Abstract
The effect of cellulose nanofibers (CNFs) on the mechanical and structural properties of poly (vinyl alcohol) (PVA) hydrogels cross-linked dually by a freezing/thawing method and a cross-linker (borax) was investigated using tensile tests, FT-IR measurements and synchrotron simultaneous small-angle/wide-angle X-ray scattering (SAXS/WAXS). The cross-linking with borax and addition of CNF greatly improved the tensile performance of the PVA hydrogels prepared in the freezing/thawing method, e.g., the dual cross-linking resulted in remarkable increase in the fracture strain, the Young’s modulus and the tensile strength. The fiber length effect on the mechanical properties of the CNF/PVA/borax hydrogels was examined, so that addition of CNF with longer fiber length increased the tensile modulus, whereas addition of CNF with shorter length caused extensibility higher than 1000% even at high CNF concentrations. SAXS/WAXS and FT-IR measurements have revealed that PVA was crystallized due to the freezing/thawing process, and both of PVA and CNF were cross-linked with borax, and hydrogen bonds between hydroxy groups of PVA (or/and CNF) were formed, indicating that the multiple cross-linking is effective for improvement of the tensile performance. In addition, the CNF/PVA/borax gel with the multi-physical cross-linking was found to possess the ability of the self-healing.
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Avolio R, Bonadies I, Capitani D, Errico ME, Gentile G, Avella M (2012) A multitechnique approach to assess the effect of ball milling on cellulose. Carbohydr Polym 87:265–273. https://doi.org/10.1016/j.carbpol.2011.07.047
Avolio R et al (2015) Effect of cellulose structure and morphology on the properties of poly(butylene succinate-co-butylene adipate) biocomposites. Carbohydr Polym 133:408–420. https://doi.org/10.1016/j.carbpol.2015.06.101
Bauer S, Bauer-Gogonea S, Graz I, Kaltenbrunner M, Keplinger C, Schwodiauer R (2014) 25th anniversary article: a soft future: from robots and sensor skin to energy harvesters. Adv Mater 26:149–162. https://doi.org/10.1002/adma.201303349
Beaucage G (1995) Approximations leading to a unified exponential power-law approach to small-angle scattering. J Appl Crystallogr 28:717–728. https://doi.org/10.1107/S0021889895005292
Beaucage G (1996) Small-angle scattering from polymeric mass fractals of arbitrary mass-fractal dimension. J Appl Crystallogr 29:134–146. https://doi.org/10.1107/S0021889895011605
Beaucage G (2004) Determination of branch fraction and minimum dimension of mass-fractal aggregates. Phys Rev E. https://doi.org/10.1103/Physreve.70.031401
Beaucage G, Schaefer DW (1994) Structural studies of complex-systems using small-angle scattering—a unified Guinier power-law approach. J Non-Cryst Solids 172:797–805. https://doi.org/10.1016/0022-3093(94)90581-9
Beaucage G, Kammler HK, Pratsinis SE (2004) Particle size distributions from small-angle scattering using global scattering functions. J Appl Crystallogr 37:523–535. https://doi.org/10.1107/S0021889804008969
Boyaci T, Orakdogen N (2016) Poly(N, N-dimethylaminoethyl methacrylate-co-2-acrylamido-2-methyl-propanosulfonic acid)/Laponite nanocomposite hydrogels and cryogels with improved mechanical strength and rapid dynamic properties. Appl Clay Sci 121–122:162–173. https://doi.org/10.1016/j.clay.2015.12.018
Chen D, Pei QB (2017) Electronic muscles and skins: a review of soft sensors and actuators. Chem Rev 117:11239–11268. https://doi.org/10.1021/acs.chemrev.7b00019
Cong HL, Radosz M, Towler BF, Shen YQ (2007) Polymer-inorganic nanocomposite membranes for gas separation. Sep Purif Technol 55:281–291. https://doi.org/10.1016/j.seppur.2006.12.017
De France KJ, Hoare T, Cranston ED (2017) Review of hydrogels and aerogels containing nanocellulose. Chem Mater 29:4609–4631. https://doi.org/10.1021/acs.chemmater.7b00531
Gentile G, Cocca M, Avolio R, Errico M, Avella M (2018) Effect of microfibrillated cellulose on microstructure and properties of poly(vinyl alcohol) foams. Polymers 10:813. https://doi.org/10.3390/polym10080813
Glatter O, Kratky O (1982) Small angle X-ray scattering. Academic Press, London
Golmohammadi H, Morales-Narvaez E, Naghdi T, Merkoci A (2017) Nanocellulose in sensing and biosensing. Chem Mater 29:5426–5446. https://doi.org/10.1021/acs.chemmater.7b01170
Han J et al (2017) Effects of nanocellulose on the structure and properties of poly(vinyl alcohol)-borax hybrid foams. Cellulose 24:4433–4448. https://doi.org/10.1007/s10570-017-1409-4
Hassan CM, Peppas NA (2000a) Structure and applications of poly(vinyl alcohol) hydrogels produced by conventional crosslinking or by freezing/thawing methods. Adv Polym Sci 153:37–65
Hassan CM, Peppas NA (2000b) Structure and morphology of freeze/thawed PVA hydrogels. Macromolecules 33:2472–2479. https://doi.org/10.1021/Ma9907587
Hoffman AS (2012) Hydrogels for biomedical applications. Adv Drug Deliv Rev 64:18–23. https://doi.org/10.1016/j.addr.2012.09.010
Holloway JL, Lowman AM, Palmese GR (2013) The role of crystallization and phase separation in the formation of physically cross-linked PVA hydrogels. Soft Matter 9:826–833. https://doi.org/10.1039/c2sm26763b
Huan SQ, Bai L, Cheng WL, Han GP (2016) Manufacture of electrospun all-aqueous poly(vinyl alcohol)/cellulose nanocrystal composite nanofibrous mats with enhanced properties through controlling fibers arrangement and microstructure. Polymer 92:25–35. https://doi.org/10.1016/j.polymer.2016.03.082
Huang M, Hou Y, Li Y, Wang D, Zhang L (2017) High performances of dual network PVA hydrogel modified by PVP using borax as the structure-forming accelerator. Des Monomers Polym 20:505–513. https://doi.org/10.1080/15685551.2017.1382433
Ilavsky J (2012) Nika: software for two-dimensional data reduction. J Appl Crystallogr 45:324–328. https://doi.org/10.1107/S0021889812004037
Kanaya T, Ohkura M, Kaji K, Furusaka M, Misawa M (1994) Structure of poly(vinyl alcohol) gels studied by wide-angle and small-angle neutron-scattering. Macromolecules 27:5609–5615. https://doi.org/10.1021/Ma00098a014
Kaneko F, Seto N, Sasaki K, Sakurai S, Kimura T (2013) Simultaneous SAXS and WAXS study on the guest exchange process of syndiotactic polystyrene: crystalline complex formation with triethylene glycol dimethyl ether. Macromol Chem Phys 214:1893–1900. https://doi.org/10.1002/macp.201300001
Kobayashi M, Kitaoka Y (1997) Complex formation of boric acids with di- and tricarboxylic acids and poly(vinyl alcohol) in aqueous solutions. Macromol Symp 114:303–308. https://doi.org/10.1002/masy.19971140141
Lee H et al (2017) Enhancement of mechanical properties of polymeric nanofibers by controlling crystallization behavior using a simple freezing/thawing process. RSC Adv 7:43994–44000. https://doi.org/10.1039/c7ra06545k
Narita T, Mayumi K, Ducouret G, Hébraud P (2013) Viscoelastic properties of poly(vinyl alcohol) hydrogels having permanent and transient cross-links studied by microrheology, classical rheometry, and dynamic light scattering. Macromolecules 46:4174–4183. https://doi.org/10.1021/ma400600f
Park S, Baker JO, Himmel ME, Parilla PA, Johnson DK (2010) Cellulose crystallinity index: measurement techniques and their impact on interpreting cellulase performance. Biotechnol Biofuels 2:3. https://doi.org/10.1186/1754-6834-3-10
Peppas NA (1975) Turbidimetric studies of aqueous poly(vinyl-alcohol) solutions. Makromol Chem 176:3433–3440
Peresin MS, Habibi Y, Zoppe JO, Pawlak JJ, Rojas OJ (2010) Nanofiber composites of polyvinyl alcohol and cellulose nanocrystals: manufacture and characterization. Biomacromolecules 11:674–681. https://doi.org/10.1021/bm901254n
Rath T et al (2014) Real time X-ray scattering study of the formation of ZnS nanoparticles using synchrotron radiation. Mater Chem Phys 144:310–317. https://doi.org/10.1016/j.matchemphys.2013.12.045
Richter D et al (1997) Polymer aggregates with crystalline cores: The system polyethylene-poly(ethylenepropylene). Macromolecules 30:1053–1068. https://doi.org/10.1021/Ma961039k
Shimizu N, Yatabe K, Nagatani Y, Saijyo S, Kosuge T, Igarashi N (2016) Software development for analysis of small-angle X-ray scattering data. AIP Conf Proc 1741:050017
Spoljaric S, Salminen A, Luong ND, Seppälä J (2014) Stable, self-healing hydrogels from nanofibrillated cellulose, poly(vinyl alcohol) and borax via reversible crosslinking. Eur Polym J 56:105–117. https://doi.org/10.1016/j.eurpolymj.2014.03.009
Stauffer SR, Peppas NA (1992) Poly(vinyl alcohol) hydrogels prepared by freezing-thawing cyclic processing. Polymer 33:3932–3936. https://doi.org/10.1016/0032-3861(92)90385-A
Takeno H (2016) Synchrotron small-angle X-Ray scattering and small-angle neutron scattering studies of nanomaterials. In: Kumar CSSR (ed) X-ray and neutron techniques for nanomaterials characterization. Springer, Berlin, pp 717–760
Takeno H, Nakamura W (2013) Structural and mechanical properties of composite hydrogels composed of clay and a polyelectrolyte prepared by mixing. Colloid Polym Sci 291:1393–1399. https://doi.org/10.1007/s00396-012-2871-z
Takeno H, Kimura Y (2016) Molecularweight effects on tensile properties of blend hydrogels composed of clay and polymers. Polymer 85:47–54. https://doi.org/10.1016/j.polymer.2016.01.008
Takeno H, Sato C (2016) Effects of molecular mass of polymer and composition on the compressive properties of hydrogels composed of Laponite and sodium polyacrylate. Appl Clay Sci 123:141–147. https://doi.org/10.1016/j.clay.2016.01.030
Takeno H, Maehara A, Yamaguchi D, Koizumi S (2012) A Structural study of an organogel investigated by small-angle neutron scattering and synchrotron small-angle X-ray scattering. J Phys Chem B 116:7739–7745. https://doi.org/10.1021/jp3008514
Takeno H, Yanagita M, Motegi Y, Kondo S (2015) Relationship between helical aggregates and polymorphs in a 12-hydroxystearic acid gel: their thermal stability and formation kinetics. Colloid Polym Sci 293:199–207
Vashist A et al (2018) Nanocomposite hydrogels: advances in nanofillers used for nanomedicine. Gels 4:75. https://doi.org/10.3390/gels4030075
Wang H (2004) Time-resolved small-angle neutron scattering study of polyethylene crystallization from solution. J Polym Sci Pol Phys 42:3133–3147. https://doi.org/10.1002/polb.20181
Wang L, Ishihara S, Hikima Y, Ohshima M, Sekiguchi T, Sato A, Yano H (2017) Unprecedented development of ultrahigh expansion injection-molded polypropylene foams by introducing hydrophobic-modified cellulose nanofibers. ACS Appl Mater Inter 9:9250–9254. https://doi.org/10.1021/acsami.7b01329
Xu XZ, Liu F, Jiang L, Zhu JY, Haagenson D, Wiesenborn DP (2013) Cellulose nanocrystals vs. cellulose nanofibrils: a comparative study on their microstructures and effects as polymer reinforcing agents. Acs Appl Mater Inter 5:2999–3009. https://doi.org/10.1021/am302624t
Zhang F, Ilavsky J, Long GG, Quintana JPG, Allen AJ, Jemian PR (2010) Glassy carbon as an absolute intensity calibration standard for small-angle scattering. Metall Mater Trans A 41A:1151–1158. https://doi.org/10.1007/s11661-009-9950-x
Zhang H, Xia H, Zhao Y (2012) Poly(vinyl alcohol) hydrogel can autonomously self-heal. ACS Macro Letters 1:1233–1236. https://doi.org/10.1021/mz300451r
Zhang W, He X, Li C, Zhang X, Lu C, Zhang X, Deng Y (2014) High performance poly (vinyl alcohol)/cellulose nanocrystals nanocomposites manufactured by injection molding. Cellulose 21:485–494. https://doi.org/10.1007/s10570-013-0141-y
Acknowledgments
This work was supported by JSPS KAKENHI Grant No. 19K05594. The synchrotron SAXS/WAXS measurements were conducted under the approval of Photon Factory Program Advisory Committee. The XRD measurements were performed at the Center for Instrumental Analysis of Gunma University, and we thank Mr. Sakamoto of the Center for his technical assistance of the measurements.
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Takeno, H., Inoguchi, H. & Hsieh, WC. Mechanical and structural properties of cellulose nanofiber/poly(vinyl alcohol) hydrogels cross-linked by a freezing/thawing method and borax. Cellulose 27, 4373–4387 (2020). https://doi.org/10.1007/s10570-020-03083-z
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DOI: https://doi.org/10.1007/s10570-020-03083-z