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Effect of Sulfate Groups from Sulfuric Acid Hydrolysis on the
Thermal Degradation Behavior of Bacterial Cellulose
Maren Roman† and William T. Winter*,‡
Department of Chemistry, Pulp and Paper Research Centre, McGill University,
Montréal, Quebec H3A 2A7, Canada, and Cellulose Research Institute and Department of Chemistry,
SUNY College of Environmental Science and Forestry, Syracuse, New York 13210
Received December 10, 2003; Revised Manuscript Received April 16, 2004
When used as fillers in polymer composites, the thermostability of cellulose crystals is important. Sulfate
groups, introduced during hydrolysis with sulfuric acid, are suspected to diminish the thermostability. To
elucidate the relationship between the hydrolysis conditions, the number of sulfate groups introduced, and
the thermal degradation behavior of cellulose crystals, bacterial cellulose was hydrolyzed with sulfuric acid
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under different hydrolysis conditions. The number of sulfate groups in the crystals was determined by
Publication Date (Web): June 29, 2004 | doi: 10.1021/bm034519+
potentiometric titration. The thermal degradation behavior was investigated by thermogravimetric analysis.
The sulfate group content increased with acid concentration, acid-to-cellulose ratio, and hydrolysis time.
Even at low levels, the sulfate groups caused a significant decrease in degradation temperatures and an
increase in char fraction confirming that the sulfate groups act as flame retardants. Profile analysis of the
derivative thermogravimetric curves indicated thermal separation of the degradation reactions by the sulfate
groups into low- and high-temperature processes. The Broido method was used to determine activation
energies for the degradation processes. The activation energies were lower at larger amounts of sulfate
groups suggesting a catalytic effect on the degradation reactions. For high thermostability in the crystals,
low acid concentrations, small acid-to-cellulose ratios, and short hydrolysis times should be used.
Table 1. Amounts of Introduced Sulfate Groups, nSO3H, and Surface Charge Densities, σ, at Different Reaction Conditions for the Sulfuric
Acid Hydrolysis of Bacterial Cellulose
hydrolysis conditionsa
sample (%(w/v)) (mmol‚g-1) (°C) (h) nSO3H ( 0.8 (mmol‚kg-1) σ ( 0.003 (e‚nm-2)b
A unhydrolyzed 0 0.000
B 12 188 104 2 2.1 0.007
C 65 66 40 1 6.5 0.021
D 65 199 40 1 8.5 0.027
E 65 663 40 1 9.8 0.031
F 65 66 40 3 10.3 0.033
G 61 618 40 3 50.8 0.162
H 65 66 60 2 73.0 0.233
a Sulfuric acid concentration, acid-to-cellulose ratio, hydrolysis temperature, hydrolysis time. b We calculated a specific surface area of 189 m2 g-1
The activation energies, Ea, of the degradation processes sulfate groups in the crystals. The amounts of sulfate groups
were determined with the Broido method using the equation20 were also larger for larger acid-to-cellulose ratios (samples
C-E and samples F and G) and longer hydrolysis times
Ea (samples C and F and samples E and G). The effect of the
( 1y) ) - R T1 + C
ln ln hydrolysis time was more pronounced at a higher acid-to-
cellulose ratio. Hydrolysis at 60 °C (sample H) gave higher
where R was the gas constant, C was a temperature sulfation than hydrolysis at 40 °C (sample F).
independent term, and y was the fraction of undecomposed The sulfate content of sample H was 73 mmol kg-1. Araki
material remaining at time t, (W - Wf)/(Wi - Wf). Wi and and Kuga hydrolyzed bacterial cellulose with 65% sulfuric
Wf are the initial and final sample weight, and W is the acid (by weight) at 70 °C for 30 min and measured a sulfate
sample weight at time t. The activation energy is obtained content of 5 mmol kg-1.21 The acid-to-cellulose ratio was
from the slope of a plot of ln(ln 1/y) versus 1/T. not specified but was 103 mmol g-1 in the author’s reference
Transmission Electron Microscopy (TEM). One drop to previously published experimental details. Considering that
(8 µL) of a 0.001% aqueous suspension of crystals was the acid concentration and probably the acid-to-cellulose ratio
allowed to dry on a Formvar and carbon coated grid (200 was higher by about one-third and the temperature by 10
mesh, treated with poly-L-lysine solution). The crystals were °C, the value of Araki and Kuga seemed to be low even
stained with uranyl acetate. Micrographs were taken at 80 after allowing for the 75% decrease in the hydrolysis time.
kV with a JEOL JEM-2000 EX electron microscope. TEM pictures of samples B and G are shown in Figure 3.
X-ray Diffraction. X-ray diffraction was carried out with In sample B, the crystalline fragments were aggregated to a
a Rigaku DMAX-1000 diffractometer and fiber attachment great extent. Sample G still showed some aggregation, but
using Ni-filtered Cu KR radiation, generated with a rotating a larger number of isolated fragments could be found. Our
anode generator operating at 50 kV and 120 mA. The results agree with the observation of Mukherjee and Woods
diffraction angle was calibrated with sodium fluoride. The that cellulose hydrolyzed under more drastic conditions
crystals were loosely inserted into the sample holder. Before aggregates less.22 Compared to cellulose crystals from
each measurement, the random orientation of the crystals in ramie,22 cotton,22 filter paper,6,8 or bleached kraft wood
the sample holder was verified by rotation of the sample pulp,4,7 the fragments from bacterial cellulose appeared to
about the transmitted beam direction and also from rotation be less uniform, which was also apparent in pictures of ref
in θ while recording intensities at fixed 2θ values corre- 2, 21, and 23. The length of the fragments ranged from about
sponding to the principal reflections in a native cellulose 200 nm to several micrometers. The reason for the nonuni-
pattern (2θ ) 14.4, 16.6, 22.5°). To determine the sample form fragmentation could be related to the predominance of
crystallinity, profile analysis was carried out with a peak the cellulose IR allomorph in bacterial cellulose or to
fitting program using Gaussian line shapes.19 The deconvo- morphological differences in the microfibrils.24
lution included the interference maxima at 2θ ) 14.4, 16.6, Thermal Degradation Behavior and Morphology. The
20.3, and 22.5° and a broad peak at the interference minimum TG and DTG curves of unhydrolyzed bacterial cellulose are
at 2θ ) 18.5° accounting for the amorphous scattering. The shown in Figure 4.
crystallinity was taken as the ratio of the sum of areas under Three maxima in the weight-loss rate were apparent. The
the crystalline diffraction peaks to the total area under the broad DTG peak centered at 50 °C, corresponding to a weight
curve between 2θ ) 10 and 27°. loss of 3.8%, was due to the evaporation of adsorbed water.
1674 Biomacromolecules, Vol. 5, No. 5, 2004 Roman and Winter
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Publication Date (Web): June 29, 2004 | doi: 10.1021/bm034519+
Figure 5. (a) TG and (b) DTG curves of unhydrolyzed (s) and sulfuric
acid hydrolyzed bacterial celluloses, samples: B (- - -), F (- -), G
(s -), H (- - -).
Between 150 and 350 °C, the DTG curves were investi-
gated by profile analysis. The degradation temperatures
(temperatures at maximum weight-loss rate), Tmax, and
maximum weight-loss rates, WLRmax, of the degradation
processes, obtained from profile analysis, are listed in Table
3.
With progressively higher sulfation, a more complex
degradation pattern was observed. Starting with sample C,
the degradation between 150 and 350 °C is best described
in terms of two processes. We propose that the lower
temperature process (termed “process 1” in Table 3) corre-
sponds to degradation of the more accessible, and therefore
more highly sulfated, amorphous regions, whereas the higher
temperature process (“process 2” in Table 3) relates to the
breakdown of the unsulfated crystal interior. At the highest
sulfation levels (samples G and H), a two-process degradation
fails to totally explain the experimental data. In the case of
sample H, we tested this possibility by adding an intermediate
Figure 6. X-ray diffraction patterns of unhydrolyzed (sample A) and
sulfuric acid hydrolyzed bacterial celluloses. temperature process and obtained an excellent fit to the
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droglucose units requires less energy than elimination of a From profile analysis of DTG curves. b Regression coefficient from
water,14 desulfation probably also occurred. The released
Publication Date (Web): June 29, 2004 | doi: 10.1021/bm034519+
(5) Revol, J.-F.; Godbout, L.; Dong, X.-M.; Gray, D. G.; Chanzy, H.; (18) Gran, G. Analyst 1952, 77, 661.
Maret, G. Liq. Cryst. 1994, 16, 127. (19) Krumm, S. WinFit, Beta Release 1.2.1; Geology Department,
(6) Dong, X. M.; Revol, J.-F.; Gray, D. G. Cellulose 1998, 5, 19. University of Erlangen: Erlangen, Germany, 1997.
(7) Araki, J.; Wada, M.; Kuga, S.; Okano, T. Colloids Surf. 1998, 142, (20) Broido, A. J. Polym. Sci., Part A-2 1969, 7, 1761.
75. (21) Araki, J.; Kuga, S. Langmuir 2001, 17, 4493.
(8) Araki, J.; Wada, M.; Kuga, S.; Okano, T. Langmuir 2000, 16, 2413. (22) Mukherjee, S. M.; Woods, H. J. Biochim. Biophys. Acta 1953, 10,
(9) Favier, V.; Chanzy, H.; Cavaillé, J. Y. Macromolecules 1995, 28, 499.
6365.
(23) Rånby, B. G. Ark. Kemi 1952, 4, 249.
(10) Helbert, W.; Cavaillé, J. Y.; Dufresne, A. Polym. Compos. 1996,
(24) Yamamoto, H.; Horii, F. Cellulose 1994, 1, 57.
17, 604.
(11) Chazeau, L.; Cavaillé, J. Y.; Canova, G.; Dendievel, R.; Boutherin, (25) Cabradilla, K. E.; Zeronian, S. H. In Thermal Uses and Properties
B. J. Appl. Polym. Sci. 1999, 71, 1797. of Carbohydrates and Lignins; Shafizadeh, F., Sarkanen, K. V.,
(12) Tang, W. K.; Neill, W. K. J. Polym. Sci., Part C 1964, 6, 65. Tillman, D. A., Eds.; Academic Press: New York, 1976; pp 73-96.
(13) Barker, R. H.; Drews, M. J. In Cellulose chemistry and its (26) Jayme, G.; Lang, F. In Methods in Carbohydrate Chemistry; Whistler,
applications; Nevell, T. P., Zeronian, S. H., Eds.; Ellis Harwood: R. L., Ed.; Academic Press: New York, 1963; Vol. 3, pp 75-83.
Chichester, U.K., 1985; p 423. (27) Shafizadeh, F. In Cellulose chemistry and its applications; Nevell,
(14) Julien, S.; Chornet, E.; Overend, R. P. J. Anal. Appl. Pyrolysis 1993, T. P., Zeronian, S. H., Eds.; Ellis Harwood: Chichester, U.K., 1985;
27, 25. pp 266-289.
(15) Kim, D.-Y.; Nishiyama, Y.; Wada, M.; Kuga, S. Cellulose 2001, 8, (28) Fung, D. P. C.; Tsuchiya, Y.; Sumi, K. Wood Sci. 1972, 5, 38.
29. (29) Black, E. L. Pulp Paper Magn. Can. 1967, 68, T-165.
(16) Parks, E. J. Tappi J. 1971, 54, 537. (30) Scheirs, J.; Camino, G.; Tumiatti, W. Eur. Polym. J. 2001, 37, 933.
(17) Verlhac, C.; Dedier, J.; Chanzy, H. J. Polym. Sci., Part A: Polym.
Chem. 1990, 28, 1171. BM034519+
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Publication Date (Web): June 29, 2004 | doi: 10.1021/bm034519+