Fabrication of pristine-multiwalled carbon nanotubes/cellulose acetate composites for removal of methylene blue

  • Mónica A. SilvaEmail author
  • L. Hilliou
  • M. T. Pessoa de Amorim
Original Paper


Here, we report the effect of mixing different amounts of pristine-multiwalled carbon nanotubes (p-MWCNTs) with the cellulose acetate (CA) on dye removal. The p-MWCNTs loadings of the composites were varied from 0 to 1.0 wt%, and the non-solvent-induced phase separation methodology was used to fabricate the composite membranes, which were extensively characterized. The rheological tests confirmed that with 1.0 wt% of p-MWCNTs there was a classical filler effect in the viscoelastic behavior of the composite solution, but with no percolation of CNTs. The ATR-FTIR spectra identified specific interactions between CNTs and acetate groups of CA. SEM images showed a top dense layer sustained by a porous support layer consisting of a sponge-like structure in the middle layer. Aggregates of CNTs were seen at higher loadings of CNTs (> 0.1 wt%). The XRD diffractograms of composite membranes showed peak shifts compared to CA membranes due to the presence of CNTs into the CA structure, and their thermal stability was effective up to 320 °C. From the water permeability experiments, the calculated values of the membrane hydraulic resistance (Rm) of the composites were higher since a dense top layer and reduced pore size were achieved. Among all the composite membranes, M7 and M8 had the most desirable antifouling properties due to the high surface hydrophilicity imparted by the CNTs, and also showed an improvement in the removal of methylene blue (MB).


Carbon nanotubes Polymer composites Membrane fabrication Adsorption Dye removal 



M. Silva acknowledges funding for this study through an Individual postdoctoral grant from Fundação para a Ciência e a Tecnologia (PROJECT UID/CTM/00264/2013). L. Hilliou thanks the Fundação para a Ciência e a Tecnologia (FCT) for an Investigator contract (IF/00606/2014). The authors thank to NECL (Network of Extreme Conditions Laboratory, IFIMUP, Porto, Portugal) for the XRD measurements and SEMAT (UMinho, Guimarães, Portugal) for SEM analysis. Besides, Dr. Silva acknowledges Professor I. Escobar and Dr. P. Wagh from University of Kentucky, USA, for proof reading and helpful discussions.

Supplementary material

289_2019_2769_MOESM1_ESM.docx (289 kb)
Supplementary material 1 (DOCX 288 kb)


  1. 1.
    Watkins K (2006) Human development report 2006. In: Ross-Larson B, de Coquereaumont M, Trott C (eds) Beyond scarcity: power, poverty and the global water crisis. The United Nations Development Programme, New YorkGoogle Scholar
  2. 2.
    Palmate SS, Pandey A, Kumar D, Pandey RP, Mishra SK (2017) Climate change impact on forest cover and vegetation in Betwa Basin, India. Appl Water Sci 7:103–114. CrossRefGoogle Scholar
  3. 3.
    Zahid M, Rashid A, Akram S, Rehan ZA, Razzaq W (2018) A comprehensive review on polymeric nano-composite membranes for water treatment. J Membrane Sci Technol 8(1):179–198. CrossRefGoogle Scholar
  4. 4.
    Kocurek P, Kolomazník K, Bařinová M (2014) Chromium removal from wastewater by reverse osmosis. WSEAS Trans Environ Dev 10:358–365Google Scholar
  5. 5.
    Kebede F, Gashaw A (2016) Removal of chromium and azo metal-complex dyes using activated carbon synthesized from tannery wastes. Open Access J Sci Technol. Google Scholar
  6. 6.
    Inyinbor Adejumoke A, Adebesin Babatunde O, Oluyori Abimbola P, Adelani-Akande Tabitha A, Dada Adewumi O, Oreofe Toyin A (2018) Water pollution: effects, prevention, and climatic impact. In: Water challenges of an urbanizing world. Matjaž Glavan, IntechOpen.
  7. 7.
    Zhang B, Song X, Nghiem LD, Li G, Luo W (2017) Osmotic membrane bioreactors for wastewater reuse: performance comparison between cellulose triacetate and polyamide thin film composite membranes. J Membrane Sci 539:383–391. CrossRefGoogle Scholar
  8. 8.
    Korenak J, Hélix-Nielsen C, Bukšek H, Petrinić I (2019) Efficiency and economic feasibility of forward osmosis in textile wastewater treatment. J Clean Prod 210:1483–1495. CrossRefGoogle Scholar
  9. 9.
    Zou S, He Z (2016) Enhancing wastewater reuse by forward osmosis with self-diluted commercial fertilizer as draw solutes. Water Res 99:235–243. CrossRefGoogle Scholar
  10. 10.
    Pu S, Xue S, Yang Z, Hou Y, Zhu R, Chu W (2018) In situ co-precipitation preparation of a superparamagnetic graphene oxide/Fe3O4 nanocomposite as an adsorbent for wastewater purification: synthesis, characterization, kinetics, and isotherm studies. Environ Sci Pollut Res 25(18):17310–17320. CrossRefGoogle Scholar
  11. 11.
    Prazeres AR, Rivas J, Almeida MA, Patainta M, Dores J, Carvalho F (2016) Agricultural reuse of cheese whey wastewater treated by NaOH precipitation for tomato production under several saline conditions and sludge management. Agric Water Manag 167:62–74. CrossRefGoogle Scholar
  12. 12.
    Shiva Shankar Y, Ankur K, Bhushan P, Mohan D (2019) Utilization of water treatment plant (WTP) sludge for pretreatment of dye wastewater using coagulation/flocculation. In: Kalamdhad A, Singh J, Dhamodharan K (eds) Advances in waste management. Springer, Singapore. Google Scholar
  13. 13.
    Da Silva LF, Barbos AD, de Paula HM, Ramuldo LL, Andrade LS (2016) Treatment of paint manufacturing wastewater by coagulation/electrochemical methods: proposal for disposal and/or reuse of treated water. Water Res 101:467–475. CrossRefGoogle Scholar
  14. 14.
    Bousbih S, Errais E, Ben Amar R, Duplay J, Trabelsi-Ayadi M, Darragi F (2019) Elaboration and characterization of new ceramic ultrafiltration membranes from natural clay: application of treatment of textile wastewater. In: Doronzo D, Schingaro E, Armstrong-Altrin J, Zoheir B (eds) Petrogenesis and exploration of the earth’s interior Advances in science, technology and innovation (IEREK Interdisciplinary Series for Sustainable Development). Springer, Cham. Google Scholar
  15. 15.
    Benito A, Garcia G, Gonzalez-Olmos F (2017) Fouling reduction by UV-based pretreatment in hollow fiber ultrafiltration membranes for urban wastewater reuse. J Membrane Sci 536:141–147. CrossRefGoogle Scholar
  16. 16.
    Jiang M, Ye K, Deng J, Lin J, Ye W, Zhao S, Van der Bruggen B (2018) Conventional ultrafiltration as effective strategy for dye/salt fractionation in textile wastewater treatment. Environ Sci Technol 52(18):10698–10708. CrossRefGoogle Scholar
  17. 17.
    Chávez AM, Gimeno O, Rey A, Pliego G, Oropesa AL, Álvarez PM, Beltrán FJ (2019) Treatment of highly polluted industrial wastewater by means of sequential aerobic biological oxidation-ozone based AOPs. Chem Eng J 361:89–98. CrossRefGoogle Scholar
  18. 18.
    Paździor K, Bilińska L, Ledakowicz S (2018) A review of the existing and emerging technologies in the combination of AOPs and biological processes in industrial textile wastewater treatment. Chem Eng J. Google Scholar
  19. 19.
    Dharupaneedi SP, Nataraj SK, Nadagouda M, Reddy KR, Shukla SS, Aminabhavi TM (2019) Membrane-based separation of potential emerging pollutants. Sep Purif Technol 210:850–866. CrossRefGoogle Scholar
  20. 20.
    Peydayesh M, Mohammadi T, Bakhtiari O (2018) Effective treatment of dye wastewater via positively charged TETA-MWCNT/PES hybrid nanofiltration membranes. Sep Purif Technol 194:488–502. CrossRefGoogle Scholar
  21. 21.
    Karisma D, Febrianto G, Mangindaan D (2018) Polyetherimide thin film composite (PEI-TFC) membranes for nanofiltration treatment of dyes wastewater. In: IOP Conference series: earth and environmental science, vol 195, p 012057.
  22. 22.
    Warsinger D, Chakraborty SW, Tow E, Plumlee M, Bellona C, Loutatidou S, Karimi L, Mikelonis AM, Achilli A, Ghassemi A, Padhye L, Snyder SA, Curcio S, Vecitis CD, Arafat H, Lienhard JH (2018) A review of polymeric membranes and processes for potable water reuse. Progr Polym Sci 81:209–237. CrossRefGoogle Scholar
  23. 23.
    Saraswathi ASA, Rana D, Alwarappan S, Gowrishankar S, Kanimozhi P, Nagendran A (2019) Cellulose acetate ultrafiltration membranes customized with bio-inspired polydopamine coating and in situ immobilization of silver nanoparticles. New J Chem. Google Scholar
  24. 24.
    Etemadi H, Yegani R, Seyfollahi M (2017) The effect of amino functionalized and polyethylene glycol grafted nanodiamond on antibiofouling properties of cellulose acetate membrane in membrane bioreactor systems. Sep Purif Technol 177:350–362. CrossRefGoogle Scholar
  25. 25.
    Nam B-U, Min K-D, Son Y (2015) Investigation of the nanostructure, thermal stability, and mechanical properties of polylactic acid/cellulose acetate butyrate/clay nanocomposites. Mater Lett 150:118–121. CrossRefGoogle Scholar
  26. 26.
    Yu J-G, Zhao X-H, Yang H, Chen X-H, Yang Q, Lin YY, Jiang J-H, Chen X-Q (2014) Aqueous adsorption and removal of organic contaminants by carbon nanotubes. Sci Total Environ 482–483:241–251. CrossRefGoogle Scholar
  27. 27.
    Eskandarian L, Arami M, Pajootan E (2014) Evaluation of adsorption characteristics of multiwalled carbon nanotubes modified by a poly(propylene imine) dendrimer in single and multiple dye solutions: isotherms, kinetics, and thermodynamics. J Chem Eng Data 59:444–454. CrossRefGoogle Scholar
  28. 28.
    Kar S, Bindal RC, Tewari PK (2012) Carbon nanotube membranes for desalination and water purification: challenges and opportunities. Nano Today 7:385–389. CrossRefGoogle Scholar
  29. 29.
    Nezam El-Din LA, El-Gendi A, Ismail N, Abed KA, Ahmed AI (2015) Evaluation of cellulose acetate membrane with carbon nanotubes additives. J Ind Eng Chem 26:259–264. CrossRefGoogle Scholar
  30. 30.
    Kunst B, Sourirajan S (1974) An approach to the development of cellulose acetate ultrafiltration membranes. J Appl Polym Sci 18(11):3423–3434. CrossRefGoogle Scholar
  31. 31.
    Zhang J, Xu Z, Mai W, Min C, Zhou B, Shan M, Li Y, Yang C, Wang Z, Qian X (2013) Improved hydrophilicity, permeability, antifouling and mechanical performance of PVDF composite ultrafiltration membranes tailored by oxidized low-dimensional carbon nanomaterials. J Mater Chem A 1:3101–3111. CrossRefGoogle Scholar
  32. 32.
    Jie G, Kongyin Z, Xinxin Z, Zhijiang C, Min C, Tian C, Junfu W (2015) Preparation and characterization of carboxyl multi-walled carbon nanotubes/calcium alginate composite hydrogel nanofiltration membrane. Mater Lett 157:112–115. CrossRefGoogle Scholar
  33. 33.
    Wee W-K, Mackley MR (1998) The rheology and processing of a concentrated cellulose acetate solution. Chem Eng Sci 53(6):1131–1144. CrossRefGoogle Scholar
  34. 34.
    Kadla JF, Korehei R (2010) Effect of hydrophilic and hydrophobic interactions on the rheological behavior and microstructure of a ternary cellulose acetate system. Biomacromol 11:1074–1081. CrossRefGoogle Scholar
  35. 35.
    Waheed S, Ahmad A, Khan SM, Jamil T, Islam A, Hussain T (2014) Synthesis, characterization, permeation and antibacterial properties of cellulose acetate/polyethylene glycol membranes modified with chitosan. Desalination 351:59–69. CrossRefGoogle Scholar
  36. 36.
    Majeed S, Fierro D, Buhr K, Wind J, Du B, Boschetti-de-Fierro A, Abetz V (2012) Multiwalled carbon nanotubes (MWCNTs) mixed polyacrylonitrile (PAN) ultrafiltration membranes. J Memb Sci 403–404:101–109. CrossRefGoogle Scholar
  37. 37.
    Sinha MK, Purkait MK (2015) Preparation of novel thermo-responsive PSF membrane, with cross linked PVCL-co-PSF copolymer for protein separation and easy cleaning. RSC Adv 5:22609–22619. CrossRefGoogle Scholar
  38. 38.
    Hassan M, Berglund L, Abou-Zeid R, Hassan E, Abou-Elseoud W, Oksman K (2019) Nanocomposite film based on cellulose acetate and lignin-rich rice straw nanofibers. Materials 12(4):595–611. CrossRefGoogle Scholar
  39. 39.
    Chakoli AN, Sui J, Amirian M, Cai W (2011) Crystallinity of biodegradable polymers reinforced with functionalized carbon nanotubes. J Polym Res 18:1249–1259. CrossRefGoogle Scholar
  40. 40.
    Saini B, Sinha MK (2018) Effect of hydrophilic poly(ethylene glycol) methyl ether additive on the structure, morphology, and performance of polysulfone flat sheet ultrafiltration membrane. J Appl Polym Sci 135:47163–47176. Google Scholar
  41. 41.
    Rodriguez FJ, Galotto MJ, Guarda A, Bruna JE (2012) Modification of cellulose acetate films using nanofillers based on organoclays. J Food Eng 110:262–268. CrossRefGoogle Scholar
  42. 42.
    Ashraf N (2012) Carbon nanotubes-cellulose acetate nanocomposites. Doctoral Dissertation, American University in Cairo, EgyptGoogle Scholar
  43. 43.
    Nakamura K, Matsumoto K (2006) Protein adsorption properties on a microfiltration membrane: a comparison between static and dynamic adsorption methods. J Memb Sci 285(1–2):126–136. CrossRefGoogle Scholar
  44. 44.
    Ai L, Zhang C, Liao F, Wang Y, Li M, Meng L, Jiang J (2011) Removal of methylene blue from aqueous solution with magnetite loaded multiwall carbon nanotube: kinetic, isotherm and mechanism analysis. J Hazard Mater 198:282–290. CrossRefGoogle Scholar
  45. 45.
    Xiong L, Yang Y, Mai JX, Sun WL, Zhang CY, Wei DP, Chen Q, Ni JR (2010) Adsorption behavior of methylene blue onto titanate nanotubes. Chem Eng J 156:313–320. CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Center for Science and Technology, Department of Textile EngineeringUniversity of MinhoGuimarãesPortugal
  2. 2.Institute for Polymers and Composites/I3NUniversity of MinhoGuimarãesPortugal

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