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Shigenori Kuga
The University of Tokyo
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Abstract
The properties of cellulose microcrystals and their colloidal suspensions obtained by acid treatments of native
cellulose have been investigated. Bleached softwood kraft pulp was treated with 65% (w/w) sulfuric acid or 4 N
hydrochloric acid and the resulting particle morphology and flow properties of the aqueous suspensions were studied.
Colloidal dispersion of the HCl-treated sample was obtained by more thorough removal of acid from the hydrolysate
than in the case of H SO treatment. The H SO -treated and HCl-treated samples had similar particle sizes and
2 4
2 4
shapes when observed by electron microscopy. Conductometric titration of suspensions revealed that the
H SO -treated sample had a surface charge of 84 m-equiv kg1 dry material due to the introduction of sulfate groups,
2 4
while that of the HCl-treated sample was undetectable. The H SO -treated suspension showed no time dependence in
2 4
viscosity, while the HCl-treated suspension was thixotropic at concentrations >0.5% (w/v) and anti-thixotropic
<0.3%. The inclination of the relative viscosityconcentration plot (Einstein coefficient) for the H SO - and HCl2 4
treated suspensions were 135 and 1380, respectively. The former value, when used in Simhas equation for rod-like
particle suspension, roughly corresponds to an axis ratio of 50 estimated from the micrographs. 1998 Elsevier
Science B.V. All rights reserved.
Keywords: Acid treatment; Cellulose microcrystals; Rod-like particles; Surface charge; Thixotropy/anti-thixotropy
1. Introduction
Treatment of native cellulose with 65 wt% sulfuric acid gives suspension of microcrystalline cellulose [17]. This is a colloidal suspension of rodlike particles (whisker) nanometers in size showing
chiral
nematic
phase
separation
[35].
Marchessault et al. studied the viscosity of
H SO -treated suspensions and found its
2 4
Newtonian behavior and dependence on particle
size [6 ].
During the preparation of this system a certain
* Corresponding author.
0927-7757/98/$ see front matter 1998 Elsevier Science B.V. All rights reserved.
PII S0 9 2 7 -7 7 5 7 ( 9 8 ) 0 0 40 4 - X
76
J. Araki et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 7582
degree of degradation of two kinds of microcrystalline cellulose samples prepared by different acids
[8]. Sulfate groups may also affect the enzyme
activity through changes in the pH of the system.
To evaluate the influences of surface charge on
the rheological behavior of the suspension, and on
the enzymatic action on cellulose particles, it is
desirable to prepare microcrystalline cellulose with
a minimal and/or a known amount of surface
charge. Use of hydrochloric acid might meet this
requirement, but no report of this kind was found.
This is simply due to the difficulty in obtaining
good dispersion of particles treated with HCl.
During the removal of acid from the H SO
2 4
hydrolysate by centrifugation [3], the fine particle
components become non-sedimenting when the
pH reaches 13. The coarse component (pellet)
can be removed at this stage conveniently. In the
case of HCl treatment, however, such a condition
is not readily attained.
In the present study the initial aim was to
establish a method for preparing colloidal suspensions of cellulose microcrystals by HCl treatment
in order to investigate difference in rheological
behavior between the samples with different levels
of surface charge.
Approximately 150 mg of the freeze-dried microcrystal sample was pressed at 200 kg cm2 into a
pellet 20 mm wide and 1 mm thick. The X-ray
diffraction pattern was obtained with Ni-filtered
Cu Ka radiation using an X-ray generator (Rigaku
RINT2000) at 30 kV, 40 mA.
J. Araki et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 7582
77
78
J. Araki et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 7582
Fig. 3. X-ray diffraction pattern (reflection mode) of microcrystals obtained by H SO and HCl treatments.
2 4
Fig. 2. Transmission electron micrograph of cellulose microcrystals prepared by (a) H SO and (b) HCl treatments. Typical
2 4
individual microcrystals are shown by arrowheads. Scale bars
show 500 nm.
J. Araki et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 7582
79
Table 1
The amounts of strong and weak acidic groups on microcrystalline cellulose
Sample
NBKP/H SO
2 4
NBKP/HCl
84
0
26
<18
84 mmol kg1, roughly corresponds to the previously reported value of surface charge density
of 0.155 e nm2 [5] for a H SO -treated cotton
2 4
sample (see Appendix A).
Though the HCl-treated suspension contained
only a small amount of weak acid groups, it could
form a stable colloid at the very low ionic strength
attained by dialysis. Its colloidal stability was
much lower than that of the H SO -treated sample;
2 4
while the latter was precipitated by electrolyte
addition only at >20 mM, the former was precipitated at ~0.4 mM. The formation of stable cellulose colloid without introduction of strong acid
groups is a novel phenomenon and leads to the
anomalous viscosity behavior described in
Section 3.2.
3.2. Viscosity behaviors
Fig. 5 shows the time dependence of viscosity of
the cellulose suspensions. While the viscosity of
H SO -treated suspension showed no time depen2 4
dence [Fig. 5(a)], that of HCl-treated suspension
showed typical thixotropy at concentrations higher
than ca 5 g l1 [Fig. 5(b)]; on the other hand, the
dilute suspensions ( less than ca 3 g l1) showed
an increase in viscosity with time (anti-thixotropy).
The viscosity of the HCl-treated suspension equilibrated after 30 min of rotation in either case.
When the rotation was stopped for a short time
and re-started, the viscosity resumed the previous
value. The viscosity, however, returned to the
initial value with elongated interruption, in ca
70 min. In this respect the HCl-treated suspension
is a typical thixotropic system at higher
concentrations.
Thixotropy of the HCl-treated suspension indicate the effect of significant inter-particle aggrega-
80
J. Araki et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 7582
f2
15( log 2f3)
2
f2
5( log 2f1)
2
14
15
(1)
(2)
J. Araki et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 7582
81
4. Conclusions
Cellulose microcrystal suspensions were prepared by treating bleached softwood kraft pulp
with 65% (w/w) sulfuric acid or 4 N hydrochloric
acid. To obtain a good dispersion of HCl-treated
microcrystals, a more thorough removal of acid
from the hydrolysate was necessary than in the
case of H SO . Conductometric titration showed
2 4
that the H SO -treated sample had a surface
2 4
charge of 84 mmol kg1 of strong acid and
26 mmol kg1 of weak acid, ascribed to sulfate
ester and carboxyl groups, respectively. No strong
acid groups and a small amount of weak acid
groups (<18 mmol kg1) were present in the HCltreated sample.
Though particle morphology, X-ray diffraction
pattern and IR spectrum were the same for these
microcrystal samples, the viscosity behavior of the
two suspensions showed remarkable differences.
The H SO -treated suspension showed no time
2 4
dependence in viscosity, while the HCl-treated
suspension was thixotropic at concentrations
>0.5% (w/v) and rheopectic <0.3%. Both suspensions were shear-thinning, and its degree for HCltreated suspension was much greater than that
of the H SO -treated suspension. The Einstein
2 4
coefficient for the H SO -treated suspension at
2 4
135, corresponded to an aspect ratio of 50 calculated from Simhas equation. The same coefficient
for the HCl-treated suspension at 1380, reflects
aggregation of particles resulting in thixotropy or
anti-thixotropy, according to the concentration.
Acknowledgement
This work was supported in part by the Grantin-Aid for a Scientific Research from Ministry of
82
J. Araki et al. / Colloids Surfaces A: Physicochem. Eng. Aspects 142 (1998) 7582
A B
1000
1.6
106
56351027
=1.111020
5.711022
6.031023
References
[1] S.M. Mukherjee, H.J. Woods, Biochim. Biophys. Acta 10
(1953) 499.
[2] R.H. Marchessault, F.F. Morehead, N.M. Walter, Nature
184 (1959) 632.
[3] J.-F. Revol, H. Bradford, J. Giasson, R.H. Marchessault,
D.G. Gray, Int. J. Biol. Macromol. 14 (1992) 170.
[4] J.-F. Revol, L. Godbout, X.M. Dong, D.G. Gray, H.
Chanzy, G. Maret, Liquid Crystals 16 (1994) 127.
[5] X.M. Dong, T. Kimura, J.-F. Revol, D.G. Gray, Langmuir
12 (1996) 2076.
[6 ] R.H. Marchessault, F.F. Morehead, M. Joan Koch,
J. Colloid Sci. 16 (1961) 327.
[7] V. Favier, H. Chanzy, J.Y. Cavaille, Macromolecules 25
(1995) 6365.
[8] M. Samejima, Personal Communication, 1997.
[9] S. Katz, R.P. Beatson, A.M. Scallan, Sven. Papperstidn. 6
(1984) 48.
[10] W. Helbert, J.Y. Cavaille, A. Dufresne, Polym. Composites
17 (1996) 604.
[11] J. Mewis, J. Non-Newtonian Fluid Mech. 6 (1979) 1.
[12] J. Mewis, A.J.B. Spaull, Adv. Colloid Interface Sci. 6
(1976) 173.
[13] H. Rasekh, K.W. Rose, W.E. Worrall, Br. Ceram. Trans.
J. 86 (1987) 132.
[14] L.M. DiMemmo, M.J. Falkiewicz, Cellulose and its
Derivatives. Wiley, New York, 1986, p. 511.
[15] R. Simha, J. Phys. Chem. 44 (1940) 25.
[16 ] A.W. Adamson, Physical Chemistry of Surfaces, 5th ed.,
Wiley, New York, 1990, p. 526.