 3 (2020) 375-389. DOI URL
[26]	M. Farahmandian, M. Saidi, S. Fazlinejad, Adv. Compos. Hybrid Mater. 5 (2022) 1490-1507. DOI URL
[27]	P. Wang, L. Yang, S. Gao, X. Chen, T. Cao, C. Wang, H. Liu, X. Hu, X. Wu, S. Feng, Adv. Compos. Hybrid Mater. 4 (2021) 639-646. DOI URL
[28]	H. Zamani, Adv. Compos. Hybrid Mater. 4 (2021) 830-844. DOI URL
[29]	S. Suresh, D. Sudhakara, B. Vinod, Adv. Compos. Hybrid Mater. 3 (2020) 243-254. DOI URL
[30]	S. Joshi, Adv. Compos. Hybrid Mater. 3 (2020) 354-364. DOI URL
[31]	S. Gao, X. Zhao, Q. Fu, T. Zhang, J. Zhu, F. Hou, J. Ni, C. Zhu, T. Li, Y. Wang, V. Murugadoss, G. Mersal, M. Ibrahim, Z. Bahy, M. Huang, Z. Guo, J. Mater. Sci. Technol. 126 (2022) 152-160. DOI URL
[32]	X. Jing, Y. Li, J. Zhu, L. Chang, S. Maganti, N. Naik, B. Xu, V. Murugadoss, M. Huang, Z. Guo, Adv. Compos. Hybrid Mater. 5 (2022) 1090-1099. DOI URL
[33]	P. Liu, W. Chen, C. Liu, M. Tian, P. Liu, Sci. Rep. 9 (2019) 1-12. DOI URL
[34]	G. Fan, Z. Wang, K. Sun, Y. Liu, R. Fan, J. Mater. Sci. Technol. 61 (2021) 125-131. DOI URL
[35]	K. Sun, J. Xin, Y. Li, Z. Wang, Q. Hou, X. Li, J. Mater. Sci. Technol. 35 (2019) 2463-2469. DOI
[36]	R. Atchudan, A. Pandurangan, J. Joo, J. Nanosci. Nanotechnol. 15 (2015) 4255-4267. PMID
[37]	M. Gomaa, C. Hugenschmidt, M. Dickmann, E. Abdel-Hady, H. Mohamed, M. Abdel-Hamed, Phys. Chem. Chem. Phys. 20 (2018) 28287-28299. DOI URL
[38]	P. Hu, M. Jia, Y. Zuo, L. He, RSC Adv. 7 (2017) 2450-2459. DOI URL
[39]	T. Liu, C. Jiao, X. Peng, Y. Chen, Y. Chen, C. He, R. Liu, H. Wang, J. Mater. Chem. B 6 (2018) 8105-8114. DOI URL
[40]	Z. Kolarova, P. Stahel, J. Sedlarikova, L. Musilova, M. Stupavska, M. Lehocky, Materials (Basel) 11 (2018) 1451 (Basel).
[41]	O. Park, J. Lee, Compos. B Eng. 144 (2018) 229-236. DOI URL
[42]	K. Sun, R. Fan, Y. Yin, J. Guo, X. Li, Y. Lei, L. An, C. Cheng, Z. Guo, J. Phys. Chem. C 121 (2017) 7564-7571. DOI URL
[43]	X. Zhang, X. Yan, Q. He, H. Wei, J. Long, J. Guo, H. Gu, J. Yu, J. Liu, D. Ding, L. Sun, S. Wei, Z. Guo, ACS Appl. Mater. Interfaces 7 (2015) 6125-6138. DOI URL
[44]	S. Zhang, W. Fan, N. Panoiu, K. Malloy, R. Osgood, S. Brueck, Phys. Rev. Lett. 95 (2005) 137404.
[45]	K. Sun, W. Duan, Y. Lei, Z. Wang, J. Tian, P. Yang, Q. He, M. Chen, H. Wu, Z. Zhang, R. Fan, Compos. Part A-Appl. Sci. Manuf. 156 (2022) 106854.
[46]	S. Nagel, S. Schnatterly, Phys. Rev. B 9 (1974) 1299. DOI URL
[47]	C. Cheng, Y. Jiang, X. Sun, J. Shen, T. Wang, G. Fan, R. Fan, Compos. Part A-Appl. Sci. Manuf. 130 (2020) 105753.
[48]	Z. Wang, P. Xie, G. Fan, Z. Zhang, Y. Liu, Q. Gu, R. Fan, Ceram. Int. 46 (2020) 9342-9346. DOI URL
[49]	B. Li, G. Sui, W. Zhong, Adv. Mater. 21 (2009) 4176-4180. DOI URL
[50]	R. Kohlman, J. Joo, Y. Wang, J. Pouget, H. Kaneko, T. Ishiguro, A. Epstein, Phys. Rev. Lett. 74 (1995) 773. PMID
[51]	H. Shetty, V. Prasad, Mater. Chem. Phys. 196 (2017) 153-159. DOI URL
[52]	K. Sun, P. Yang, Q. He, R. Fan, Z. Wang, J. Tian, X. Yang, W. Duan, X. Wu, Z. Wang, Ceram. Int. 48 (2022) 8417-8422. DOI URL
[53]	Z. Wang, K. Sun, P. Xie, Y. Liu, Q. Gu, R. Fan, J. Wang, J. Mater. 6 (2020) 145-151.
[54]	H. Shetty, V. Prasad, Mater. Chem. Phys. 196 (2017) 153-159. DOI URL
[55]	Q. Li, S. Bao, Y. Sun, J. Li, Z. Yu, Y. Li, S. Zhang, Y. Liu, Z. Cheng, J. Alloy. Compd. 735 (2018) 2081-2086. DOI URL
[56]	Z. Wang, K. Sun, P. Xie, Y. Liu, R. Fan, J. Phys. Condens. Matter 29 (2017) 365703.
[57]	Z. Wang, K. Sun, P. Xie, Q. Hou, Y. Liu, Q. Gu, R. Fan, Acta Mater. 185 (2020) 412-419. DOI URL
[58]	K. Sun, J. Xin, Z. Wang, S. Feng, Z. Wang, R. Fan, H. Liu, Z. Guo, J. Mater. Sci. Mater. Electron. 30 (2019) 14745-14754. DOI URL
[59]	Z. Dang, Y. Lin, C. Nan, Adv. Mater. 15 (2003) 1625-1629. DOI URL
[60]	Z. Shi, R. Fan, Z. Zhang, L. Qian, M. Gao, M. Zhang, L. Zheng, X. Zhang, L. Yin, Adv. Mater. 24 (2012) 2349-2352. DOI URL
[61]	Z. Yu, Z. Yan, F. Zhang, J. Wang, Q. Shao, V. Murugadoss, A. Alhadhrami, G. Mer-sal, M. Ibrahim, Z. Bahy, Y. Li, M. Huang, Z. Guo, Prog. Org. Coat. 168 (2022) 106875.
[62]	D. Pan, G. Yang, H. Dief, J. Dong, F. Su, C. Liu, Y. Li, B. Xu, V. Murugadoss, N. Naik, S. Bahy, Z. Bahy, M. Huang, Z. Guo, Nano Micro Lett. 14 (2022) 108. DOI URL