, Volume 26, Issue 1, pp 597–615 | Cite as

Carboxymethyl cellulose/poly(acrylic acid) interpenetrating polymer network hydrogels as multifunctional adsorbents

  • Paulo V. O. Toledo
  • Diego P. C. Limeira
  • Nicolas C. Siqueira
  • Denise F. S. PetriEmail author
Original Paper


Interpenetrating polymer network (IPN) hydrogels were prepared by mixing carboxymethyl cellulose (CMC) solution and crosslinked poly(acrylic acid) (cPAA) single IPN hydrogel at mass ratios 100:0, 25:75, 50:50, 75:25 and 0:100 and subsequent crosslinking of CMC chains with citric acid, aimed towards the creation of full IPN hydrogels. The resulting CMC:cPAA hydrogels were freeze-dried for the determination of density, swelling degree, compressive modulus and thermal behavior. Morphological and structural parameters were determined by means of scanning electron microscopy, Fourier transform infrared spectroscopy in the attenuated total reflectance mode (FTIR-ATR) and X-ray microtomography (CT) analyses. The efficiency of CMC:cPAA hydrogels as adsorbents for methylene blue (MB) dye at pH 7 and Cu2+ ions at pH 4.5 was systematically investigated at (24 ± 1) °C and evaluated with Langmuir, Freundlich and Dubinin–Radushkevitch adsorption models and kinetic equations. The CMC:cPAA 50:50 hydrogels were particularly interesting because they presented the highest compression modulus (141 ± 3 kPa), swelling degree of 58 ± 2 gwater/g and maximum adsorption capacity (qmax) for MB dye and Cu2+ ions as 613 mg g−1 and 250 mg g−1, respectively. The adsorption kinetics of MB and Cu2+ ions followed the pseudo-second order equation. Fitting with the intraparticle diffusion model showed that in both cases, the adsorbate molecules first diffuse rapidly from the medium to the adsorbent surface, and then in a second slower stage, they diffuse into the network macropores. The hydrogels could be recycled five times without losing efficiency.

Graphical abstract


Carboxymethyl cellulose Interpenetrating polymer networks Hydrogels Adsorption Methylene blue Copper ions 



Authors gratefully acknowledge financial support from Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq Grant 306848/2017 and 157034/2017-8) and Unified Scholarship Program from the University of São Paulo. We also thank LNNano-CNPEM (Project Micro CT-22728, Campinas, Brazil) for the micro tomography measurements. This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - Brasil (CAPES) - Finance Code 001.

Supplementary material

10570_2018_2232_MOESM1_ESM.docx (2.1 mb)
Supplementary material 1 (DOCX 2109 kb)


  1. Bajpai AK, Mishra A (2004) Ionizable interpenetrating polymer networks of carboxymethyl cellulose and poly(acrylic acid): evaluation of water uptake. J Appl Polym Sci 93:2054–2065. CrossRefGoogle Scholar
  2. Bajpai AK, Mishra A (2005) Preparation and characterization of tetracyclin-loaded interpenetrating polymer networks of carboxymethyl cellulose and poly(acrylic acid): water sorption and drug release study. Polym Int 54:1347–1356. CrossRefGoogle Scholar
  3. Benaïssa H, Elouchdi MA (2007) Removal of copper ions from aqueous solutions by dried sunflower leaves. Chem Eng Process Process Intensif 46:614–622. CrossRefGoogle Scholar
  4. Bueno VB, Petri DFS (2014) Xanthan hydrogel films: molecular conformation, charge density and protein carriers. Carbohydr Polym 101:897–904. CrossRefPubMedGoogle Scholar
  5. Bueno VB, Bentini R, Catalani LH, Petri DFS (2013) Synthesis and swelling behavior of xanthan-based hydrogels. Carbohydr Polym 92:1091–1099. CrossRefPubMedGoogle Scholar
  6. Cai Y, Yuan F, Wang X et al (2017) Synthesis of core–shell structured Fe3O4@carboxymethyl cellulose magnetic composite for highly efficient removal of Eu(III. Cellulose 24:175. CrossRefGoogle Scholar
  7. Crini G (2005) Recent developments in polysaccharide-based materials used as adsorbents in wastewater treatment. Prog Polym Sci 30:38–70. CrossRefGoogle Scholar
  8. Dai H, Ou S, Huang Y, Liu Z, Huang H (2017) Enhanced swelling and multiple-responsive properties of gelatin/sodium alginate hydrogels by the addition of carboxymethyl cellulose isolated from pineapple peel. Cellulose 25:593–606. CrossRefGoogle Scholar
  9. Deville S (1993) Ice-templating, freeze-casting: beyond material processing. J Mater Res 28:2202–2219CrossRefGoogle Scholar
  10. Dragan ES (2014) Design and applications of interpenetrating polymer network hydrogels. A review. Chem Eng J 243:572–590. CrossRefGoogle Scholar
  11. Eftekhari-Sis B, Rahimkhoei V, Akbari A, Araghi HY (2018) Cubic polyhedral oligomeric silsesquioxane nano-cross-linked hybrid hydrogels: synthesis, characterization, swelling and dye adsorption properties. React Funct Polym 128:47–57. CrossRefGoogle Scholar
  12. Fekete T, Borsa J, Takács E et al (2014) Synthesis of cellulose derivative based superabsorbent hydrogels by radiation induced crosslinking. Cellulose 21:4157. CrossRefGoogle Scholar
  13. Foo KY, Hameed BH (2010) Insights into the modeling of adsorption isotherm systems. Chem Eng J 156:2–10. CrossRefGoogle Scholar
  14. Giannouli P, Morris ER (2003) Cryogelation of xanthan. Food Hydrocolloids 17:495–501. CrossRefGoogle Scholar
  15. Gibson LJ, Ashby MF (1997) Cellular solids: structure and properties, 2nd edn. Cambridge University Press, CambridgeCrossRefGoogle Scholar
  16. Heinze T, Koschella A (2005) Carboxymethyl ethers of cellulose and starch: a review. Macromol Symp 223:13–40. CrossRefGoogle Scholar
  17. Impert O, Katafias A, Kita P, Mills A, Pietkiewicz-Graczyk A, Wrzeszcz G (2003) Kinetics and mechanism of a fast leuco-methylene blue oxidation by copper(II)–halide species in acidic aqueous media. Dalton Trans 0:348–353. CrossRefGoogle Scholar
  18. Li Y, Shoemaker CF, Ma J, Shen X, Zhong F (2008) Paste viscosity of rice starches of different amylose content and carboxymethylcellulose formed by dry heating and the physical properties of their films. Food Chem 109:616–623. CrossRefGoogle Scholar
  19. Lin Q, Gao M, Chang J, Ma H (2016) Adsorption properties of crosslinking carboxymethyl cellulose grafting dimethyldiallylammonium chloride for cationic and anionic dyes. Carbohydr Polym 151:283–294. CrossRefPubMedGoogle Scholar
  20. Liu Y, Wang W, Wang A (2010) Adsorption of lead ions from aqueous solution by using carboxymethyl cellulose-g-poly (acrylic acid)/attapulgite hydrogel composites. Desalination 259:258–264. CrossRefGoogle Scholar
  21. Marani PL, Bloisi GD, Petri DFS (2015) Hydroxypropylmethyl cellulose films crosslinked with citric acid for control release of nicotine. Cellulose 22:3907–3918CrossRefGoogle Scholar
  22. Mariano M, Hantao LW, Bernardes JS, Strauss M (2018) Microstructural characterization of nanocellulose foams prepared in the presence of cationic surfactants. Carbohydr Polym 195:153–162. CrossRefPubMedGoogle Scholar
  23. Martins BF, Toledo PVO, Petri DFS (2017) Hydroxypropyl methylcellulose based aerogels: synthesis, characterization and application as adsorbents for wastewater pollutants. Carbohydr Polym 155:173–181. CrossRefPubMedGoogle Scholar
  24. Ngah WSW, Fatinathan S (2008) Adsorption of Cu(II) ions in aqueous solution using chitosan beads, chitosan–GLA beads and chitosan–alginate beads. Chem Eng J 143:62–72. CrossRefGoogle Scholar
  25. Roland CM (2013) Interpenetrating polymer networks (IPN): structure and mechanical behavior. In: Kobayashi S, Müllen K (eds) Encyclopedia of polymeric nanomaterials. Springer, Berlin. CrossRefGoogle Scholar
  26. Saber-Samandari S, Saber-Samandari S, Heydaripour S, Abdouss M (2016) Novel carboxymethyl cellulose based nanocomposite membrane: synthesis, characterization and application in water treatment. J Environ Manag 166:457–465. CrossRefGoogle Scholar
  27. Scotti KL, Dunand DC (2018) Freeze casting: a review of processing, microstructure and properties via the open data repository, Prog Mater Sci 94:243–305. CrossRefGoogle Scholar
  28. Seki Y, Altinisik A, Demircioğlu B, Tetik C (2014) Carboxymethylcellulose (CMC)–hydroxyethylcellulose (HEC) based hydrogels: synthesis and characterization. Cellulose 21:1689–1698. CrossRefGoogle Scholar
  29. Silverstein RM, Webster FX, Kiemle DJ, Bryce DL (2014) Spectrometric identification of organic compounds, 8th edn. Wiley, New YorkGoogle Scholar
  30. Smirnova I, Gurikov P (2017) Aerogels in chemical engineering: strategies toward tailor-made aerogels. Annu Rev Chem Biomol Eng 8:1410–1428. CrossRefGoogle Scholar
  31. Soares KV, Masini JC, Torresi RM, Carmona-Ribeiro AM, Petri DFS (2005) Hybrid particles of polystyrene and carboxymethyl cellulose as substrates for copper ions. Langmuir 21:8515–8519. CrossRefPubMedGoogle Scholar
  32. Souza IFT, Petri DFS (2018) β-Cyclodextrin hydroxypropyl methylcellulose hydrogels for bisphenol A adsorption. J Mol Liq 266:640–648. CrossRefGoogle Scholar
  33. Thielking H, Schmidt M (2012) Ullmann encyclopedia of industrial chemistry, vol 7. Wiley, Weinheim, pp 381–397Google Scholar
  34. Tran HN, You SJ, Hosseini-Bandegharaei A, Chao HP (2017) Mistakes and inconsistencies regarding adsorption of contaminants from aqueous solutions: a critical review. Water Res 120:88–116. CrossRefPubMedGoogle Scholar
  35. Vasić S, Grobéty B, Kuebler J, Graule T, Baumgartner L (2007) X-ray computed micro tomography as complementary method for the characterization of activated porous ceramic preforms. J Mater Res 22:1414–1424. CrossRefGoogle Scholar
  36. Wang W, Wang Q, Wang A (2011) PH-responsive carboxymethylcellulose-g poly (sodium acrylate)/poly(vinylpyrrolydone) semi-IPN hydrogels withenhanced responsive and swelling properties. Macromol Res 19:57–65. CrossRefGoogle Scholar
  37. Weber JW, Morris JC (1963) Kinetics of adsorption of carbon from solution. J Sanit Eng Div Am Soc Civ Eng 89:31–39Google Scholar
  38. Yang S, Fu S, Liu H, Zhou Y, Li X (2010) Hydrogel beads based on carboxymethyl cellulose for removal heavy metal ions. J Appl Polym Sci 119:1204–1210. CrossRefGoogle Scholar
  39. Zirak M, Abdollahiyan A, Eftekhari-Sis B, Saraei M (2017) Carboxymethyl cellulose coated Fe3O4@SiO2 core–shell magnetic nanoparticles for methylene blue removal: equilibrium, kinetic, and thermodynamic studies. Cellulose 25:503–515. CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.Institute of ChemistryUniversity of São PauloSão PauloBrazil

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