Improved adsorption performance of rubber-based hydrogel: optimisation through response surface methodology, isotherm, and kinetic studies


Batch adsorption experiments were carried out for the removal of methylene blue (MB) cationic dye from its aqueous solution using rubber-based hydrogel. In this work, the adsorption of two rubber-based hydrogels, namely maleated liquid natural rubber/acrylic acid hydrogel (LNR-g-MaH/AAc) and maleated liquid natural rubber/acrylic acid/montmorillonite hydrogel (LNR-g-MaH/AAc/MMT), was optimised by response surface methodology (RSM) using a central composite rotatable design (CCRD). The effects of various parameters, such as adsorbent mass and initial concentrations of MB, were examined. The hydrogels were characterised using field emission scanning electron microscopy, thermogravimetric analysis (TGA), and fourier-transform infrared (FTIR). A total of 13 experiments were conducted to establish a quadratic model. Among those two rubber-based hydrogels, LNR-g-MaH/AAc/MMT hydrogel had higher optimum adsorption efficiency with 99.07% of dye removal percentage. The optimum dye performance of LNR-g-MaH/AAc hydrogel was also effective as the dye removal percentage was about 95.46%. Those responses were recorded when the adsorbent mass and initial concentration of MB were optimally set as 0.55 g, and 5.50 mg L−1, respectively. The Freundlich isotherm model was found to be best fitted to adsorption for those two hydrogels. The maximum adsorption capacities were 1.85 mg/g for LNR-g-MaH/AAc and 9.74 mg/g for LNR-g-MaH/AAc. Two kinetic models were tested to correlate the experimental data and the sorption was discovered to fit well with the pseudo-second-order kinetic model. It was found that by introducing of montmorillonite (MMT) could improve the adsorption ability of the LNR-g-MaH/AAc hydrogel.


  • We show that rubber-based hydrogel performs the best when intercalated with montmorillonite.

  • Rubber-based hydrogel with montmorillonite shows better adsorption capability towards methylene blue.

  • Rubber-based hydrogel has thermal stability and usable in any aqueous solution.

This is a preview of subscription content, access via your institution.

Scheme 1
Scheme 2
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5


  1. 1.

    Chiou M-S, Ho P-Y, Li H-Y (2004) Adsorption of anionic dyes in acid solutions using chemically cross-linked chitosan beads. Dye Pigment 60:69–84

    CAS  Google Scholar 

  2. 2.

    Dastkhoon M, Ghaedi M, Asfaram A et al. (2017) Improved adsorption performance of nanostructured composite by ultrasonic wave: Optimization through response surface methodology, isotherm and kinetic studies. Ultrason Sonochem 37:94–105

    CAS  Google Scholar 

  3. 3.

    Liu C, Omer AM, Ouyang X (2018) Adsorptive removal of cationic methylene blue dye using carboxymethyl cellulose/k-carrageenan/activated montmorillonite composite beads: isotherm and kinetic studies. Int J Biol Macromol 106:823–833

    CAS  Google Scholar 

  4. 4.

    Mandal B, Ray SK (2016) Removal of safranine T and brilliant cresyl blue dyes from water by carboxy methyl cellulose incorporated acrylic hydrogels: isotherms, kinetics and thermodynamic study. J Taiwan Inst Chem Eng 60:313–327

    CAS  Google Scholar 

  5. 5.

    Mohammadzadeh Pakdel P, Peighambardoust SJ (2018) A review on acrylic based hydrogels and their applications in wastewater treatment. J Environ Manag 217:123–143

    CAS  Google Scholar 

  6. 6.

    Vudjung C, Saengsuwan S (2017) Synthesis and properties of biodegradable hydrogels based on cross-linked natural rubber and cassava starch. J Elastomers Plast 49:574–594

    CAS  Google Scholar 

  7. 7.

    Mohamed MA, W. Salleh WN, Jaafar J et al. (2017) Physicochemical characterization of cellulose nanocrystal and nanoporous self-assembled CNC membrane derived from Ceiba pentandra. Carbohydr Polym 157:1892–1902

    CAS  Google Scholar 

  8. 8.

    Rosman N, Salleh WN, Mohamed MA et al. (2018) Hybrid membrane filtration-advanced oxidation processes for removal of pharmaceutical residue. J Colloid Interface Sci 532:236–260

    CAS  Google Scholar 

  9. 9.

    Mohamed MA, Awang NA, Salleh WNW, Ismail AF (2019) Introduction to green polymeric membranes. In: Bio monomers for green polymeric composite materials. John Wiley & Sons, Inc., Chichester, p 95–116

  10. 10.

    Alias NH, Jaafar J, Samitsu S et al. (2020) Mechanistic insight of the formation of visible-light responsive nanosheet graphitic carbon nitride embedded polyacrylonitrile nanofibres for wastewater treatment. J Water Process Eng 33:101015

    Google Scholar 

  11. 11.

    Mutalib MA, Aziz F, Jamaludin NA et al. (2018) Enhancement in photocatalytic degradation of methylene blue by LaFeO3-GO integrated photocatalyst-adsorbents under visible light irradiation. Korean J Chem Eng 35:548–556

    Google Scholar 

  12. 12.

    Mohamed MA, W. Salleh WN, Jaafar J et al. (2016) Regenerated cellulose membrane as bio-template for in-situ growth of visible-light driven C-modified mesoporous titania. Carbohydr Polym 146:166–173

    CAS  Google Scholar 

  13. 13.

    Popli S, Patel UD (2015) Destruction of azo dyes by anaerobic–aerobic sequential biological treatment: a review. Int J Environ Sci Technol 12:405–420

    CAS  Google Scholar 

  14. 14.

    Sarvajith M, Reddy GKK, Nancharaiah YV (2018) Textile dye biodecolourization and ammonium removal over nitrite in aerobic granular sludge sequencing batch reactors. J Hazard Mater 342:536–543

    CAS  Google Scholar 

  15. 15.

    Chen D, Zeng Z, Zeng Y et al. (2016) Removal of methylene blue and mechanism on magnetic γ-Fe2O3/SiO2 nanocomposite from aqueous solution. Water Resour Ind 15:1–13

    Google Scholar 

  16. 16.

    Wang L, Zhang J, Wang A (2008) Removal of methylene blue from aqueous solution using chitosan-g-poly(acrylic acid)/montmorillonite superadsorbent nanocomposite. Colloids Surf A Physicochem Eng Asp 322:47–53

    CAS  Google Scholar 

  17. 17.

    Ahmed EM (2015) Hydrogel: preparation, characterization, and applications: a review. J Adv Res 6:105–121

    CAS  Google Scholar 

  18. 18.

    Sabadini RC, Silva MM, Pawlicka A, Kanicki J (2018) Gellan gum-O,O′-bis(2-aminopropyl)-polyethylene glycol hydrogel for controlled fertilizer release. J Appl Polym Sci 135:45636

    Google Scholar 

  19. 19.

    Lim LS, Ahmad I, Mat Lazim A (2015) pH Sensitive hydrogel based on poly(acrylic acid) and cellulose nanocrystals. Sains Malaysiana 44:779–785

    CAS  Google Scholar 

  20. 20.

    Zhou Y, Zhao Y, Wang L et al. (2012) Radiation synthesis and characterization of nanosilver/gelatin/carboxymethyl chitosan hydrogel. Radiat Phys Chem 81:553–560

    CAS  Google Scholar 

  21. 21.

    Aflaki Jalali M, Dadvand Koohi A, Sheykhan M (2016) Experimental study of the removal of copper ions using hydrogels of xanthan, 2-acrylamido-2-methyl-1-propane sulfonic acid, montmorillonite: Kinetic and equilibrium study. Carbohydr Polym 142:124–132

    CAS  Google Scholar 

  22. 22.

    Fosso-Kankeu E, Mittal H, Waanders F, Ray SS (2017) Thermodynamic properties and adsorption behaviour of hydrogel nanocomposites for cadmium removal from mine effluents. J Ind Eng Chem 48:151–161

    CAS  Google Scholar 

  23. 23.

    Nakhjiri MT, Marandi GB, Kurdtabar M (2018) Poly(AA-co-VPA) hydrogel cross-linked with N-maleyl chitosan as dye adsorbent: Isotherms, kinetics and thermodynamic investigation. Int J Biol Macromol 117:152–166

    CAS  Google Scholar 

  24. 24.

    Paulino AT, Guilherme MR, Reis AV et al. (2006) Removal of methylene blue dye from an aqueous media using superabsorbent hydrogel supported on modified polysaccharide. J Colloid Interface Sci 301:55–62

    CAS  Google Scholar 

  25. 25.

    Salama A, Shukry N, El-Sakhawy M (2015) Carboxymethyl cellulose-g-poly(2-(dimethylamino) ethyl methacrylate) hydrogel as adsorbent for dye removal. Int J Biol Macromol 73:72–75

    CAS  Google Scholar 

  26. 26.

    Abdel-Halim ES, Al-Deyab SS (2014) Preparation of poly(acrylic acid)/starch hydrogel and its application for cadmium ion removal from aqueous solutions. React Funct Polym 75:1–8

    CAS  Google Scholar 

  27. 27.

    Amnuaypanich S, Kongchana N (2009) Natural rubber/poly(acrylic acid) semi-interpenetrating polymer network membranes for the pervaporation of water-ethanol mixtures. J Appl Polym Sci 114:3501–3509

    CAS  Google Scholar 

  28. 28.

    Firdaus F, Idris MSF, Yusoff SFM (2019) Adsorption of nickel ion in aqueous using rubber-based hydrogel. J Polym Environ 27:1770–1780

    CAS  Google Scholar 

  29. 29.

    Mohd Noor NF, Yusoff SFM (2020) Ultrasonic-enhanced synthesis of rubber-based hydrogel for waste water treatment: kinetic, isotherm and reusability studies. Polym Test 81:106200

    Google Scholar 

  30. 30.

    Mohamed MA, Salleh WNW, Jaafar J et al. (2015) Incorporation of N-doped TiO2 nanorods in regenerated cellulose thin films fabricated from recycled newspaper as a green portable photocatalyst. Carbohydr Polym 133:429–437

    CAS  Google Scholar 

  31. 31.

    Yi D, Yang H, Zhao M et al. (2017) A novel, low surface charge density, anionically modified montmorillonite for polymer nanocomposites. RSC Adv 7:5980–5988

    CAS  Google Scholar 

  32. 32.

    Mahdavinia GR, Aghaie H, Sheykhloie H et al. (2013) Synthesis of CarAlg/MMt nanocomposite hydrogels and adsorption of cationic crystal violet. Carbohydr Polym 98:358–365.

    Article  CAS  Google Scholar 

  33. 33.

    Purwanto M, Atmaja L, Mohamed MA et al. (2016) Biopolymer-based electrolyte membranes from chitosan incorporated with montmorillonite-crosslinked GPTMS for direct methanol fuel cells. RSC Adv 6:2314–2322

    CAS  Google Scholar 

  34. 34.

    He F, Zhou Q, Wang L et al. (2019) Fabrication of a sustained release delivery system for pesticides using interpenetrating polyacrylamide/alginate/montmorillonite nanocomposite hydrogels. Appl Clay Sci 183:105347

    CAS  Google Scholar 

  35. 35.

    Tekay E, Aydınoğlu D, Şen S (2019) Effective adsorption of Cr(VI) by high strength chitosan/montmorillonite composite hydrogels involving spirulina biomass/microalgae. J Polym Environ 27:1828–1842

    CAS  Google Scholar 

  36. 36.

    Olad A, Zebhi H, Salari D et al. (2018) A promising porous polymer-nanoclay hydrogel nanocomposite as water reservoir material: synthesis and kinetic study. J Porous Mater 25:665–675

    CAS  Google Scholar 

  37. 37.

    Jesus CRN, Molina EF, Pulcinelli SH, Santilli CV (2018) Highly controlled diffusion drug release from ureasil–poly(ethylene oxide)–Na+–montmorillonite hybrid hydrogel nanocomposites. ACS Appl Mater Interfaces 10:19059–19068

    CAS  Google Scholar 

  38. 38.

    Alver E, Metin Aü (2012) Anionic dye removal from aqueous solutions using modified zeolite: adsorption kinetics and isotherm studies. Chem Eng J 200–202:59–67

    Google Scholar 

  39. 39.

    Kargarzadeh H, Ahmad I, Abdullah I et al. (2015) Functionalized liquid natural rubber and liquid epoxidized natural rubber: a promising green toughening agent for polyester. J Appl Polym Sci 132:41292–411307

    Google Scholar 

  40. 40.

    Nakason C, Kaesaman A, Supasanthitikul P (2004) The grafting of maleic anhydride onto natural rubber. Polym Test 23:35–41

    CAS  Google Scholar 

  41. 41.

    Wan T, Huang R, Zhao Q et al. (2013) Synthesis of wheat straw composite superabsorbent. J Appl Polym Sci 130:3404–3410

    CAS  Google Scholar 

  42. 42.

    Mittal H, Maity A, Sinha Ray S (2015) The adsorption of Pb2+ and Cu2+ onto gum ghatti-grafted poly(acrylamide-co-acrylonitrile) biodegradable hydrogel: isotherms and kinetic models. J Phys Chem B 119:2026–2039

    CAS  Google Scholar 

  43. 43.

    Langmuir I (1916) The constitution and fundamental properties of solids and liquids. Part I. Solids. J Am Chem Soc 38:2221–2295

    CAS  Google Scholar 

  44. 44.

    Freundlich HMF (1906) Over the adsorption in solution. J Phys Chem 57:385–471

    CAS  Google Scholar 

  45. 45.

    Lagergren S (1898) About the theory of so-called adsorption of soluble substances. K Sven Vetenskapsakademiens Handl 24:1–39

    Google Scholar 

  46. 46.

    Ho Y, McKay G (1999) Pseudo-second order model for sorption processes. Process Biochem 34:451–465

    CAS  Google Scholar 

  47. 47.

    Zhang J, Wang L, Wang A (2007) Preparation and properties of chitosan-g-poly(acrylic acid)/montmorillonite superabsorbent nanocomposite via in situ intercalative polymerization. Ind Eng Chem Res 46:2497–2502

    CAS  Google Scholar 

  48. 48.

    Azhar NHA, Rasid HM, Yusoff SFM (2016) Chemical modifications of liquid natural rubber. In: AIP Conference Proceedings. AIP Publishing LLC, New York, USA, p 030024-1–030024-6

  49. 49.

    Mohamed MA, Jaafar J, Ismail A, et al (2017) Fourier Transform Infrared (FTIR) Spectroscopy. In: Membrane characterization. Elsevier, Amsterdam, Netherlands, p 3–29

  50. 50.

    Wongthong P, Nakason C, Pan Q et al. (2013) Modification of deproteinized natural rubber via grafting polymerization with maleic anhydride. Eur Polym J 49:4035–4046

    CAS  Google Scholar 

  51. 51.

    Sezgin N, Balkaya N (2016) Adsorption of heavy metals from industrial wastewater by using polyacrylic acid hydrogel. Desalin Water Treat 57:2466–2480

    CAS  Google Scholar 

  52. 52.

    Liang R, Yuan H, Xi G, Zhou Q (2009) Synthesis of wheat straw-g-poly(acrylic acid) superabsorbent composites and release of urea from it. Carbohydr Polym 77:181–187

    CAS  Google Scholar 

  53. 53.

    Carone E, Kopcak U, Gonçalves M, Nunes S (2000) In situ compatibilization of polyamide 6/natural rubber blends with maleic anhydride. Polymer 41:5929–5935

    CAS  Google Scholar 

  54. 54.

    Bhullar N, Kumari K, Sud D (2018) A biopolymer-based composite hydrogel for rhodamine 6G dye removal: its synthesis, adsorption isotherms and kinetics. Iran Polym J 27:527–535

    CAS  Google Scholar 

  55. 55.

    Thakur S, Pandey S, Arotiba OA (2016) Development of a sodium alginate-based organic/inorganic superabsorbent composite hydrogel for adsorption of methylene blue. Carbohydr Polym 153:34–46

    CAS  Google Scholar 

  56. 56.

    Bezerra MA, Santelli RE, Oliveira EP et al. (2008) Response surface methodology (RSM) as a tool for optimization in analytical chemistry. Talanta 76:965–977

    CAS  Google Scholar 

  57. 57.

    Shojaeimehr T, Rahimpour F, Khadivi MA, Sadeghi M (2014) A modeling study by response surface methodology (RSM) and artificial neural network (ANN) on Cu2+ adsorption optimization using light expended clay aggregate (LECA). J Ind Eng Chem 20:870–880

    CAS  Google Scholar 

  58. 58.

    Bartels-Caspers C, Tusel-Langer E, Lichtenthaler RN (1992) Sorption isotherms of alcohols in zeolite-filled silicone rubber and in PVA-composite membranes. J Memb Sci 70:75–83

    CAS  Google Scholar 

  59. 59.

    Senthil Kumar P (2014) Adsorption of lead(II) ions from simulated wastewater using natural waste: a kinetic, thermodynamic and equilibrium study. Environ Prog Sustain Energy 33:55–64

    CAS  Google Scholar 

Download references


The authors would like to kindly acknowledge Universiti Kebangsaan Malaysia (UKM) for the research grants (GUP-2017-004) and Centre of Research and Instrumentation (CRIM) at UKM for their facilities.

Author information



Corresponding author

Correspondence to Siti Fairus M. Yusoff.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

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

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Ahmad, N.H., Mohamed, M.A. & Yusoff, S.F.M. Improved adsorption performance of rubber-based hydrogel: optimisation through response surface methodology, isotherm, and kinetic studies. J Sol-Gel Sci Technol 94, 322–334 (2020).

Download citation


  • Rubber
  • Acrylic acid
  • Montmorillonite
  • Adsorption
  • Methylene blue
  • Response surface methodology