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Cellulose

, Volume 26, Issue 7, pp 4325–4344 | Cite as

Deconstruction of microfibrillated cellulose into nanocrystalline cellulose rods and mesogenic phase formation in concentrated low-modulus sodium silicate solutions

  • Luca BertollaEmail author
  • Ivo Dlouhý
  • Eva Bartoničková
  • Jaromír Toušek
  • Jiří Nováček
  • Petra Mácová
Original Research
  • 196 Downloads

Abstract

This work demonstrates for the first time the deconstruction of microfibrillated cellulose (MFC) into rod-like cellulose nanocrystals (CNCs) in concentrated low modulus sodium silicate solutions. To this aim, MFC suspensions at different concentrations were first treated in sodium hydroxide solutions and then amorphous silica powder was added. Optical microscopy and transmission electron microscopy observation showed how MFC was efficiently deconstructed into CNCs, evidencing the occurrence of a phase separation into an isotropic and mesogenic phase. The extracted CNCs were characterized by a remarkably higher length (600–1200 nm) in comparison with the plant-derived ones commonly reported in literature. FT-IR spectroscopy and 29Si MAS NMR confirmed that the Qn equilibrium of the suspended silicate species was affected, proportionally to the amount of MFC. It was also shown, that due to the excluded volume effect exerted by silicate anions, nematic or smectic ordering could be achieved for CNC concentrations far below the critical rod concentration predicted by the Doi-Edwards model.

Graphical abstract

Keywords

Microfibrillated cellulose Cellulose nanocrystal Sodium silicate 

Abbreviations

WG

Water glass (aqueous sodium silicate solution)

MFC

Microfibrillated cellulose

Na-MFC

MFC treated in 10 M NaOH solution

CNCs

Cellulose nanocrystals

List of symbols

n

SiO2/Na2O molar ratio, modulus

Msol

Solid mass in the suspension obtained by weighting the solid residual (g)

MWG

WG mass obtained by stoichiometric calculations (g)

Mtot

Suspension mass (g)

MMFC

Mass MFC (wet) (g)

cs = 0.02

Dry content of MFC

ws

Solid weight fraction = \(\frac{M_{sol} }{M_{tot} }\)

wMFC

MFC fibrils weight fraction = \(\frac{M_{MFC} \cdot c_{s} }{M_{WG} }\)

wCNC

The weight fraction of CNCs (wCNC) on the suspension mass (Mtot) = \(\frac{M_{MFC} \cdot c_{s} }{M_{tot} }\)

ρWG

Density of a water glass suspension as a function of the solid content solution (g cm−3)

ρCNC

Density of CNCs (g cm−3)

MFC0

Pure water glass

MFC1

WG/MFC suspension with wMFC = 0.01

MFC2

WG/MFC suspension with wMFC = 0.02

\(Q_z^n\)

Silicate consisting of z interconnected Qn units

wCNC = wMFC·ws

CNCs weight fraction on the whole suspension mass

ϕCNC

Volume fraction of CNCs

ϕWG

Volume fraction of silicate anions

LCNC

CNC’s length (m)

dCNC

CNC’s diameter (m)

ν = ϕCNC/(π/4)·dCNC2LCNC

Number of rods per unit volume of solution

β

Flow index

K

Consistency index

\(\dot{\gamma }\)

Shear rate (s−1)

η0

Zero shear viscosity (Pa s)

η0.01

Viscosity at shear rate = 0.01 s−1 (Pa s)

ηs

Viscosity of the suspending medium (Pa s)

σy

Yield stress (Pa)

G′, G

Storage and loss moduli (Pa s)

kB

Boltzmann’s constant (J K−1)

T

Temperature (K)

d*CNC

Increased CNC’s diameter due to silicate adsorption (m)

drod

Diameter of a generic rod (Dogic and Frenkel) (m)

Lrod

Length of a generic rod (Dogic and Frenkel) (m)

dWG

Diameter of a spherical silicate anion (m)

δmin

Minimum interfibrillar distance (m)

s

± number of brushes/4

DCNC

Rotatory diffusivity of CNCs in diluted regime (m2 s−1)

\(D_{CNC}^{\prime }\)

Rotatory diffusivity of CNCs in semidiluted regime (m2 s−1)

ω

Frequency (Hz)

ωc

Crossover frequency (Hz)

Notes

Acknowledgments

This work was realised at CEITEC IPM—Central European Institute of Technology with research infrastructure supported by the project CZ.1.05/1.1.00/02.0068 financed from European Regional Development Fund. The support from the project Materials Research Centre at FCH BUT- Sustainability and Development REG LO1211 and the project LO1219 with financial support from the National Program for Sustainability I (Ministry of Education, Youth and Sports) is gratefully acknowledged. CIISB research infrastructure project LM2015043 funded by MEYS CR at the CF Biomolecular Interactions and Crystallization is also gratefully acknowledged. Finally, a special mention goes to Dr. Jiří Smilek, Dr. Alberto Viani, Dr. Jiri Holas and Prof. Giulio Malucelli for the support provided for the rheological tests, DIC microscopy, XRD analysis and data interpretation, respectively.

Supplementary material

10570_2019_2364_MOESM1_ESM.docx (872 kb)
Supplementary material 1 (DOCX 872 kb)

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Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  • Luca Bertolla
    • 1
    Email author
  • Ivo Dlouhý
    • 1
  • Eva Bartoničková
    • 2
  • Jaromír Toušek
    • 3
  • Jiří Nováček
    • 3
  • Petra Mácová
    • 4
  1. 1.Institute of Physics of Materials AVČRCEITEC IPMBrnoCzechia
  2. 2.Materials Research Centre, Faculty of ChemistryBrno University of TechnologyBrnoCzechia
  3. 3.CEITEC – Central European Institute of TechnologyMasaryk UniversityBrnoCzechia
  4. 4.Institute of Theoretical and Applied Mechanics of the Czech Academy of SciencesCentre of Excellence TelčTelčCzechia

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