HOW IMPURITIES (HEMICELLULOSES, INK AND LIGNIN) AFFECT THE FUNCTIONALIZATION OF CELLULOSE FIBRES

A. Salvador1, J. Hidalgo1, M. Azpeitia1, P. Orsolini2, P. Tingaut2, T. Zimmermann2 and A. Tejado1

1Tecnalia 2EMPA,

Research & Innovation, Sustainable Construction Div., Spain

Swiss Federal Laboratories for Materials Science and Technology, Switzerland

Objective

Cellulosic fibres offer sustainable reinforcement for polymer-based biocomposites (e.g. WPC), but usually require some chemical modification to achieve good compatibility. Since cellulose reactivity largely depends on pulp characteristics, especially on purity of the samples, the reaction rate of four different pulp samples, namely bleached softwood kraft (b-SKP), virgin thermo-mechanical (TMP), recycled TMP and acetosolv weat straw, has been compared. Functionalization of cellulose fibres has been carried out through a set of oxidation reactions expected to benefit fibrillation and thus reinforcing ability.

CELLULOSE SAMPLES
Cell-A b-SKP
Bleached Softwood Kraft

FUNCTIONALIZATION
Cell-D WS
Acetosolv Wheat Straw

Cell-B TMP
Virgin Thermo Mechanical

Cell-C Recycled
Recycled TMP

Chemistry

A well-known and highly efficient reaction (carboxylation of dialdehyde cellulose)[1] was used to compare the behaviour of the different pulps under equal conditions.

Kinetics

Oxidation reactions were initially monitored through pH evolution. Proton (H+) generation rate and yield were determined.
pH vs time
10 9 8 7 pH 6 5 4 3 0 1 2 3 4 Time (h) 5 15 20 Diffusion of reactants into the fibre wall

Reaction rate (R) vs pH

1000 m

1000 m

1000 m

1000 m

Reaction yield vs time

IMPURITIES Highly pure Non-damaged High lignin % FIBRES Damaged with lots of fines Highly damaged Short and thin-walled COMPOSITION (%) (C: Cellulose, H: Hemicellulose, L: Lignin, O: Other impurities) 30% ink + inorganics High hemicellulose %

Sample pH for Rmax pH for R>80% Cell-A Cell-B Cell-C Cell-D 4.2 4.3 3.9 4.2 4.2 - 4.5 4.2 - 4.5 3.8 - 4.5 4.1 - 4.3

C H L O

99.5 0.5 0 0

58.7 14.3 26 1

36.2 25.8 8.4 29.6

58.2 40.3 1.3 0.2

Effects on fibres The presence of negatively charged groups induces fibrillation and disintegration of fibres.
Disintegration (Optical Micrographs of Cell-A)
200 m

Fibres before treatment (SEM)

100 m

1000 m

100 m

Fibrillation (SEM of Cell-A)

References
[1] Tejado et al. 2012 Cellulose 19(3):831-842; Yan et al. (2012) Langmuir 28:7834-7842; Tejado et al. (2011) Prov. Patent Appl. USPTO 61/450,222.

The impurities present on recycled newspapers (mainly ink and inorganic fillers) delay the reactivity of cellulose fibres, apparently by hampering the diffusion of reactants into the fibre wall and buffering the reaction medium at alkaline pH. Virgin TMP, with no buffering effect, shows a rapid pH evolution and fast reaction related to the damaged fibres and extensive presence of fines. On the other hand, the hemicelluloses present on wheat straw pulp participate of the reaction and increase the overall rate due to their ready accessibility. Furthermore, the short and thin-walled WS fibres also collaborate to accelerate the reaction by allowing a rapid diffusion of reactants into the fibre wall, contrary to the thick-walled non-damaged softwood kraft pulp. Regarding the reaction yield, measured here as total [H+] generated, hemicelluloses (WS) do contribute to increase the total amount, while lignin (TMP) and impurities (Recycled) reduce the extent of the reaction. This work also states that the pH range for maximum reaction rate is not significantly affected by the presence of the impurities.

Conclusions

Acknowledgements

La Compagnie Industrielle de la Matire Vgtal, FR (Bouchra Benjelloun) and ECOPulp Oy, FI (Ari Hentonnen), valuable partners of the INNOBITE consortium, and Smurfit Kappa Nervion, ES (Javier Prez) are greatfully acknowledged for providing the pulp samples for this study. Esther Strub and Anja Huch (EMPA, CH) are greatfully acknowledged for the SEM imaging.