Modification of microcrystalline cellulose with acrylamide under microwave irradiation and its application as flocculant

  • Xiuling Yu
  • Xuejiao Huang
  • Changzhuang Bai
  • Xiaopeng XiongEmail author
Research Article


Grafting polyacrylamide (PAM) chains onto microparticles may combine the advantages of the flocculation property of the former and the fast sedimentation of the later to realize better flocculation performance. In this work, inexpensive microcrystalline cellulose (MCC) microparticles, and monomer of acrylamide (AM) were mixed, and then irradiated under microwave. The obtained material was characterized by Fourier transform infrared spectroscopy and X-ray diffraction, and the results demonstrated successful modification of MCC with AM on the particle surface. The modification procedure has been carefully investigated to obtain an optimum preparation condition. Kaolin suspension was selected as a model to evaluate the flocculation properties of the obtained AM-MCC. Our results indicate that the AM-MCC with the highest grafting ratio of 95.5% exhibits the best flocculation performance, which is even better than that of PAM, and the turbidity can be decreased to 1.4% of the naked kaolin suspension within 2.5 min. Therefore, this work provides a low cost strategy to prepare biodegradable AM-MCC, which may have promising potential application in the water treatment and other fields.


Microcrystalline cellulose (MCC) Polyacrylamide Surface modification Microwave Flocculation 


Funding information

This work received financial supports from the Natural Science Foundation of China (51273166) and the Fundamental Research Funds for Xiamen University (20720172007).


  1. Ali I (2012) New generation adsorbents for water treatment. Chem Rev 112:5073–5091CrossRefGoogle Scholar
  2. Antunes E, Garcia FAP, Ferreira P, Blanco A, Negro C, Rasteiro MG (2008) Use of new branched cationic polyacrylamides to improve retention and drainage in papermaking. Ind Eng Chem Res 47(23):9370–9375CrossRefGoogle Scholar
  3. Antunes E, Garcia FAP, Ferreira P, Blanco A, Negro C, Rasteiro MG (2010) Modelling PCC flocculation by bridging mechanism using population balances: effect of polymer characteristics on flocculation. Chem Eng Sci 65(12):3798–9807CrossRefGoogle Scholar
  4. Bai CZ, Huang XJ, Xie F, Xiong XP (2018) Microcrystalline cellulose surface-modified with acrylamide for reinforcement of hydrogels. ACS Sustain Chem Eng 6:12320–12327CrossRefGoogle Scholar
  5. Balea A, Monte MC, de la Fuente E, Negro C, Blanco A (2017) Application of cellulose nanofibers to remove water-based flexographic inks from wastewaters. Environ Sci Pollut Res 24:5049–5059CrossRefGoogle Scholar
  6. Blanco A, Negro C, Fuente E, Tijero J (2005) Effect of shearing forces and flocculant overdose on filler flocculation mechanisms and floc properties. Ind Eng Chem Res 44:9105–9112CrossRefGoogle Scholar
  7. Blanco A, Monte MC, Campano C, Balea A, Merayo N, Negro C (2018) Chapter 5 Nanocellulose for industrial use: cellulose nanofibers (CNF), cellulose nanocrystals (CNC), and bacterial cellulose (BC). In: Hussain CM (ed) Handbook of Nanomaterials for industrial applications. Elsevier, Amsterdam, pp 74–126CrossRefGoogle Scholar
  8. Cadotte M, Tellier ME, Blanco A, Fuente E, van de Ven TGM, Paris J (2007) Flocculation, retention and drainage in papermaking: a comparative study of polymeric additives. Can J Chem Eng 85(2):240–248CrossRefGoogle Scholar
  9. Cai T, Li HJ, Yang R, Wang YW, Li RH, Yang H, Li AM, Cheng RS (2015) Efficient flocculation of an anionic dye from aqueous solutions using a cellulose-based flocculant. Cellulose 22:1439–1449CrossRefGoogle Scholar
  10. Campano C, Lopez-Exposito P, Blanco A, Negro C, van de Ven TGM (2019) Hairy cationic nanocrystalline cellulose as a novel flocculant of clay. J Colloid Interface Sci 545:153–161CrossRefGoogle Scholar
  11. Cao Z, Chen Y, Zhang C, Cheng J, Wu D, Ma W, Liu C, Fu Z (2019) Preparation of near-infrared laser responsive hydrogels with enhanced laser marking performance. Soft Matter 15:2950–2959CrossRefGoogle Scholar
  12. Chen LH, Zhu JY, Baez C, Kitin P, Elder T (2016) Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids. Green Chem 18:3835–3843CrossRefGoogle Scholar
  13. Das R, Ghorai S, Pal S (2013) Flocculation characteristics of polyacrylamide grafted hydroxypropyl methyl cellulose: an efficient biodegradable flocculant. Chem Eng J 229:144–152CrossRefGoogle Scholar
  14. Djibrine BZ, Zheng H, Wang M, Liu S, Tang X, Khan S, Jimenez AN, Feng L (2018) An effective flocculation method to the kaolin wastewater treatment by a cationic polyacrylamide (CPAM): preparation, characterization, and flocculation performance. Int J Polym Sci Article ID 5294251Google Scholar
  15. Ebeling JM, Rishel KL, Sibrell PL (2005) Screening and evaluation of polymers as flocculation aids for the treatment of aquacultural effluents. Aquacult Eng 33:235–249CrossRefGoogle Scholar
  16. French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896CrossRefGoogle Scholar
  17. Girma KB, Lorenz V, Blaurock S, Edelmann FT (2005) Coordination chemistry of acrylamide. Coordin Chem Rev 249:1283–1293CrossRefGoogle Scholar
  18. Guezennec AG, Michel C, Bru K, Touze S, Desroche N, Mnif I, Motelica-Heino M (2015) Transfer and degradation of polyacrylamide-based flocculants in hydrosystems: a review. Environ Sci Pollut Res 22:6390–6406CrossRefGoogle Scholar
  19. Hasan A, Fatehi P (2018) Stability of kaolin dispersion in the presence of lignin-acrylamide polymer. Appl Clay Sci 158:72–82CrossRefGoogle Scholar
  20. Huang XJ, Xie F, Xiong XP (2018) Surface-modified microcrystalline cellulose for reinforcement of chitosan film. Carbohydr Polym 201:367–373CrossRefGoogle Scholar
  21. Kan HMK, Li J, Wijesekera K, Cranston ED (2013) Polymer-grafted cellulose nanocrystals as pH-responsive reversible flocculants. Biomacromolecules 14:3130–3139CrossRefGoogle Scholar
  22. Kang HL, Liu R, Huang Y (2015) Graft modification of cellulose: methods, properties and applications. Polymer 70:A1–A16CrossRefGoogle Scholar
  23. Klemm D, Heublein B, Fink HP, Bohn A (2005) Cellulose: fascinating biopolymer and sustainable raw material. Angew Chem Int Ed 44:3358–3393CrossRefGoogle Scholar
  24. Kopperud HM, Hansen FK, Nystrom B (1998) Effect of surfactant and temperature on the rheological properties of aqueous solutions of unmodified and hydrophobically modified polyacrylamide. Macromol Chem Phys 199:2385–2394CrossRefGoogle Scholar
  25. Lee CS, Robinson J, Chong MF (2014) A review on application of flocculants in wastewater treatment. Process Saf Environ 92:489–508CrossRefGoogle Scholar
  26. Lewandowska K (2006) Comparative studies of rheological properties of polyacrylamide and partially hydrolyzed polyacrylamide solutions. J Appl Polym Sci 103:2235–2241CrossRefGoogle Scholar
  27. Liu DH, Luo W, Lin CX, Du CY, Liu MH (2015a) Preparation of cellulose graft copolymer based on the combination of ionic liquids and microwave heating. Mater Res Innov 19:566–569Google Scholar
  28. Liu L, Gao ZY, Su XP, Chen X, Jiang L, Yao JM (2015b) Adsorption removal of dyes from single and binary solutions using a cellulose-based bioadsorbent. ACS Sustain Chem Eng 3:432–442CrossRefGoogle Scholar
  29. Liu T, Xue F, Ding EY (2016) Cellulose nanocrystals grafted with polyacrylamide assisted by macromolecular RAFT agents. Cellulose 23:3717–3735CrossRefGoogle Scholar
  30. Ma JY, Shi J, Ding HC, Zhu GC, Fu K, Fu X (2017) Synthesis of cationic polyacrylamide by low-pressure UV initiation for turbidity water flocculation. Chem Eng J 312:20–29CrossRefGoogle Scholar
  31. Machida S, Narita H, Katsura T (1971) Flocculation properties of cellulose- acrylamide graft copolymers. Angew Makromol Chem 20(1):47–56CrossRefGoogle Scholar
  32. Mohammed N, Grishkewich N, Tam KC (2018) Cellulose nanomaterials: promising sustainable nanomaterials for application in water/wastewater treatment processes. Environ Sci: Nano 5:623–658Google Scholar
  33. Negro C, Blanco A, Fuente E, Sánchez LM, Tijero J (2005) Influence of flocculant molecular weight and anionic charge on flocculation behaviour and on the manufacture of fibre cement composites by the Hatschek process. Cement Concrete Res 35(11):2095–2103CrossRefGoogle Scholar
  34. Negro C, Blanco A, Pío IS, Tijero J (2006) Methodology for flocculant selection in fibre–cement manufacture. Cement Concrete Comp 28:90–96CrossRefGoogle Scholar
  35. Oguzlu H, Danumah C, Boluk Y (2017) Colloidal behavior of aqueous cellulose nanocrystal suspensions. Curr Opin Colloid Interface Sci 29:46–56CrossRefGoogle Scholar
  36. Raj P, Blanco A, de la Fuente E, Batchelor W, Negro C, Garnier G (2017) Microfibrilated cellulose as a model for soft colloid flocculation with polyelectrolytes. Colloids Surf A: Physicochem Eng Aspects 516:325–335CrossRefGoogle Scholar
  37. Rasteiro MG, Garcia FAP, Ferreira P, Blanco A, Negro C, Antunes E (2008) Evaluation of flocs resistance and reflocculation capacity using the LDS technique. Powder Technol 183:231–238CrossRefGoogle Scholar
  38. Roy D, Semsarilar M, Guthrie JT, Perrier S (2009) ChemInform abstract: Cellulose modification by polymer grafting: a review. Chem Soc Rev 38:2046–2064CrossRefGoogle Scholar
  39. Sarika R, Kalogerakis N, Mantzavinos D (2005) Treatment of olive mill effluents Part II. Complete removal of solids by direct flocculation with poly-electrolytes. Environ Int 31:297–304CrossRefGoogle Scholar
  40. Shaikh SMR, Nasser MS, Hussein I, Benamor A, Onaizi SA, Qiblawey H (2017) Influence of polyelectrolytes and other polymer complexes on the flocculation and rheological behaviors of clay minerals: a comprehensive review. Sep Purif Technol 187:137–161CrossRefGoogle Scholar
  41. Singh V, Tiwari A, Tripathi DN, Sanghi R (2006) Microwave enhanced synthesis of chitosan-graft-polyacrylamide. Polymer 47:254–260CrossRefGoogle Scholar
  42. Song YB, Gan WP, Li Q, Guo Y, Zhou JP, Zhang L (2011) Alkaline hydrolysis and flocculation properties of acrylamide-modified cellulose polyelectrolytes. Carbohydr Polym 86:171–176CrossRefGoogle Scholar
  43. Swerin A, Risinger G, Odberg L (1997) Flocculation in suspensions of microcrystalline cellulose by microparticle retention aid systems. J Pulp Pap Sci 23:J374–J381Google Scholar
  44. Thakur VK, Thakur MK, Gupta RK (2013) Rapid synthesis of graft copolymers from natural cellulose fibers. Carbohydr Polym 98:820–828CrossRefGoogle Scholar
  45. Trache D, Hussin MH, Chuin CTH, Sabar S, Fazita MRN, Taiwo OFA, Hassan TM, Haafiz MKM (2016) Microcrystalline cellulose: isolation, characterization and bio-composites application-a review. Int J Biol Macromol 93:789–804CrossRefGoogle Scholar
  46. Tran VV, Duckshin P, Lee YC (2018) Hydrogel applications for adsorption of contaminants in water and wastewater treatment. Environ Sci Pollut Res 25:24569–24599CrossRefGoogle Scholar
  47. Wang JP, Chen YZ, Wang Y, Yuan SJ, Sheng GP, Yu HQ (2012) A novel efficient cationic flocculant prepared through grafting two monomers onto chitosan induced by gamma radiation. RSC Adv 2:494–500CrossRefGoogle Scholar
  48. Wang JP, Yuan SJ, Wang Y, Yu HQ (2013) Synthesis, characterization and application of a novel starch-based flocculant with high flocculation and dewatering properties. Water Res 47:2643–2648CrossRefGoogle Scholar
  49. Wei H, Gao BQ, Ren J, Li A, Yang H (2018) Coagulation/flocculation in dewatering of sludge: a review. Water Res 143:608–631CrossRefGoogle Scholar
  50. Wong SS, Teng TT, Ahmad AL, Zuhairi A, Najafpour G (2006) Treatment of pulp and paper mill wastewater by polyacrylamide (PAM) in polymer induced flocculation. J Hazard Mater 135:378–388CrossRefGoogle Scholar
  51. Wu H, Liu ZZ, Li A, Yang H (2017) Evaluation of starch-based flocculants for the flocculation of dissolved organic matter from textile dyeing secondary wastewater. Chemosphere 174:200–207CrossRefGoogle Scholar
  52. Xiong XP, Duan JJ (2012) Chapter 6 Dissolution and application of cellulose in NaOH/urea aqueous solution. In Xie HB, Gathergood N (eds) The role of green chemistry in biomass processing and conversion. John Wiley & Sons, Inc, Wheim, pp 205–240Google Scholar
  53. Xiong B, Loss RD, Shields D, Pawlik T, Hochreiter R, Zydney A, Kumar M (2018) Polyacrylamide degradation and its implications in environmental systems. NPJ Clean Water 1:17CrossRefGoogle Scholar
  54. Yang Z, Yuan B, Huang X, Zhou JY, Cai J, Yang H, Li A, Cheng R (2012) Evaluation of the flocculation performance of carboxymethyl chitosan-graft- polyacrylamide, a novel amphoteric chemically bonded composite flocculant. Water Res 46:107–114CrossRefGoogle Scholar
  55. Zhu GC, Liu JF, Yin J, Li ZW, Ren BZ, Sun YJ, Wan P, Liu YS (2016) Functionalized polyacrylamide by xanthate for Cr (VI) removal from aqueous solution. Chem Eng J 288:390–398CrossRefGoogle Scholar

Copyright information

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

Authors and Affiliations

  1. 1.Department of Materials Science and Engineering, College of MaterialsXiamen UniversityXiamenChina

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