Cellulose 00: 1–8, 2002.

1
© 2002 Kluwer Academic Publishers. Printed in the Netherlands.

Changes in cellulose supramolecular structure and molecular weight

distribution during steam explosion of aspen wood

Tomas Josefsson 1,2, Helena Lennholm 1,* and Göran Gellerstedt 1

1
Department of Pulp and Paper Chemistry and Technology, Division of Wood Chemistry, Royal Institute of
Technology, SE-100 44 Stockholm, Sweden; 2Current address: Foritec AB, Lejonstigen 4, SE-181 32 Lidingö,
Sweden; *Author for correspondence (e-mail: lennholm@pmt.kth.se; phone: +46-8-790-8110; fax:
+46-8-790-6166)
Received 9 November 2000; accepted in revised form 11 September 2001

Key words: Molecular weight distribution, Populus tremula, Size exclusion chromatography, Solid state NMR,
Steam explosion

Abstract

We have studied the cellulose supramolecular structure in pulps obtained by steam explosion of aspen wood. The
pulps were bleached with hydrogen peroxide in an OQP-sequence and characterised by size exclusion chromato-
graphy and 13C cross polarisation magic angle spinning (CP/MAS) NMR-spectroscopy. With CP/MAS-NMR-
spectroscopy and chemometrics we were able to separate the supramolecular structural changes taking place dur-
ing steam explosion into two independent processes. One process was related to the extent of processing and
showed degradation and dissolution of cellulose, hemicellulose and lignin accompanied by an increase in cellu-
lose content. The second process was displayed by pulps having molecular weights below approximately 100000
and was interpreted as showing the removal of dislocations and an increase in crystalline and/or paracrystalline
cellulose in the cellulose fibrils.

Introduction process. They show, for example, a higher porosity in

Steam explosion is a method of separating lignocel-
lulosic material into its main components, cellulose,
lignin, and hemicellulose (Mason 1928; Hemmingson
and Newman 1985; Schwald and Bobleter 1989;
Kokta 1990; Ibrahim and Glasser 1999). In a steam
explosion process, wood chips or shavings are treated
with pressurised steam and are then released quickly
through a valve. After a steam explosion, about 50%
of the wood is obtained as a solid residue. The resi-
due consists mainly of cellulose and hemicellulose,
but also some lignin. The lignin may be removed by
a subsequent alkali extraction, but it can be recovered
and used for the production of various chemicals.
Some of the possible end products of steam-exploded
wood are dissolving pulp, paper pulp, ethanol, xyli-
tol, lactic acid and furfural.
Steam-exploded pulps have different morphologies
from those of pulps produced by the sulphite or kraft
the fibre fragments (Samaranayake et al. 1994). The
changes in cellulose supramolecular structure during
the steam explosion of wood have been less studied.
Tanahashi et al. (1989) studied the steam explosion
of white birch and observed increases in lateral cel-
lulose fibril size, an increased aggregation of fibrils
and a decrease in fibril length of the cellulose. Some
work has been devoted to the steam explosion of pure
cellulose (Kamide et al. 1992). Yamashiki et al.
(1990) observed an increase in cellulose fibril size
when pulp was subjected to steam explosion.
13
C-cross-polarisation magic angle spinning nu-
clear magnetic resonance (CP/MAS-NMR) spectra of
cellulose and pulp contain information regarding the
amounts and structures of the different cellulose poly-
morphs and of unordered cellulose (Isogai et al. 1989;
VanderHart and Atalla 1984). Recently it has been
shown that NMR-spectra also contain information
about the cellulose supramolecular structure (New-

XPS 69918 (CELL) – product element 387205 – Grafikon

2

man 1998; Larsson et al. 1999; Wickholm et al. Table 1. Experimental conditions for the steam explosions (the se-
1998). NMR-spectra of wood pulp samples, however, verity data are given in order to enable these studies to be com-
pared with other work).
contain broad and overlapping peaks. This problem
can be overcome by using chemometrics or spectral Sample no. Temp (°C) Time (min) 10 log R 0
fitting. NMR-spectra of wood cellulose have recently
1 180 2 2.67
been thoroughly assigned using spectral fitting (Wick- 2 180 5 3.06
holm et al. 1998). In earlier work (Lennholm et al. 3 180 10 3.36
1994; Lennholm 1998), chemometrics has been 4 190 2 2.95
shown to be a powerful tool to evaluate NMR-spec- 5 191 5 3.39
tra of cellulose. 6 189 10 3.62
The molecular weight and the molecular weight 7 199 2 3.22
distribution of the wood polymers are important char- 8 200 5 3.65
acteristics of cellulose and pulp. Size Exclusion 9 200 10 3.96
Chromatography (SEC) is one of the most common 10 210 2 3.53
analytical techniques to determine the molecular 11 209 5 3.92
weight distribution of polydisperse polymers (Val- 12 210 10 4.24
tasaari and Saarela 1975; Fengel and Wegener 1989; 13 219 2 3.81
Sjöholm 1999). Studies of hemicellulose and lignin 14 220 5 4.23
after steam explosion treatment by SEC (Bouchard et 15 220 10 4.54
al. 1991; Jakobsons et al. 1995) are important tech-
niques in monitoring the degradation of the wood opened and the treated chips were collected. The
polymers. The water fraction after steam explosion of treatment times and temperatures, which were chosen
biomass has also been analysed by SEC (Glasser and according to a factorial design, are given in Table 1.
Wright 1995). To enable different processes and conditions (tem-
In this work, we have used the steam explosion perature and time) to be compared, the severity R 0 of
process to separate the components of aspen wood. the treatment (Overend and Chornet 1987) was cal-
To achieve variations in the cellulose supramolecular culated as:
structure and molecular weight distribution, we car-
共T ⫺ 100兲
ried out a series of steam explosions where the time R o ⫽ te 14.75
and temperature were varied according to a factorial
design. Thereafter, we bleached the cellulose-rich where t is the time in min and T is the temperature in
fractions with an OQP-sequence. The resulting pulps °C. In practice 10log(R 0) is often used instead of R 0.
were characterised by SEC and 13C-CP/MAS-NMR-
spectroscopy. Alkali extraction

The pulps were washed with deionised water at room

Methods
Steam explosion
Air-dried chips from aspen wood (Populus tremula)
were milled in a Whiley-mill with a 10 mm sieve be-
fore the steam-treatment. 100–120 g oven-dry mate-
rial was loaded in the steam explosion unit (Eklund
et al. 1988). The chips were pre-treated with low-
pressure steam (0.1–0.2 MPa) to achieve a uniform
humidity. The milled and pre-steamed chips were
placed in an autoclave with a volume of 2 l. High-
pressure steam was applied using a steam boiler pro-
ducing steam at 4 MPa. When the desired tempera-
ture and treatment time were reached, a valve was
temperature. The pulps were then extracted for 120
min under nitrogen with 2 M NaOH (aq) at 80 °C.
The liquor-pulp ratio was 10:1. After the extraction,
the pulps were washed with deionised water until the
water had a pH of 7.
Bleaching
The pulps were bleached in an OQP-sequence:
Oxygen bleaching (O):
• The pulps (10 g oven dry) were impregnated with
magnesium sulfate (0.4% Mg on pulp) for 5 min
at 5.5% consistency. After dewatering, alkali and
water (4.0% NaOH on pulp, 12% consistency)
 3

Table 2. Results of lignin and carbohydrate analysis of bleached Carbanilation

pulps (%).

Sample no. Lignin Rha + Ara Xyl Man Gal Glc The pulps were thoroughly dried over Silica Gel SiO 2
(Merck) under vacuum and thereafter derivatised with
Aspen wood 18.6 1.1 23.6 2.9 0.7 53.0
phenylisocyanate according to Evans et al. (1989).
1 19.2 < 0.5 7.5 0.7 1.2 71.1
About 25 mg of dry pulp was soaked in 4 ml pyri-
2 17.8 < 0.5 5.7 1.4 0.7 74.3
dine, and 0.5 ml phenyl isocyanate was added. The
3 6.6 < 0.5 3.2 0.9 0.3 88.8
reaction mixture was kept at 70 °C for 70 h. After the
4 16.4 < 0.5 4.4 1.2 0.4 77.0
5 6.9 < 0.5 2.6 0.5 0.4 89.4
reaction, the solution was cooled and 1 ml methanol
6 3.3 < 0.5 1.9 0.4 0.3 93.7
was added to eliminate the unreacted phenyl isocyan-
7 7.1 < 0.5 1.9 0.4 0.3 90.2 ate. The mixture was then poured into a solution of
8 5.9 < 0.5 1.5 0.3 0.2 91.9 water–methanol (3:7). The cellulose tricarbanilates
9 7.1 < 0.5 0.9 0.2 0.2 91.3 were purified by repeated washing with water–meth-
10 4.1 < 0.5 3.1 0.8 0.2 91.2 anol, and thereafter water. They were then dried un-
11 4.0 < 0.5 1.5 0.2 0.2 94.0 der vacuum.
12 5.5 < 0.5 0.7 0.2 0.1 93.1
13 4.7 < 0.5 1.5 0.3 0.2 93.2 SEC analysis
14 3.7 < 0.5 1.0 0.1 0.2 94.8
15 1.5 < 0.5 1.1 0.1 0.2 96.9 The derivatives were analysed on a SEC system con-
sisting of four columns with pore sizes of 10 6, 10 5,
10 4 and 10 3 Å (Ultrastyragel, Waters). The system
were added, and the oxygen bleaching was
was made up of a Waters 515 HPLC Pump, Rheodyne
performed in steel autoclaves (2.5 l) at 0.7 MPa
injector and a Waters 484 Tuneable Absorbance De-
O 2 and 100 °C during 45 min. After the
tector. Data were collected with a Hewlett-Packard
bleaching, the pH was checked to be 11–12, and
3396 integrator and the files were evaluated with al-
the pulp was thereafter washed with deionised
gorithms in MatLab (MathWorks Inc.). Thereafter the
water.
files were converted to a format compatible with the
Complexing agent (Q):
PL Caliber® 7.0-AIA software (Polymer Laborato-
• After oxygen bleaching and washing, the pulp
ries). Tetrahydrofuran (THF) was used for eluation
was run through a complexing agent step at a
and the flow rate was 0.6 ml/min at 25 °C. The cel-
pulp consistency of 4%. A total of 0.2% on pulp
lulose tricarbanilates dissolved in THF (0.05%) were
DTPA was added and the mixture was acidified
injected (60 ml) on the column system and detected
with sulphuric acid to pH 5. The mixture was
with the UV-detector at 236 nm. The system was cal-
mixed and then kept at 90 °C for 60 min. The
ibrated with eight standards of pullulan, M p from
pulp was then washed with deionised water.
5600 to 1.52 × 10 6 (Polymer Standards Service
Hydrogen peroxide bleaching (P):
GmbH, Mainz, Germany). Before calibration, the pul-
• The peroxide bleaching was performed at 10%
lulan standards were carbanilated in the same way as
pulp consistency and 3% hydrogen peroxide on
the pulp samples (see above).
pulp. Before the bleaching, the pH was adjusted
to 11.5 with NaOH. The mixture was kept at 95
NMR-spectroscopy
°C for 6 h. After the bleaching, the pH was
checked to be 10–12, and the pulp was then
The 13C-CP/MAS NMR spectra were recorded on
washed with deionised water.
wet samples (50% water) on a Bruker AMX-300 in-
• With this OQP-sequence, the brightness was
strument at ambient temperature. The spectrometer
significantly increased to almost 90%.
operated at 75.47 MHz using a double air-bearing
• Carbohydrate and lignin analyses were performed
probe and ZrO 2 rotors. The spinning rate was 5 kHz,
on the bleached pulps, according to Theander and
the contact time was 0.8 ms, the acquisition time was
Westerlund (1986). The results are given in
37 ms, the sweep width was 368 ppm and the delay
Table 2.
between pulses was 2.5 s. For each spectrum, 3000
transients were accumulated with 2048 data points
and zero-filled to 4096 data points. The spectra were
4
referenced to the carbonyl in external glycine
(␦ =176.03 ppm).
Chemometrics
Principal component analysis, PCA (Jolliffe 1986)
was used to analyse the NMR-spectra. The intensities
of 779 evenly distributed data points in each of the
NMR spectra formed the X-matrix. Two principal
components (PCs) were obtained in which 79.3 and
9.6% respectively of the total variance was explained.
Subspectra were constructed by plotting the loadings
for each PC versus variable numbers. PCA was car-
ried out using the SIMCA 7.0 software.
Results and discussion
In birch and spruce wood, cellulose constitutes about
40–50% of the cell wall and is composed of fibrils
with an almost square cross-section with lateral di-
mensions of 4–5 nm, the side length of the square
corresponding to about 7–9 cellulose polymers (Fen-
gel and Wegener 1989; Larsson et al. 1999; Hult et
al. 2000). When spruce wood is pulped in a kraft
cook, the aggregation is increased due to the removal
of hemicellulose and lignin (Hult et al. 2000). A simi-
lar process has been observed in the steam explosion
of birch wood (Tanahashi et al. 1989). In this work,
we used the steam explosion process to separate the
components of aspen wood. To achieve controlled
variations in the cellulose supramolecular structure
and molecular weight distribution, we carried out a
series of steam explosions where the time and tem-
perature were varied according to a factorial design
(Table 1). Thereafter we washed, alkali-extracted and
bleached the cellulose-rich fractions. To analyse the
supramolecular changes in the cellulose fibrils and the
molecular weight distribution, we performed 13C-CP/
MAS-NMR-spectroscopy and SEC on the steam-ex-
ploded aspen wood samples.
SEC chromatography
Figure 1 shows the SEC chromatograms of the pulps
produced under the steam explosion conditions given
in Table 1. The chromatograms in Figure 1a–c gener-
ally show a peak at a molecular weight of approxi-
mately 500000. In Figure 1a (steam explosion at 180
°C, severity 2.67), a peak at a molecular weight of
20000 is also seen. Such a bimodal distribution of the
SEC chromatogram has been observed in studies of
birch kraft pulps (Sjöholm et al. 2000), and has been
shown to arise from cellulose (high molecular weight)
and xylan (low molecular weight). As pulp no. 1 in
Figure 1 has 7% xylose left, see Table 2, the peak at
molecular weight 20000 may correspond to xylan.
At higher steam explosion temperatures (190–220
°C; Figure 1b–e), the low molecular weight peak dis-
appears. The xylose content in these pulps is also
lower (4–1%, Table 2).
In the work by Glasser and Wright (1998), no
polymeric xylan could be obtained in material ob-
tained from steam explosion of biomass. The amount
of xylan in the exploded material was very low at a
severity of 3.7 or higher (Glasser and Wright 1998;
Van Winkle and Glasser 1995). Pulp no. 1 in the
present work was produced at a severity of 2.67, and
probably still contained some polymeric xylan. When
the severity was increased to above 3.0 (steam explo-
sion temperatures above 190 °C, Table 2), the xylan
was probably degraded, cf. Figure 1b, c.
The degradation of cellulose in the pulps from the
steam explosion experiments can easily be followed
in Figure 1a–e. At low steam explosion temperatures
(180–190 °C) the cellulose has a peak molecular
weight of approximately 500000 (Figure 1a, b). In
Figure 1c (200 °C) the SEC chromatograms show that
the different explosion times have led to pulps with
differences in their molecular weight distributions.
Pulp no. 8 (5 min at 200 °C) has a broad cellulose
peak with a molecular weight ranging between
500000–100000, indicating that this sample contains
both undegraded and highly degraded cellulose. In
pulp no. 9 (10 min at 200 °C) more of the cellulose is
degraded, and the cellulose peak has a maximum at a
molecular weight of about 30000. A similar pattern is
observed in Figure 1d. At the highest temperature
used in our experiments (220 °C), severe cellulose
degradation was evident already after 2 min (Figure
1e). The longest treatment time (10 min at 220 °C,
pulp no. 15) results in cellulose with a peak molecu-
lar weight of about 30000. This corresponds to a se-
verity of 4.54 (Table 1).
Van Winkle and Glasser (1995) obtained cellulose
with a similar molecular weight distribution after
steam explosion of yellow poplar wood at a severity
of 4.2.
The steam explosion process is known to produce
heterogeneously degraded material. At higher temper-
atures and using large chips (8–12 mm) in the steam
 5

Figure 1. a–e. SEC chromatograms of cellulose tricarbanilates from pulps produced under the steam conditions given in Table 1. The mo-
lecular mass is given in relation to pullulan standards, derivatized in the same way as the pulps. The pulps are produced at 180 °C and 2, 5
and 10 min (a); 190 °C and 2, 5, 10 min (b); 200 °C and 2, 5, 10 min (c); 210 °C and 2, 5, 10 min (d); 220 °C and 2, 5, 10 min (e). Detection
by UV at 236 nm.

explosion, Ballesteros et al. (2000) obtained an ex- found in the samples, and parts of the samples were
ploded material with lower heterogeneity. In this hard to dissolve in the carbanilations. The largest
work, we have observed a heterogeneous degradation amount of heterogeneously degraded material was
of the exploded material, such that fiber bundles were
6
Figure 2. 13C-CP/MAS- NMR-spectra of pulps nos 1, 4, 7, 10, 14
and slightly processed aspen wood (CTMP). Cellulose signals from
the respective carbon atoms are denoted C1–C6, hemicellulose is
denoted H and lignin L.
found in the samples exploded at low temperature, in
agreement with the work of Ballesteros et al. (2000).
13
C-CP/MAS-NMR-spectroscopy
Figure 2 shows 13C-CP/MAS-NMR-spectra of some
of the pulps, together with lightly processed aspen
wood (chemithermomechanical pulp, CTMP). Cellu-
lose signals from the respective carbon atoms are de-
noted C1–C6, hemicellulose is denoted H and lignin
L. In the spectrum of CTMP, the signals correspond-
ing to hemicellulose and lignin have higher intensi-
ties than in the pulps nos 1–15, cf. Table 2.
To extract the systematic differences in the spec-
tra, we performed a principal component analysis
(PCA) of the NMR-spectra from pulps nos 1–15. Sta-
tistical multivariate data analysis techniques such as
PCA (Jolliffe 1986) can be used to decompose NMR
spectra into several contributing subspectra. If several
separate processes, e.g. alternative reaction mecha-
nisms are hidden in a series of spectra, these may be
unveiled as independent PCA components.
The results showed that the NMR-spectra indi-
cated variations in the cellulose according to two pro-
cesses, described by two principal components (PCs).
The score plot of the two PCs is shown in Figure 3.
The numbers correspond to the NMR-spectra of the
pulps numbered according to Table 1. Along PC1 the
samples are clearly grouped according to ‘extent of
processing’, i.e. the pulps processed for short time
Figure 3. Score plot of PC1 and PC2. The numbers correspond to
those given in Table 1.
and low temperatures have low score values, whereas
the pulps processed for long time and high tempera-
tures have high score values. Pulp no. 1 is found to
the left in Figure 3, then comes pulp no. 2, etc. Pulps
nos 13–15, the pulps exploded at the highest temper-
atures, are found to the right in Figure 3.
The variations in NMR-spectra resulting from the
first process are shown in Figure 4A. This subspec-
trum shows positive peaks corresponding to cellulose
and negative peaks corresponding to hemicellulose
and lignin. This process was therefore interpreted as
showing a general removal of hemicellulose and lig-
nin in the steam explosions with increasing tempera-
ture and explosion time, resulting in an increase in
cellulose content.
The second process, expressed by PC2 in Figure 3,
is more complex. The NMR spectra of pulps nos 1–5
are located along a line, which may indicate that these
pulps are evenly affected by the process along PC2.
Pulps nos 7, 9, 10 and 12 are most affected, as they
have PC2 scores of large magnitude. An inspection of
the SEC chromatograms (Figure 1a–e) reveals that, in
the pulps with PC2 scores of large magnitude, the
cellulose has been degraded to a molecular mass be-
low approximately 100000 (degree of polymerisation
approximately 600). The variations in NMR-spectra
resulting from the second process are shown in Fig-
ure 4B. This subspectrum shows positive peaks cor-
responding to crystalline and paracrystalline cellulose
and negative peaks corresponding to surfaces of cel-
lulose fibrils, cf. Larsson et al. 1997; Wickholm et al.
1998. A process leading to such a subspectrum must

Figure 4. The PCA subspectra corresponding to PC1 (A) and PC2
(B).
involve a decrease in fibril surfaces (inner or outer),
and an increase in the interior order of the cellulose
(i.e. crystalline and paracrystalline). Dislocations in
the fibrils lead to inner surfaces, as is schematically
shown in Figure 5. A removal of or decrease in such
dislocations would lead to a decrease in inner fibril
surfaces. It would also lead to a slight increase in the
interior order of the fibril, probably resulting in more
crystalline and/or paracrystalline cellulose. A similar
process has been observed during ball-milling of cel-
lulose powder (Wormald et al. 1996). In the work of
Wormald et al., the ball-milling introduced disloca-
tions in the fibrils and this was seen in NMR-spectra
as unordered cellulose. Surface cellulose transformed
to crystalline and paracrystalline cellulose, which is
the opposite of what is seen in Figure 4B. The pro-
cess displayed by PC2 in Figure 3 was therefore in-
terpreted as showing the removal of dislocations in
the cellulose fibrils during the steam explosion. It
should, however, be emphasized that the variance ex-
plained by PC2 is very small, so that it may be diffi-
cult to quantify the removal of dislocations with other
methods.
We believe that the process corresponding to PC2
in the NMR-spectra (Figure 3) may be interpreted as
showing severe cellulose degradation, to a peak mo-
lecular weight below 40000, accompanied by a de-
crease in fibril dislocations and an increase in crys-
talline and/or paracrystalline cellulose.
7
Figure 5. Schematic drawing of a squared section of a cellulose
fibril. During steam explosion dislocations (inner surfaces) de-
crease, and this leads to larger domains of crystalline cellulose.
Both the SEC and the NMR method characterise
the bulk of the samples, i.e. there is no distinction be-
tween intact and degraded cellulose fibrils and poly-
mers. The degradation of the samples is probably het-
erogeneous due to the process conditions, as dis-
cussed above. Since we had difficulties in determin-
ing the yield of the exploded material, we cannot
exclude that wood fibres composed of severely dislo-
cated cellulose fibrils may have been totally degraded.
Such a degradation would lead to an increase in crys-
tallinity of the exploded material.
Conclusions
With NMR-spectroscopy and chemometrics we were
able to divide the cellulose supramolecular structure
changes upon steam explosion into two independent
processes. One process was related to the extent of
processing and showed the degradation and dissolu-
tion of cellulose, hemicellulose and lignin accompa-
nied by an increase in cellulose content. The second
process was displayed by pulps having molecular
weights below approximately 100000 and was inter-
preted as showing the removal of dislocations and an
increase in crystalline and/or paracrystalline cellulose
in the cellulose fibrils.
Acknowledgements
Financial support from the graduate school Wood and
Wood Fibre, sponsored by the Swedish Council for
Forestry and Agricultural Research (SJFR), is greatly
acknowledged. Thanks are expressed to Prof Tommy
Iversen for valuable comments on the manuscript. We
are also indebted to Prof Guido Zacchi at Lund Uni-
versity for the use of the steam-explosion equipment.
8
References
Ballesteros I., Oliva J.M., Navarro A.A., Gonzalez A., Carrasco J.
and Ballesteros M. 2000. Effect of chip size steam explosion
pretreatment of softwood. Appl. Biochem. Biotechnol. 84–86:
97–110.
Bouchard J., Nguyen T.S., Chornet E. and Overend R.P. 1991.
Analytical methodology for biomass pretreatment. Part 2. Char-
acterization of the filtrates and cumulative product distribution
as a function of treatment severity. Bioresour. Technol. 36: 121.
Eklund R., Galbe M. and Zacchi G. 1988. Two-stage steam pre-
treatment of willow for increased pentose yield. J. Wood Chem.
Technol. 8: 379.
Evans R., Wearne R.H. and Wallis A.F.A. 1989. Molecular weight
distribution of cellulose as its tricarbanilate by high perform-
ance size exclusion chromatography. J. Appl. Polymer Sci. 37:
3291.
Fengel D. and Wegener G. 1989. Wood. Chemistry, Ultrastructure,
Reactions. Walter de Gruyter, Berlin, Germany.
Glasser W.G. and Wright R.S. 1998. Steam-assisted biomass frac-
tionation. II. Fractionation behaviour of various biomass re-
sources. Biomass Bioener. 14: 219.
Hemmingson J.A. and Newman R.H. 1985. A CP/MAS 13C NMR
study of the effect of steam explosion processes on wood com-
position and structure. J. Wood Chem. Technol. 5: 159.
Hult E.-L., Larsson P.T. and Iversen T. 2000. A comparative CP/
MAS 13C-NMR study of cellulose structure in spruce wood and
kraft pulp. Cellulose 7: 35–55.
Ibrahim M. and Glasser W.G. 1999. Steam-assisted biomass frac-
tionation. Part III: a quantitative evaluation of the “clean frac-
tion” concept. Bioresour. Technol. 70: 181.
Isogai A., Usuda M., Kato T., Uryu T. and Atalla R.H. 1989. Solid
state CP/MAS 13C NMR study of cellulose polymorphs. Mac-
romolecules 22: 3168.
Jakobsons J., Hortling B., Erins P. and Sundquist J. 1995. Charac-
terization of alkali soluble fraction of steam exploded birch
wood. Holzforschung 49: 51.
Jolliffe I.T. 1986. Principal Component Analysis. Springer-Verlag,
New York.
Kamide K., Okajima K. and Kowsaka K. 1992. Dissolution of
natural cellulose into aqueous solution: role of super-molecular
structure of cellulose. Polym. J. 24: 71.
Kokta B.V. 1990. Steam explosion pulping of aspen. Drev. Vysk.
127: 23.
Larsson P.T., Hult E.-L., Wickholm K., Pettersson E. and Iversen
T. 1999. CP/MAS 13C-NMR spectroscopy applied to structure
and interaction studies on cellulose I. Solid State Magn. Reson.
15: 31.
Larsson P.T., Wickholm K. and Iversen T. 1997. A CP/MAS 13C
NMR investigation of molecular ordering in celluloses. Carbo-
hydr. Res. 302: 19.
Lennholm H. 1998. The supramolecular structure of cellulose II.
Studies with 13C-CP/MAS-NMR and chemometrics. Cellucon
’98, Åbo Akademy University, Finland.
Lennholm H., Larsson T. and Iversen T. 1994. Determination of
cellulose I␣ and I␤ in lignocellulosic materials. Carbohydr.
Res. 261: 119.
Mason W.H. 1928. Apparatus for a Process of Explosion Fibration
of Lignocellulose Material, U.S. Patent 1,655,618.
Newman R.H. 1998. Evidence for assignment of 13C NMR signals
to cellulose crystallite surfaces in wood, pulp and isolated cel-
luloses. Holzforschung 52: 157.
Overend R.P. and Chornet E. 1987. Fractionation of lignocellu-
losics by steam-aqueous pretreatments. Phil. Trans. R. Soc.
London Ser A 321: 523.
Samaranayake G., Li X. and Glasser W.G. 1994. Solvent accessi-
bility of steam-exploded cellulose. Holzforschung 48: 69.
Schwald W. and Bobleter O. 1989. Hydrothermolysis of cellulose
under static and dynamic conditions at high temperatures. J.
Carbohydr. Chem. 8: 565.
Sjöholm E. 1999. Characterisation of kraft pulps by size-exclusion
chromatography and kraft lignin samples by capillary zone
electrophoresis. Ph.D. Thesis, Royal Institute of Technology,
Stockholm, Sweden.
Sjöholm E., Gustafsson K., Berthold F. and Colmsjö A. 2000. In-
fluence of the carbohydrate composition on the molecular
weight distribution of hardwood kraft pulps. Carbohydr. Poly-
mers 41: 1–7.
Tanahashi M., Goto T., Horii F., Hirai A. and Higuchi T. 1989.
Characterization of steam-exploded wood III. Transformation
of cellulose crystals and changes of crystallinity. Mokuzai Gak-
kaishi 35: 654.
Theander O. and Westerlund E.A. 1986. Improved procedures for
analysis of dietary fiber. J. Agric. Food Chem. 34: 330.
Valtasaari L. and Saarela K. 1975. Determination of chain length
distribution of cellulose by gel permeation chromatography us-
ing the tricarbanilate derivate. Pap. Puu 57: 5.
Van Winkle S.C. and Glasser W.G. 1995. Chemical cellulose from
steam – exploded wood by peracetic acid treatment. J. Pulp
Pap. Sci. 21: J37.
VanderHart D.L. and Atalla R.H. 1984. Studies of microstructure
in native celluloses using solid state 13C NMR. Macromole-
cules 17: 1465.
Wickholm K., Larsson P.T. and Iversen T. 1998. Assignment of
non-crystalline forms in cellulose I by CP/MAS 13C NMR
spectroscopy. Carbohydr. Res. 312: 123.
Wormald P., Wickholm K., Larsson P.T. and och Iversen T. 1996.
Conversions between ordered and disordered cellulose. Effects
of mechanical treatment followed by cyclic wetting and dry-
ing. Cellulose 3: 141.
Yamashiki T., Matsui T., Saitoh M., Matsuda Y., Okajima K., Ka-
mide K. et al. 1990. Characterization of cellulose treated by the
steam explosion method. Part 3: Effect of crystal forms (cellu-
lose I, II and III) of original cellulose on changes in morphol-
ogy, degree of polymerization, solubility and supermolecular
structure by steam explosion. Br. Polym. J. 22: 201.