Skip to main content

Advertisement

SpringerLink
Log in

Super-tough hydrogels from shape-memory polyurethane with wide-adjustable mechanical properties

  • Original Paper
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

Recoverable hydrogels with high strength and toughness have been fabricated from hydrophilic and thermoplastic polyurethane (HTPU), which chains consist of hydrophilic polyethylene glycol (PEG) segment of high crystallinity and hydrophobic segment with strong hydrogen-bonding groups. This HTPU absorbed high amount of water, during which the PEG crystals swollen and dissolved, while the hydrophobic segments still held the adjacent chains together, forming a stable hydrogel. Even at equilibrium swelling state (89 wt% water), the HTPU hydrogel exhibited high modulus (0.4 MPa), high strength (2.6 MPa), and large strain at break (~500%). The effect of water content on the tensile properties of HTPU hydrogels was carefully studied at different levels of swelling. Interestingly, the hydrogels demonstrated a transition from a typical tough plastic to a tough elastomer when the water content reached 35 wt% of the hydrogel, with breaking strength of 10.0 MPa and fracture energy of 59.7 MJ/m3 at maximum strain over 1600%. The results from differential scanning calorimetry, Fourier transform infrared spectroscopy, and microscope measurements showed that the wide adjustability of this HTPU mechanical property was a result of the changes in its crystallinity, hydrogen-bonding, and hydrophobic association. Furthermore, the shape-memory performance of the HTPU was studied with heat and water stimuli and found faster at heating to 70 °C than that by immersion in water: 10 s versus 10 min. This study may widen the application of HTPU biodegradable polymers and provide new frontiers for the design of tough hydrogels by network structure control.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6
Figure 7
Figure 8
Figure 9

Similar content being viewed by others

References

  1. Malda J, Visser J, Melchels FP et al (2013) 25th anniversary article: engineering hydrogels for biofabrication. Adv Mater 25:5011–5028

    Article  Google Scholar 

  2. Li G, Li F, Zheng Z et al (2016) Silk microfiber-reinforced silk composite scaffolds: fabrication, mechanical properties, and cytocompatibility. J Mater Sci 51:3025–3035. doi:10.1007/s10853-015-9613-9

    Article  Google Scholar 

  3. Utech S, Boccaccini AR (2016) A review of hydrogel-based composites for biomedical applications: enhancement of hydrogel properties by addition of rigid inorganic fillers. J Mater Sci 51:271–310. doi:10.1007/s10853-015-9382-5

    Article  Google Scholar 

  4. Annabi N, Tamayol A, Uquillas JA et al (2014) 25th anniversary article: rational design and applications of hydrogels in regenerative medicine. Adv Mater 26:85–124

    Article  Google Scholar 

  5. Buenger D, Topuz F, Groll J (2012) Hydrogels in sensing applications. Prog Polym Sci 37:1678–1719

    Article  Google Scholar 

  6. Corkhill PH, Hamilton CJ, Tighe BJ (1989) Synthetic hydrogels VI. Hydrogel composites as wound dressings and implant materials. Biomaterials 10:3–10

    Article  Google Scholar 

  7. Fei B, Wach RA, Mitomo H, Yoshii F, Kume T (2000) Hydrogel of biodegradable cellulose derivatives. I. radiation-induced crosslinking of CMC. J Appl Polym Sci 78:278–283

    Article  Google Scholar 

  8. Beebe DJ, Moore JS, Bauer JM et al (2000) Functional hydrogel structures for autonomous flow control inside microfluidic channels. Nature 404:588–590

    Article  Google Scholar 

  9. Li J, Tong J, Li X, Yang Z, Zhang Y, Diao G (2016) Facile microfluidic synthesis of copolymer hydrogel beads for the removal of heavy metal ions. J Mater Sci 51:10375–10385. doi:10.1007/s10853-016-0258-0

    Article  Google Scholar 

  10. Bin Imran A, Esaki K, Gotoh H et al (2014) Extremely stretchable thermosensitive hydrogels by introducing slide-ring polyrotaxane cross-linkers and ionic groups into the polymer network. Nat Commun 5(5124):1–8

    Google Scholar 

  11. Hao X, Zhou W, Yao R, Xie Y, ur Rehman S, Yang H (2013) A new class of thermo-switchable hydrogel: application to the host–guest approach. J Mater Chem A 1:14612–14617

    Article  Google Scholar 

  12. Haraguchi K, Takehisa T (2002) Nanocomposite hydrogels: a unique organic–inorganic network structure with extraordinary mechanical, optical, and swelling/de-swelling properties. Adv Mater 14:1120–1124

    Article  Google Scholar 

  13. Gaharwar AK, Dammu SA, Canter JM, Wu C-J, Schmidt G (2011) Highly extensible, tough, and elastomeric nanocomposite hydrogels from poly(ethylene glycol) and hydroxyapatite nanoparticles. Biomacromolecules 12:1641–1650

    Article  Google Scholar 

  14. Gong JP, Katsuyama Y, Kurokawa T, Osada Y (2003) Double-network hydrogels with extremely high mechanical strength. Adv Mater 15:1155–1158

    Article  Google Scholar 

  15. Sun J-Y, Zhao X, Illeperuma WRK et al (2012) Highly stretchable and tough hydrogels. Nature 489:133–136

    Article  Google Scholar 

  16. Lu X, Chan CY, Lee KI et al (2014) Super-tough and thermo-healable hydrogel—promising for shape-memory absorbent fiber. J Mater Chem B 2:7631–7638

    Article  Google Scholar 

  17. Zhang HJ, Sun TL, Zhang AK et al (2016) Tough physical double-network hydrogels based on amphiphilic triblock copolymers. Adv Mater 28:4884–4890

    Article  Google Scholar 

  18. Guo M, Pitet LM, Wyss HM, Vos M, Dankers PYW, Meijer EW (2014) Tough stimuli-responsive supramolecular hydrogels with hydrogen-bonding network junctions. J Am Chem Soc 136:6969–6977

    Article  Google Scholar 

  19. Hu J, Meng H, Li G, Ibekwe SI (2015) A review of stimuli-responsive polymers for smart textile applications. Smart Mater Struct 21(053001):1–24

    Google Scholar 

  20. Abraham GA, Basu A, Battiston KG et al (2015) Advances in polyurethane biomaterials. Woodhead Publishing, Elsevier

    Google Scholar 

  21. Yoo H-J, Kim H-D (2008) Synthesis and properties of waterborne polyurethane hydrogels for wound healing dressings. J Biomed Mater Res B 85B:326–333

    Article  Google Scholar 

  22. Naficy S, Spinks GM, Wallace GG (2014) Thin, tough, pH-sensitive hydrogel films with rapid load recovery. ACS Appl Mater Interfaces 6:4109–4114

    Article  Google Scholar 

  23. Tanaka T (1986) Kinetics of phase transition in polymer gels. Physica 140A:261–268

    Article  Google Scholar 

  24. Li Y, Tanaka T (1992) Phase transitions of gels. Annu Rev Mater Sci 22:243–277

    Article  Google Scholar 

  25. Itagaki H, Kurokawa T, Furukawa H, Nakajima T, Katsumoto Y, Gong JP (2010) Water-induced brittle-ductile transition of double network hydrogels. Macromolecules 43:9495–9500

    Article  Google Scholar 

  26. Ahmed S, Nakajima T, Kurokawa T, Anamul Haque M, Gong JP (2014) Brittle–ductile transition of double network hydrogels: mechanical balance of two networks as the key factor. Polymer 55:914–923

    Article  Google Scholar 

  27. Stauffer SR, Peppast NA (1992) Poly (vinyl alcohol) hydrogels prepared by freezing-thawing cyclic processing. Polymer 33:3932–3936

    Article  Google Scholar 

  28. Mori Y, Tokura H, Yoshikawa M (1997) Properties of hydrogels synthesized by freezing and thawing aqueous polyvinyl alcohol solutions and their applications. J Mater Sci 32:491–496. doi:10.1023/A:1018586307534

    Article  Google Scholar 

  29. SB Majee (2016) Emerging concepts in analysis and applications of hydrogels. InTech

  30. Lee KI, Wang X, Guo X, Yung K-F, Fei B (2016) Highly water-absorbing silk yarn with interpenetrating network via in situ polymerization. Int J Biol Macromol. doi:10.1016/j.ijbiomac.2016.11.090

    Google Scholar 

  31. Qiu W, Wunderlich B (2006) Reversible melting of high molar mass poly(oxyethylene). Thermochim Acta 448:136–146

    Article  Google Scholar 

  32. Wang X, Hu H, Yang Z, He L, Kong Y, Fei B, Xin JH (2014) Smart hydrogel-functionalized textile system with moisture management property for skin application. Smart Mater Struct 23(125027):1–10

    Google Scholar 

  33. Kolhe P, Kannan RM (2003) Improvement in ductility of chitosan through blending and copolymerization with PEG: FTIR investigation of molecular interactions. Biomacromolecules 4:173–180

    Article  Google Scholar 

  34. Ping ZH, Nguyen QT, Chen SM, Zhou JQ, Ding YD (2001) States of water in different hydrophilic polymers—DSC and FTIR studies. Polymer 42:8461–8467

    Article  Google Scholar 

  35. Fei B, Chen C, Wu H, Peng S, Wang X, Dong L, Xin JH (2004) Modified poly(3-hydroxybutyrate-co-3-hydroxyvalerate) using hydrogen bonding monomers. Polymer 45:6275–6284

    Article  Google Scholar 

  36. Fei B, Chen C, Wu H, Peng S, Wang X, Dong L (2003) Quantitative FTIR study of PHBV/bisphenol A blends. Eur Polymer J 39:1939–1946

    Article  Google Scholar 

  37. Argon AS (2013) The physics of deformation and fracture of polymers. Cambridge University Press, Cambridge

    Book  Google Scholar 

  38. Liu J, Chen C, He C, Zhao J, Yang X, Wang H (2012) Synthesis of graphene peroxide and its application in fabricating super extensible and highly resilient nanocomposite hydrogels. ACS Nano 6:8194–8202

    Article  Google Scholar 

  39. Hu Z, Chen G (2014) Novel nanocomposite hydrogels consisting of layered double hydroxide with ultrahigh tensibility and hierarchical porous structure at low inorganic content. Adv Mater 26:5950–5956

    Article  Google Scholar 

  40. Hu Y, Du Z, Deng X et al (2016) Dual physically cross-linked hydrogels with high stretchability, toughness, and good self-recoverability. Macromolecules 49:5660–5668

    Article  Google Scholar 

  41. Nakajima T, Sato H, Zhao Y et al (2012) A universal molecular stent method to toughen any hydrogels based on double network concept. Adv Funct Mater 22:4426–4432

    Article  Google Scholar 

  42. Chen Q, Zhu L, Zhao C, Wang Q, Zheng J (2013) A robust, one-pot synthesis of highly mechanical and recoverable double network hydrogels using thermoreversible sol-gel polysaccharide. Adv Mater 25:4171–4176

    Article  Google Scholar 

  43. Luo F, Sun TL, Nakajima T et al (2015) Oppositely charged polyelectrolytes form tough, self-healing, and rebuildable hydrogels. Adv Mater 27:2722–2727

    Article  Google Scholar 

  44. Jeon I, Cui J, Illeperuma WRK, Aizenberg J, Vlassak JJ (2016) Extremely stretchable and fast self-healing hydrogels. Adv Mater 28:4678–4683

    Article  Google Scholar 

  45. You J, Xie S, Cao J et al (2016) Quaternized chitosan/poly(acrylic acid) polyelectrolyte complex hydrogels with tough, self-recovery, and tunable mechanical properties. Macromolecules 49:1049–1059

    Article  Google Scholar 

  46. Lin P, Ma S, Wang X, Zhou F (2015) Molecularly engineered dual-crosslinked hydrogel with ultrahigh mechanical strength, toughness, and good self-recovery. Adv Mater 27:2054–2059

    Article  Google Scholar 

  47. Galeski A, Argon AS, Cohen RE (1988) Changes in the morphology of bulk spherulitic nylon 6 due to plastic deformation. Macromolecules 21:2761–2770

    Article  Google Scholar 

  48. Akagi Y, Gong JP, Chung UI, Sakai T (2013) Transition between phantom and affine network model observed in polymer gels with controlled network structure. Macromolecules 46:1035–1040

    Article  Google Scholar 

  49. Naficy S, Brown HR, Razal JM, Spinks GM, Whitten PG (2011) Progress toward robust polymer hydrogels. Aust J Chem 64:1007–1025

    Article  Google Scholar 

  50. Hu J, Zhu Y, Huang H, Lu J (2012) Recent advances in shape–memory polymers: structure, mechanism, functionality, modeling and applications. Prog Polym Sci 37:1720–1763

    Article  Google Scholar 

  51. Langer R, Tirrell DA (2004) Designing materials for biology and medicine. Nature 428:487–492

    Article  Google Scholar 

Download references

Acknowledgements

We gratefully acknowledge the financial support from the National Natural Science Foundation of China (NSFC 51373146) and PolyU Internal Fund (PolyU G-UC30).

Author information

Authors and Affiliations

  1. Institute of Textile and Clothing, The Hong Kong Polytechnic University, Hong Kong, People’s Republic of China

    Feng Wu, Lei Chen, Yangling Li, Ka I Lee & Bin Fei

Authors
  1. Feng Wu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Lei Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yangling Li
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Ka I Lee
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Bin Fei
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Bin Fei.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 55 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wu, F., Chen, L., Li, Y. et al. Super-tough hydrogels from shape-memory polyurethane with wide-adjustable mechanical properties. J Mater Sci 52, 4421–4434 (2017). https://doi.org/10.1007/s10853-016-0689-7

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-016-0689-7

Keywords

Search

Navigation