SpringerLink
Log in

Carboxymethyl cellulose foams: fabrication, aqueous stability, and water capture

  • Polymers & biopolymers
  • Published:
Journal of Materials Science Aims and scope Submit manuscript

Abstract

This paper describes the fabrication of biopolymer foams from aqueous solutions of carboxymethyl cellulose (CMC), as well as effective methods for stabilizing CMC foams in aqueous environments so as to prevent their conversion to gels that results from pore collapse. CMC foams were produced easily by lyophilization of aqueous solutions of high molecular weight CMC, but the considerable hydrophilicity of this anionic polyelectrolyte led to rapid pore collapse and gelation of the material upon its contact with liquid water. However, the porous structure of the CMC foam was stabilized in the presence of aqueous solutions of CaCl2. Mechanical measurements showed the foams to be stiffer in the presence of higher salt concentrations. In addition, CMC foams crosslinked with poly(acrylic acid) (PAA), via the residual hydroxyl groups on the CMC scaffold, were stable in liquid water. When covalent crosslinking was combined with the presence of CaCl2, and/or cellulose additives, the resultant CMC foams exhibited excellent aqueous stability for months or longer and withstood multiple compression cycles without loss of mechanical performance (i.e., by maintaining their porous foam structure). These hydrophilic foams absorbed many times their own weight of water (> 30 g of liquid water per gram of foam) and were amenable to ion exchange, absorption/desorption of organic substances and heavy metals, and water uptake at levels that make them attractive materials for applications in water recovery.

Graphical Abstract

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

Access this article

Log in via an institution

Subscribe and save

Springer+ Basic
EUR 32.99 /Month
  • Get 10 units per month
  • Download Article/Chapter or Ebook
  • 1 Unit = 1 Article or 1 Chapter
  • Cancel anytime
Subscribe now

Buy Now

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

Similar content being viewed by others

Data availability

Not applicable.

Code availability

Not applicable.

References

  1. Hunter D (1978) Papermaking: the history and technique of an ancient craft; Courier Corporation

  2. Politzer A, Teng JC, Singh T (1960) The method of producing a regenerate cellulose sponge. US Patent NO. 3110602

  3. Blanc PD (2016) Fake Silk: the lethal history of viscose rayon. Yale University Press

    Book  Google Scholar 

  4. Song J, Chen C, Zhu S, Zhu M, Dai J, Ray U, Li Y, Kuang Y, Li Y, Quispe N, Yao Y, Gong A, Leiste UH, Bruck HA, Zhu JY, Vellore A, Li H, Minus ML, Jia Z, Martini A, Li T, Hu L (2018) processing bulk natural wood into a high-performance structural material. Nature 554(7691):224–228. https://doi.org/10.1038/nature25476

    Article  CAS  Google Scholar 

  5. Wang S, Lu A, Zhang L (2016) Recent advances in regenerated cellulose materials. Prog Polym Sci 53:169–206. https://doi.org/10.1016/j.progpolymsci.2015.07.003

    Article  CAS  Google Scholar 

  6. Sayyed AJ, Deshmukh NA, Pinjari DV (2019) A critical review of manufacturing processes used in regenerated cellulosic fibres: viscose, cellulose acetate, cuprammonium, LiCl/DMAc, ionic liquids, and NMMO based lyocell. Cellulose 26:2913–2940. https://doi.org/10.1007/s10570-019-02318-y

    Article  CAS  Google Scholar 

  7. Siró I, Plackett D (2010) Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose 17:459–494. https://doi.org/10.1007/s10570-010-9405-y

    Article  CAS  Google Scholar 

  8. Turbak AF, Snyder FW, Sandberg KR (1983) Microfibrillated cellulose, a new cellulose product: properties, uses, and commercial potential. J Appl Polym Sci Appl Polym Symp 37:815–827

    CAS  Google Scholar 

  9. Cui J, Cueto C, Bien C, Preda D, Gamliel D, Emrick T (2022) Robust polymer foams from 2-hydroxyethyl cellulose: fabrication, stability, and chemical functionalization. Polymer (Guildf) 256:125131. https://doi.org/10.1016/j.polymer.2022.125131

    Article  CAS  Google Scholar 

  10. Hollabaugh CB, Burt LH, Walsh AP (1945) Carboxymethylcellulose. Uses and applications. Ind Eng Chem 37(10):943–947. https://doi.org/10.1021/ie50430a015

    Article  CAS  Google Scholar 

  11. Grant GT, Morris ER, Rees DA, Smith PJC, Thom D (1973) Biological interactions between polysaccharides and divalent cations: the egg-box model. FEBS Lett 32(1):195–198. https://doi.org/10.1016/0014-5793(73)80770-7

    Article  CAS  Google Scholar 

  12. Hua M, Wu S, Ma Y, Zhao Y, Chen Z, Frenkel I, Strzalka J, Zhou H, Zhu X, He X (2021) Strong tough hydrogels via the synergy of freeze-casting and salting out. Nature 590(7847):594–599. https://doi.org/10.1038/s41586-021-03212-z

    Article  CAS  Google Scholar 

  13. Wu S, Hua M, Alsaid Y, Du Y, Ma Y, Zhao Y, Lo C, Wang C, Wu D, Yao B, Strzalka J, Zhou H, Zhu X, He X (2021) Poly(vinyl alcohol) hydrogels with broad-range tunable mechanical properties via the hofmeister effect. Adv Mater 33(11):2007829. https://doi.org/10.1002/adma.202007829

    Article  CAS  Google Scholar 

  14. Hosny WM, Hadi AKA, El-Saied H, Basta AH (1995) Metal chelates with some cellulose derivatives. Part III. Synthesis and structural chemistry of nickel (II) and copper (II) complexes with carboxymethyl cellulose. Polym Int 37(2):93–96. https://doi.org/10.1002/pi.1995.210370202

    Article  CAS  Google Scholar 

  15. Basta AH, El-Saied H, Hasanin MS, El-Deftar MM (2018) Green carboxymethyl cellulose-silver complex versus cellulose origins in biological activity applications. Int J Biol Macromol 107:1364–1372. https://doi.org/10.1016/j.ijbiomac.2017.11.061

    Article  CAS  Google Scholar 

  16. Hsiao P-Y, Luijten E (2006) Salt-induced collapse and reexpansion of highly charged flexible polyelectrolytes. Phys Rev Lett 97(14):148301. https://doi.org/10.1103/PhysRevLett.97.148301

    Article  CAS  Google Scholar 

  17. Hua J, Mitra MK, Muthukumar M (2012) Theory of volume transition in polyelectrolyte gels with charge regularization. J Chem Phys 136(13):134901. https://doi.org/10.1063/1.3698168

    Article  CAS  Google Scholar 

  18. Peterson EA, Sober HA (1956) Chromatography of proteins. I. Cellulose ion-exchange adsorbents. J Am Chem Soc 78(4):751–755. https://doi.org/10.1021/ja01585a016

    Article  CAS  Google Scholar 

  19. Mann AW, Deutscher RL (1977) Solution geochemistry of copper in water containing carbonate, sulphate and chloride ions. Chem Geol 19(1–4):253–265. https://doi.org/10.1016/0009-2541(77)90018-3

    Article  CAS  Google Scholar 

  20. Gregor HP (1951) Gibbs-donnan equilibria in ion exchange resin systems. J Am Chem Soc 73(2):642–650. https://doi.org/10.1021/ja01146a042

    Article  CAS  Google Scholar 

  21. Turse R, Rieman W (1961) Kinetics of ion exchange in a chelating resin. J Phys Chem 65(10):1821–1824. https://doi.org/10.1021/j100827a031

    Article  CAS  Google Scholar 

  22. Katchalsky A (1954) Problems in the physical chemistry of polyelectrolytes. J Polym Sci 12(1):159–184. https://doi.org/10.1002/pol.1954.120120114

    Article  CAS  Google Scholar 

  23. Zhulina EB, Rubinstein M (2012) Ionic strength dependence of polyelectrolyte brush thickness. Soft Matter 8(36):9376. https://doi.org/10.1039/c2sm25863c

    Article  CAS  Google Scholar 

  24. Tanaka T (1978) Collapse of gels and the critical endpoint. Phys Rev Lett 40(12):820–823. https://doi.org/10.1103/PhysRevLett.40.820

    Article  CAS  Google Scholar 

  25. Katchalsky A, Michaeli I (1955) Polyelectrolyte gels in salt solutions. J Polym Sci 15(79):69–86. https://doi.org/10.1002/pol.1955.120157906

    Article  CAS  Google Scholar 

  26. Horkay F, Tasaki I, Basser PJ (2000) Osmotic swelling of polyacrylate hydrogels in physiological salt solutions. Biomacromol 1(1):84–90. https://doi.org/10.1021/bm9905031

    Article  CAS  Google Scholar 

  27. Marshall TJ (1958) A relation between permeability and size distribution of pores. J Soil Sci 9(1):1–8. https://doi.org/10.1111/j.1365-2389.1958.tb01892.x

    Article  Google Scholar 

  28. Beebe DJ, Moore JS, Bauer JM, Yu Q, Liu RH, Devadoss C, Jo B-H (2000) Functional hydrogel structures for autonomous flow control inside microfluidic channels. Nature 404(6778):588–590. https://doi.org/10.1038/35007047

    Article  CAS  Google Scholar 

  29. Zwieniecki MA, Melcher PJ, Michele Holbrook N (2001) Hydrogel control of xylem hydraulic resistance in plants. Science (1979) 291(5506):1059–1062. https://doi.org/10.1126/science.1057175

    Article  CAS  Google Scholar 

Download references

Acknowledgements

This material is based upon work supported by Defense Advanced Research Projects Agency (DARPA) under Contract No. HR001121C0032. Any opinions, findings, conclusions, and/or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of DARPA. We appreciate the use of the mechanical characterization laboratories of Alfred Crosby and Alan Lesser at UMass Amherst, as well as porosity measurements by Mark Biron at the University of Connecticut Center for Clean Energy. We appreciate the technical support of William Kidd and Tiffany Yu of Physical Sciences, Inc.

Author information

Authors and Affiliations

  1. Polymer Science & Engineering Department, Conte Center for Polymer Research, University of Massachusetts, Amherst, MA, 01003, USA

    Jianxun Cui, Jordan Varma & Todd Emrick

  2. Physical Sciences Inc., 20 New England Business Center, Andover, MA, 01810, USA

    Caitlin Bien, Dorin Preda & David Gamliel

Authors
  1. Jianxun Cui
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jordan Varma
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Todd Emrick
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Caitlin Bien
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Dorin Preda
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. David Gamliel
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

The authors contributed to this manuscript through conception of the project (JC, TE, DG), experimental design (all authors), conducting measurements (JC, JV, CB), and manuscript composition (JC, JV, CB, TE, DG).

Corresponding author

Correspondence to Todd Emrick.

Ethics declarations

Ethical approval

Not applicable.

Conflict of interest

The authors state that they have no competing financial interests or known personal relationships associated with the work in this article.

Additional information

Handling Editor: Stephen Eichhorn.

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file 1 (DOCX 10488 KB)

Supplementary file 2 (MP4 75683 KB)

Rights and permissions

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Cui, J., Varma, J., Emrick, T. et al. Carboxymethyl cellulose foams: fabrication, aqueous stability, and water capture. J Mater Sci 58, 8230–8240 (2023). https://doi.org/10.1007/s10853-023-08514-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10853-023-08514-3

Search

Navigation