Skip to main content
Log in

Strong cationic polyelectrolyte adsorption on a water swollen cellulosic biomaterial and its relevance on microstructure and rheological properties

  • Original Paper
  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

A multiscale approach was taken to study the swelling and viscosifying properties of a cellulose-rich biomaterial as a function of environmental conditions. First, the impact of pH and ionic strength on the surface properties of the fiber was investigated by means of potentiometry and cationic polyelectrolyte adsorption. Three adsorption regimes were identified: the first one occurred in acidic conditions and was related to the ionization of the carboxylic groups of pectin. A very sharp adsorption was then observed in the mild-acidic to neutral region which was most likely related to a conformation change in the plant cell wall architecture. The third adsorption regime happened in the alkaline region and was related to ionization effects. Based on this information, the impact of environmental conditions on the hydrated microstructure was studied in DSC by means of thermoporosimetry. It clearly demonstrated a structural collapse of the hydrated fiber when pH decreased or the amounts of ions increased. This phenomenon was in line with the surface charge measurements. Finally, the link between the wet microstructure and the macroscale behavior of the fiber was demonstrated by studying the flow properties of the reconstituted fiber, below and above its percolation threshold. In line with the surface properties and microstructure data, yield stresses increased when the pH was adjusted from acidic to alkaline conditions. Salt addition resulted in a loss of the texturizing properties.

Graphical Abstract

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

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5

Similar content being viewed by others

Abbreviations

DSC:

Differential scanning calorimetry

TPM:

Thermoporosimetry

polyDADMAC:

Polydimethyl diallyl ammonium chloride

PES-Na:

Poly(sodium ethene sulfonate)

DE:

Degree of esterification

GalA:

Galacturonic acid

HB:

Herschel–Bulkley

References

  • Aarne N, Kontturi E, Laine J (2012a) Carboxymethyl cellulose on a fiber substrate: the interactions with cationic polyelectrolytes. Cellulose 19:2217–2231

    Article  CAS  Google Scholar 

  • Aarne N, Kontturi E, Laine J (2012b) Influence of adsorbed polyelectrolytes on pore size distribution of a water-swollen biomaterial. Soft Matter 8:4740–4749

    Article  CAS  Google Scholar 

  • Alince B (2002) Porosity of swollen pulp fibers revisited. Nord Pulp Pap Res J 17(1):71–73

    Article  CAS  Google Scholar 

  • Ambjörnsson HA, Schenzel K, Germgard U (2013) Carboxymethyl cellulose produced at different mercerization conditions and characterized by NIR FT Raman spectroscopy in combination with multivariate analytical methods. BioResources 8(2):1918–1932

    Google Scholar 

  • Andreasson B, Forsström J, Wagberg L (2005) Determination of fibre pore structure: influence of salt, pH and conventional wet strength resins. Cellulose 12:253–265

    Article  CAS  Google Scholar 

  • Barbucci R, Magnani A, Consumi M (2000) Swelling behavior of carboxymethylcellulose hydrogels in relation to crosslinking, pH and charge density. Macromolecules 33:7475–7480

    Article  CAS  Google Scholar 

  • Barzyk D, Page DH, Ragauskas A (1997) Acidic group topochemistry and fiber-to-fiber specific bond strength. J Pulp Pap Sci 23:56–61

    Google Scholar 

  • Blues J, Bayliss D, Buckley M (2004) The use and calibration of piston-operated volumetric pipettes. National Physical Laboratory, Teddington

    Google Scholar 

  • Böckenhoff K, Fischer WR (2001) Determination of electrokinetic charge with a particle-charge detector, and its relationship to the total charge. Fresenius J Anal Chem 371:670–674

    Article  CAS  PubMed  Google Scholar 

  • Borrega M, Kärenlampi P (2011) Cell wall porosity in Norway spruce wood as affected by high-temperature drying. Wood Fiber Sci 43(2):206–214

    CAS  Google Scholar 

  • Budd J, Herrington T (1989) Surface charge and surface area of cellulose fibres. Colloids Surf 36:273–288

    Article  CAS  Google Scholar 

  • Conway BE (1977) The state of water and hydrated ions at interfaces. Adv Colloid Interface Sci 8:91–212

    Article  CAS  Google Scholar 

  • Cosgrove DJ (2000) Loosening of plant cell wall by expansins. Nature 407:321–326

    Article  CAS  PubMed  Google Scholar 

  • Cosgrove DJ (2005) Growth of the plant cell wall. Nature 6:850–861

    CAS  Google Scholar 

  • Czaja WK, Young DJ, Kawecki M, Malcolm Brown R Jr (2007) The future prospects of microbial cellulose in biomedical applications. Biomacromolecules 8:1–12

    Article  CAS  PubMed  Google Scholar 

  • Dalmas P (2000) Conductivity measurement on pure water according to the recommendations of the USP Pharmacopeia USP24-NF19. International Laboratory News

  • Debon S, Wallecan J, Mazoyer J (2012) A rapid rheological method for the assessment of the high pressure homogenization of citrus pulp fibres. Appl Rheol 22(6):63919–63930

    Google Scholar 

  • Deleris I, Wallecan J (2017) Relationship between processing history and functionality recovery after rehydration of dried cellulose-based suspensions. Adv Colloid Interface Sci Issue. https://doi.org/10.1016/j.cis.2017.06.013

    Article  Google Scholar 

  • Fahlen J, Salmen L (2005) Pore and matrix distribution in the fiber wall revealed by atomic force microscopy and image analysis. Biomacromol 6:433–438

    Article  CAS  Google Scholar 

  • Gregory J (1996) Polymer adsorption and flocculation. In: Finch CA (ed) Industrial water soluble polymers. The Royal Society of Chemistry, Cambridge, pp 62–75

    Google Scholar 

  • Grignon J, Scallan A (1980) Effect of pH and neutral salts upon the swelling of cellulose gels. J Appl Polym Sci 25:2829–2843

    Article  CAS  Google Scholar 

  • Guéron M, Weisbuch G (1980) Polyelectrolyte theory. I. Counterion accumilation, site-binding, and their insensitivity to polyelectrolyte shape in solutions containing finite salt concentrations. Biopolymers 19:353–382

    Article  Google Scholar 

  • Hidayat BJ, Thygesen LG, Johansen KS (2013) pH within pores in plant fiber cell walls assessed by fluorescence ratio imaging. Cellulose 20:1041–1055

    Article  CAS  Google Scholar 

  • Horvath E (2003) Appropriate conditions for polyelectrolyte titration to determine the charge of cellulosic fibers. Royal Institute of Technology, Stockholm

    Google Scholar 

  • Hubbe MA, Venditti RA, Rojas OJ (2007) What happens to cellulosic fibers during papermaking and recycling? A review. BioResources 2(4):739–788

    CAS  Google Scholar 

  • Isogai A, Kato Y (1998) Preparation of polyuronic acid from cellulose by TEMPO-mediated oxidation. Cellulose 5(3):153–164

    Article  CAS  Google Scholar 

  • Junka K, Filpponen I, Lindström T, Laine J (2013) Titrimetric methods for the determination of surface and total charge of functionalized nanofibrillated/microfibrillated cellulose (NFC/MFC). Cellulose 20:2887–2895

    Article  CAS  Google Scholar 

  • Kasper DR (1971) Theoretical and experimental investigations of the flocculation of charged particles in aqueous solutions by polyelectrolytes of opposite charge. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechTHESIS:04232014-095415213

  • Ki Lin C et al (2013) Food waste as a valuable resource for the production of chemicals, materials and fuels. Current situation and global perspective. Eng Environ Sci 6(2):426–464

    Google Scholar 

  • Kieliszewski MJ, Lamport DTA (1994) Extensin: repetitive motifs, functional sites, post-translational codes, and philogeny. Plant J 5(2):157–172

    Article  CAS  PubMed  Google Scholar 

  • Klitzing RV, Kolarić B, Jaeger W, Brandt A (2002) Structuring of poly(DADMAC) chains in aqueous media: a comparison between bulk and free-standing film measurement. Phys Chem Chem Phys 4:1907–1914

    Article  CAS  Google Scholar 

  • Lopez-Sanchez P, Farr R (2012) Power laws in the elasticity and yielding of plant particle suspensions. Food Biophys 7:15–27

    Article  Google Scholar 

  • Mabire F, Audebert R, Quivoron C (1984) Flocculation properties of some water-soluble cationic copolymers toward silica suspensions: a semiquantitative interpretation of the role of molecular weight and cationicity through a “patchwork” model. J Colloid Interface Sci 97(1):120–136

    Article  CAS  Google Scholar 

  • Maloney T, Paulapuro H (1999) The formation of pores in the cell wall. J Pulp Pap Sci 25(12):430–436

    CAS  Google Scholar 

  • Manning GS (1978) The molecular theory of polyelectrolyte solutions with applications to the electrostatic properties of polynucleotides. Quat Rev Biophys 11(2):179–246

    Article  CAS  Google Scholar 

  • Notley SM (2008) Effect of introduced charge in cellulose gels on surface interactions and the adsorption of highly charged cationic polyelectrolytes. Phys Chem Chem Phys 10:1819–1825

    Article  CAS  PubMed  Google Scholar 

  • Park YB, Cosgrove DJ (2012) A revised architecture of primary cell walls based on biomechanical changes induced by substrate-specific endoglucanases. Plant Physiol 158:1933–1943

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Park S, Venditti R, Jameel H, Pawlak J (2006) Changes in pore size distribution during the drying of cellulose fibers as measured by differential scanning calorimetry. Carbohyd Polym 66:97–103

    Article  CAS  Google Scholar 

  • Pönni R, Vuorinen T, Kontturi E (2012) Proposed nano-scale coalescence of cellulose in chemical pulp fibers during technical treatments. BioResources 7(4):6077–6108

    Article  Google Scholar 

  • Redgewell R, Curti D, Gehin-Delval C (2008) Physicochemical properties of cell wall materials from apple, kiwifruit and tomato. Eur Food Res Technol 227:607

    Article  CAS  Google Scholar 

  • Rees D (1995) Essential statistics, 3rd edn. Chapman & Hall, London

    Google Scholar 

  • Rehman M, Kim I, Han J-I (2012) Adsorption of methylene blue from aqueous solution by sugar extracted spent rice biomass. Carbohyd Polym 90:1314–1322

    Article  CAS  Google Scholar 

  • Saarikoski E, Saarinen T, Salmela J, Seppälä J (2012) Flocculated flow of microfibrillated cellulose water suspensions: an imaging approach for characterisation of rheological behaviour. Cellulose 19:647–659

    Article  CAS  Google Scholar 

  • Schiessel H (1999) Counterion condensation on flexible polyelectrolytes: dependence on ionic strength and chain concentration. Macromolecules 32:5673–5680

    Article  CAS  Google Scholar 

  • Sczostak A (2009) Cotton linters: an alternative cellulosic raw material. Macromol Symp 280(1):45–53

    Article  CAS  Google Scholar 

  • Simon J, Muller HP, Koch R, Muller V (1998) Thermoplastic and biodegradable polymers of cellulose. Polym Degrad Stab 59:107–115

    Article  CAS  Google Scholar 

  • Sjostrom E (1989) The origin of charge on cellulosic fibers. Nord Pulp Pap Res J 4(2):90–93

    Article  Google Scholar 

  • Thibault J-F, Rinaudo M (1985) Interactions of mono- and divalent counterion with alkali- and enzyme-deesterified pectins in salt-free solutions. Biopolymers 24:2131–2143

    Article  CAS  Google Scholar 

  • Van Buggenhout S et al (2015) Influence of high-pressure homogenization on functional properties of orange pulp. Innov Food Sci Emerg Technol 30:51–60

    Article  CAS  Google Scholar 

  • Wågberg L, Winter L, Ödberg L, Lindström T (1987) On the charge stoichiometry upon adsorption of a cationic polyelectrolyte on cellulosic materials. Colloids Surf 27:163–173

    Article  Google Scholar 

  • Wallecan J et al (2015) Emulsifying and stabilizing properties of functionalized orange pulp fibers. Food Hydrocolloids 47:115–123

    Article  CAS  Google Scholar 

  • Zhang Z, O’Hara I, Kent G, Doherty W (2013) Comparative study on adsorption of two cationic dyes by milled sugarcane bagasse. Ind Crops Prod 42:41–49

    Article  CAS  Google Scholar 

  • Zhang X, Wang Y, Lu C, Zhang W (2014) Cellulose hydrogels prepared from micron-sized bamboo cellulose fibers. Carbohydr Polym. https://doi.org/10.1016/j.carbpol.2014.08.012

    Article  PubMed  Google Scholar 

Download references

Acknowledgments

We thank the Cargill Texturizing Systems and Cargill Ingredient, Material & Nutrition R&D organisation for their support and in particular Jacques Mazoyer, Geert Maesmans and Didier Bonnet. The authors would like to thank one of the reviewers for his thorough and very constructive contribution on the hypothesis presented in this paper.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Joel Wallecan.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Wallecan, J., Debon, S.J.J. Strong cationic polyelectrolyte adsorption on a water swollen cellulosic biomaterial and its relevance on microstructure and rheological properties. Cellulose 25, 4437–4451 (2018). https://doi.org/10.1007/s10570-018-1887-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-018-1887-z

Keywords

Navigation