Cellulose (2010) 17:1193–1202
DOI 10.1007/s10570-010-9454-2
Effect of high pressure treatment on structure
and properties of cellulose in eucalypt pulps
Andreia Figueiredo • Dmitry Evtuguin •
Jorge Saraiva
Received: 14 June 2010 / Accepted: 22 September 2010 / Published online: 8 October 2010
Ó Springer Science+Business Media B.V. 2010
Abstract Bleached acid sulphite and kraft Euca-
lyptus globulus pulps were subjected to treatment at
high hydrostatic pressure (400 MPa during 10 min).
The associated structural changes of cellulose were
evaluated by X-ray scattering, solid-state NMR and
infrared spectroscopy. The high pressure treatment
promoted the growth of crystalline domains predom-
inantly via lateral aggregation (cocrystallization) and,
to some extent, due to the accretion of cellulose from
noncrystalline domains (recrystallization). The trea-
ted pulps exhibited increment of the amount of
strongly bound water and improved accessibility to
amorphous domains. The high pressure treatment of
dried sulphite pulp led to restoration, at least
partially, of its swelling capacity thus diminishing
the hornification features. Pressure treated dried
sulphite pulp showed improved fibre bonding capac-
ity at simultaneously increased bulk of the produced
handsheets. The results obtained clearly showed the
potential of high pressure treatments for the modifi-
cation of cellulosic fibres in different applications.
A. Figueiredo  D. Evtuguin (&)
CICECO, Chemistry Department, University of Aveiro,
Campus de Santiago, 3810-193 Aveiro, Portugal
e-mail: Dmitrye@ua.pt
J. Saraiva
QOPNA, Chemistry Department, University of Aveiro,
Campus de Santiago, 3810-193 Aveiro, Portugal
Keywords Cellulose  High pressure processing 
Swelling  Hornification
Introduction
The physical and chemical properties of cellulose are
strongly affected by its swelling ability in water
(Warwicker 1971; Clark 1985). Being a fibrillar polar
polymer cellulose properties are vulnerable to moist-
ening-drying cycles. During drying of cellulose
materials the rearrangement of cellulose molecules
and interfibril aggregation in virgin (never-dried)
fibres takes place leading to irreversible structural
changes (Hult et al. 2001a; Newman 2004). This
phenomenon is known as hornification and was
widely discussed for chemical pulps (Minor 1994;
Weise 1998). The fibres of dried pulp become less
swollen than virgin fibres, possess higher stiffening,
surface collapse and shrinkage. Complete rehydration
of pulp is impossible even after mechanical defibra-
tion (beating) or after pre-treatment under alkaline
solutions (Klungness and Caulfield 1982; Evtuguin
et al. 1996). Hornification is responsible for the
drastic decrease in papermaking properties of chem-
ical pulps and, especially, of recycled fibres thus
limiting their reutilization (Nazhad and Paszner 1994;
Kato and Cameron 1999). The extent of cellulose
hornification in pulp depends on the pulping method
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1194
applied and decreases with the increase of amount of
residual hemicelluloses that impede the fibrils aggre-
gation (Oksanen et al. 1997; Rebuzzi and Evtuguin
2006).
One way to overcome the problems of rewetting of
cellulosic materials and to introduce structurally
associated water may be the treatment at high
hydrostatic pressures (hyperbaric treatment). High
pressure (HP) technology was applied for many years
in the production of ceramics, composite materials,
plastics and artificial diamond and is now an
expanding technology that has attracted increased
attention for food preservation and processing,
mainly due to the advantages that it offers in
comparison to thermal processing. The application
of HP to foods causes microbial destruction, leading
to food pasteurization, while keeping their nutritional
value and organoleptic properties (Ramirez et al.
2009; Oey et al. 2008; Rastogi et al. 2007; Torrecilla
et al. 2004). A broad range of pressure processed/
pasteurized food products are now commercially
available worldwide (Ramirez et al. 2009). In these
processes pressures of up to 600 MPa are usually
used (Oey et al. 2008; Rastogi et al. 2007). Apart
from these food preservation applications, high
pressure is being increasingly studied for modifying
food texture as a technological basis for innovative
foods with modified functional properties or struc-
tures (Rademacher and Hinrichs 2006) and for
biotechnological applications (Salvador et al. 2010).
Moreover, high pressure can cause protein and
enzyme denaturation (Castro et al. 2006) and change
the structure and functionality of biomacromolecules,
such as starch (Gomes et al. 1998; Oh et al. 2008). It
has been shown that starch is gelatinized by a
two-step mechanism while applying a hydrostatic
pressure of 450 MPa at room temperature (Gomes
et al. 1998; Oh et al. 2008). In the first step, hydration
of amorphous parts of the starch granules occurs,
which leads to swelling of the granules and distortion
of the crystalline regions. In the second step, the
crystalline regions become accessible to water (Oh
et al. 2008).
High pressure has never been applied before on
cellulosic pulps and was the main challenge of this
study. The effect of a high pressure of 400 MPa
during 10 min on structure and some physical and
chemical properties of cellulose in chemical pulps
was evaluated.
123
Cellulose (2010) 17:1193–1202
Materials and methods
Cellulosic pulps
Cellulosic pulps used in this work were never-dried
industrial eucalypt pulps: (1) acidic sulphite pulp of 89%
ISO brightness and intrinsic viscosity of 950 cm3/g
supplied by CAIMA Companhia de Celulose (Portu-
gal); (2) kraft pulp of 91% ISO brightness and intrinsic
viscosity of 920 cm3/g supplied by PORTUCEL (Por-
tugal). The sulphite pulp contained 6.5% of pentosans
and 0.7% of residual lignin and kraft pulp contained
16.5% of pentosans and 0.1% of residual lignin. Pulps
were analysed for pentosans and residual lignin as
described previously (Rebuzzi and Evtuguin 2006). The
pulps were dried on air at 20 °C to humidity of around
8% or, alternatively at 140 °C for 1 h to ca. 2% humidity.
High pressure treatment
Dried chemical pulps were swollen in distilled water
for 12 h under moderate agitation before the high
pressure processing (hydromodulus about 60). About
20.0 mL of pulp suspension, containing 0.33 g (dry
weight) of pulp were closed into a heat-sealed plastic
bag that was introduced in a second plastic bag,
which was heat-sealed under vacuum and submitted
to 400 MPa during 10 min at room temperature (ca
20 °C). HP processing was carried out in a High
Pressure U33 device (Institute of High Pressure
Physics, Poland), with a high pressure vessel of
approximately 100 cm3 capacity, filled with a pressure
transmitting medium (propylene glycol:water, 1:1,
v/v). After HP treatment, the sample was dried in an
oven for 3 h at 105 °C, and stored in a desiccator. For
comparison reasons, a sample of oven-dried pulp at
140 °C was swelled in distilled water and HP-treated
under the same conditions as described above.
Analyses
Pulp hornification was assessed by comparison
between water retention value (WRV) of never-dried
(WRV0) and dried (WRV1) pulps (Weise 1998):
WRV0  WRV1
Hornification; % ¼  100 ð1Þ
WRV0
WRV was determined according to a commonly used
procedure (Jayme 1958).
Cellulose (2010) 17:1193–1202 1195

X-ray diffraction scattering analysis of pulps was reflection (rad); k is the wavelength of the X-ray
carried out on a Philipps X0 Pert MPD diffractometer source (k = 0.154 nm), dL is a parameter related to
using Cu-Ka source (k = 0.154 nm) in the 2h range the lattice distortion perpendicular to 200 plane
2–40° and scanning step width of 0.02°/scan. Pulps direction (0.05) and dL represents the average
were analysed as textured samples. Pulp pellets of distance between (200) lattice planes (0.395 nm).
1.2 cm diameter and about 1 mm thickness were The dimensions of cell unit were calculated from
prepared by pressing (50 MPa). Each analysis was Bragg’s equation relating the spacing between the
twice repeated. The background scattering was sub- scattered planes, d, and the angle between the
tracted from pulp diffraction diagram. The amor- incident ray and the scattering planes (h, deg.):
phous halo was defined and the crystalline reflection nk
profiles were fitted using Gaussian function. The d¼ ð5Þ
2 sin h
degree of cellulose crystallinity (DC0) was calculated
from the diffraction profiles using the integral Calculations were done for the first order diffracted
scattering intensities of crystalline (Ic) and amor- beam (n = 1).
phous (Ia) regions (Fig. 1): Fourier transform infrared spectra (FTIR) were
recorded on a Mattson FT-IR spectrometer Model
Ic
DC0 ; % ¼  100 ð2Þ 7300 in KBr pellets at 4 cm-1 resolution and
Ic þ Ia acquiring 128 scans per set over the spectral range
The degree of crystallinity (DC) was corrected for of 4,000–525 cm-1. The crystallinity parameter
the presence of non-cellulosic components in pulp (CrP) was determined using the ratio of the trans-
(Ioelovitch et al. 1989) thus calculating the crystal- mittance peaks registered at 1,372 cm-1, T1372, and at
linity of the cellulose portion, for which the weight 2,900 cm-1, T2900 (Tripp 1971):
fraction is w:
   T1372
1 CrP; % ¼  100 ð6Þ
DC; % ¼ DC0  1 þ 0:3 1 ð3Þ T2900
w
13
C solid-state Cross Polarization—Magic Angle
The average width of crystallite in 200 lattice plane
Spinning Nuclear Magnetic Resonance (13C CP-
was determined using the Scherer equation taking into
MAS NMR) spectra were registered on a Bruker
account the crystallite defects (Ioelovitch et al. 1989):
Avance 400 spectrometer. Samples were packed into
"   2 #12 a zirconia’s rotor sealed with Kel-FTM caps and spun
b200 cos h200 2 dL
D200 ; nm ¼  ð4Þ at 9 kHz. Acquisition parameters were as follows: ca
k dL 7000 scans with a 90° proton pulse, a cross-
polarization contact time of 1 ms and a recovery
where b200 is the width on the middle height of 200
delay of 2.5 s. Glycine was used for the Hartman–
reflection (rad); h200 is the maximum of (200)
Hahn matching procedure and as external standard
200 for the calibration of the chemical shift scale relative
101 to tetramethylsilane ((CH3)4Si).13C CP-MAS NMR
spectra were registered using humidified pulp sam-
γ
200 ples (ca. 50–60% humidity) to improve signal
a

101 Ic
resolution. The crystallinity index (CrI) was deter-
101
b 101 mined from relationship between the integration
Ic
areas of the ordered (A86–92 ppm) and amorphous
040
Ia (A79–86 ppm) C-4 signals in cellulose (Liitiä et al.
10 15 20 25 30 35 40 2000):
2θ, deg.
A8692 ppm
CrI; % ¼  100 ð7Þ
Fig. 1 X-ray scattering diffractogram of acid sulphite pulp A8692 ppm þ A79986 ppm
showing fitted crystalline reflections and the amorphous halo.
The projected cellulose cell unit depicts basic cell dimensions Thermogravimetric analyses (TGA) were carried
and lattice plans out on a Shimazu TGA-50 instrument under a

123
1196
nitrogen atmosphere in the range 25–800 °C, with a
heating rate of 5 °C/min, using about 8 mg of sample
placed in a platinum cap.
The dilute acid (1.8 M H2SO4) hydrolysis of pulps
(hydromodulus 50) was carried out under reflux.
Pulps were washed to neutral pH by distilled water,
filtered off and dried at 105 °C for 3 h to determine
the yield. The intrinsic viscosity in cupriethylenedi-
amine (CED) solution and the degree of the poly-
merization (DP) of hydrocellulose was determined
according to SCAN-CM 15:88 ([g] = 0.42DP).
The analysis of water suspension of pulps by optic
microscopy in a polarized light was carried out on an
optic microscope OLYMPUS BX51 equipped with a
digital camera OLYMPUS C4040 (4.1 megapixel
resolution).
The preparation of pulp handsheets and the
evaluation of its physical properties were carried
out according to ISO standard procedures.
Results and discussion
Effect of high pressure treatment on cellulose
structure
The conditions of hyperbaric treatments (400 MPa,
10 min) for previously dried (105 °C) acidic sulphite
(ASP) and kraft (KP) eucalypt pulps were invariant in
this study and selected according to general consid-
erations, such as average pressure conventionally
applied in industrial and laboratory practice for food
processing or for the modification of natural poly-
mers, such as starch (Oh et al. 2008). The changes in
supramolecular structure of cellulose that took place
during HP treatment were assessed by wide angle
X-ray scattering (WAXS), solid-state 13C NMR and
FTIR.
The HP treatments did not show any significant
changes in the parameters of cell unit in cellulose
Table 1 Crystalline
Sample b (±0.02 nm)
parameters of cellulose in
pulps ASP 0.801
ASP-HP 0.800
KP 0.800
KP-HP 0.797
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Cellulose (2010) 17:1193–1202
from both pulps as revealed by WAXS analysis
(Table 1). However, the average width of cellulose
crystallites assessed in (200) lattice plane (D200)
increased notably, especially for the kraft cellulose. It
is known that during wood pulping the D200 in
cellulose increases due to the partial junction of
crystalline domains in adjacent elementary fibrils—
cocrystallization (Ioelovitch et al. 1991). This is
favoured by liberation of fibril surfaces from con-
comitant lignin and hemicellulose molecules as well
as by cellulose molecular rearrangement and fibrils
aggregation (Ioelovitch et al. 1991; Hult et al. 2001b).
The cocrystallization of eucalypt cellulose under the
conditions of kraft pulping is stronger than during
acidic sulphite pulping (Rebuzzi and Evtuguin 2006).
Probably this was the reason for the more pronounced
cocrystallization of cellulose crystallites in KP than
in ASP upon HP treatment, where larger crystallites
have formed wider crystal aggregates (Table 1).
Since some cocrystallization may take place while
drying the cellulosic materials to low residual
humidity (Newman 2004), the D200 of HP-treated
pulps was always compared with those of untreated
pulps after their drying at 105 °C. Hence high
hydrostatic pressure promotes structural rearrange-
ments in cellulose fibrils leading to the junction of
appropriately oriented adjacent cellulose crystallites,
which surfaces are sufficiently close to each other,
free of associated hemicelluloses and thermodynam-
ically compatible. This feature is schematically
depicted in Fig. 2.
Usually, the cocrystallization that takes place
during wood pulping is accompanied by a small
increase of cellulose crystallinity. This was tenta-
tively explained by ordering of ‘paracrystalline‘
cellulose on the surface of fibrils (Ioelovitch et al.
1991; Newman 2004; Rebuzzi and Evtuguin 2006).
The degree of cellulose crystallinity (DC) after the
HP treatment was always increased as revealed from
analysis of pulps either by WAXS, 13C CP-MAS
a (±0.02 nm) c (±0.02 nm) c (±0.1 deg.) D200 (±0.1 nm)
0.790 1.033 93.3 4.9
0.788 1.033 93.6 5.2
0.787 1.034 93.0 5.3
0.787 1.034 93.2 5.9
Cellulose (2010) 17:1193–1202 1197

Fig. 2 Schematic
representation of cross-
section of microfibril
assembled by three
elementary fibrils. The
hyperbaric treatment
promotes the aggregation of
appropriately oriented
crystallites. Some water is
trapped in internal cavities
of fibril aggregates
remaining upon drying
(strongly bound water)

Table 2 Crystallinity of cellulose in pulps assessed by
WAXS, 13C NMR and FTIR
Sample DC (±0.3%) CrI (±1%) CrP (±1%)
ASP 70.8 50 55
ASP-HP 73.0 52 60
KP 72.7 45 53
KP-HP 76.5 50 58
NMR or FTIR (Table 2). The increase of absolute
values of DC was more pronounced for KP than for
ASP, which is in agreement with the aforementioned
higher increment of D002 in KP cellulose. The
cocrystallization upon the HP treatment was also
evident employing solid-state 13C NMR (Fig. 3). The
intensity of signal at 84.9 ppm in 13C CP-MAS
NMR spectra, assigned to C4 in accessible surfaces
of well-ordered cellulose crystallites (Wickholm
et al. 1998; Newman 2004), decreased remarkably
after the HP treatment of pulps, as expected when
coalescent surfaces become the interiors of crystal-
line domains.
HP treatment of pulps is pronouncedly endother-
mic. The temperature in pulps bags submersed in the
high pressure vessel decreased at least 10 °C upon the
HP treatment. This fact may be explained by cleavage
of strong hydrogen bonds between inaccessible
cellulose surfaces since the free hydration enthalpy
is lower than the enthalpy of intermolecular bounding
between them. Hence, the treatment at high hydro-
static pressure must open initially inaccessible cellu-
lose surfaces. Such features may take place in
semi-ordered amorphous cellulose and in surfaces
involved in strong interfibril binding (Fig. 4). In the
last case the fibril aggregates lost their integrity.
The forced hydration of pulps, promoted by high
pressure leads to increased amounts of strongly
bound water (SBW). This may be concluded based
on the increased oven dried weight of pulp after HP
treatment and confirmed by thermogravimetric anal-
ysis. The comparative analysis by TGA of air-dried
ASP and KP and the corresponding HP-treated pulps
revealed the remarkable difference in weight loss at
100–250 °C and retarded thermal degradation
(Fig. 5). The retarding weight loss of 1.5–2.0% for
ASP-HP and 3.0–4.0% for KP-HP, when compared to
untreated pulps, was assigned to SBW. TGA curves
of non-treated and HP-treated pulps crossed at ca.
380 °C indicating the complete removal of SBW at
temperatures higher than those corresponding to
maximal degradation rate (ca. 350 °C). Speculating
the origin of increased SBW it may be proposed that
fibril rearrangement under HP treatment may cause
trapping of water molecules in internal cavities of
fibril aggregates (Fig. 2) or between the surfaces of
fibrils (Fig. 4). These water molecules become
immobile and were not removed even at high
temperatures (100–250 °C). The more pronounced
amounts of SBW in HP-treated KP than in HP-treated
ASP may be determined by more intensive fibrils
aggregation in the former. However, the coincidence
between the highest amounts of SBW and the highest
abundance of glucuronoxylan (16.5% in KP contrast
6.5% in ASP) in HP-treated KP might be relevant.
This point needs further investigation.
The increase in accessibility of amorphous cellu-
lose regions upon HP treatment was confirmed by

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1198 Cellulose (2010) 17:1193–1202

C2,3,5 Fig. 4 Schematic representation of secondary wall fragment c

showing elementary fibrils (EF) assembled in microfibriles and
surrounded by hemicelluloses (HC). Strong interfibril bounding
provides the formation of inaccessible regions. These become
C1 accessible upon HP treatment

C6
C4 Effect of high pressure treatment on pulp
84.9 hornification

ASP-HP
The observed structural changes in cellulose upon
hyperbaric treatment must reflect notable changes in
ASP
pulp properties. In particular, the swelling behaviour
should be affected, taken into consideration the
100 90 80 70 60
ppm (t1)
proposed water introduction between fibril aggregates
and inaccessible fibril surfaces. This possibility was
examined comparing the swelling behaviour of ASP
and ASP-HP. The acidic sulphite pulps, unlike kraft
pulps, are highly susceptible to hornification causing
strong deterioration of their papermaking properties
(Young 1994) and decreased reactivity during chem-
ical processing (Röder and Sixta 2004). Eucalypt
84.9 sulphite pulp is not ruled out and shows worst
strength properties than kraft pulp, which is associ-
KP-HP ated to some extent with hornification upon drying
(Rebuzzi and Evtuguin 2006).
KP
The swelling capacity of ASP and ASP-HP was
assessed via water retention value (WRV) using
100 90 80 70 60
centrifugation method proposed by Jayme (1958) and
ppm (t1)
calculation of the hornification degree according to
Fig. 3 13C CP-MAS NMR spectra of eucalypt sulphite (ASP), Weise (Eq. 3). ASP was dried on air at 20 °C and at
sulphate (KP) pulps and those after the HP treatment (ASP-HP 140 °C in air-circulating oven simulating the condi-
and KP-HP, respectively)
tions of industrial airborne drying. As could be
expected the pulp drying, especially at increased
temperature, led to diminished water retention in pulp
kinetic studies of heterogeneous acid hydrolysis at and hornification (Table 3). The pulp dried at 140 °C
100 °C with diluted (1.8 M) sulphuric acid. Thus, the exhibited after HP treatment higher WRV (i.e. lower
yield of non-hydrolysed residue at the levelling point hornification) than the control untreated pulp, but also
of ASP-HP was about 5% lower than that of ASP, lower than the air-dried pulp, though the difference
indicating a faster hydrolysis and a more accessible with the latter was minimal. The problem of swelling
amorphous regions in the former (Fig. 6). At the assessment of HP-treated pulp via WRV consists in
same time, the levelling-off degree of the polymer- the presence of SBW thus giving rise always
ization (DPL) of cellulose from both pulps was underestimated WRV. The analysis of ASP and
creditably different (315 for ASP and 299 for ASP- ASP-HP by optic microscopy in a polarized light
HP). Hence, the increased crystallinity of cellulose in showed much higher internal swelling and flexibility
pulps during HP treatment was not caused by of HP-treated fibres (Fig. 7), thus confirming a
recrystallization in the longitudinal direction of recover of its ability to swell in water. Therefore,
crystallites and determined essentially by ordering HP treatments may be considered as a promising
of part of ‘paracrystalline’ cellulose on fibril surface technological tool to diminish hornification of cellu-
as it was discussed previously. losic pulps.

123
Cellulose (2010) 17:1193–1202 1199

HC

EF

EF
EF
EF

H OH OH
H H OH
O OH H H
OH H H H H OH
HO H O OHH H
HO H O
HO H O H H H O O O OH H
H
O HO H O
O HO HH O
HO H
H
O
H
H HO H OH
H OH H H OH H O HO O
OH H H OH OH H H O
OH H OH H OHH H
H H OH OH OH
OH H H H H OH
HO H
O O OH H H
OHH H H
HO H O
HO H
H
O H HO H O H
O O OH H
HO H O HO H HO H O H HO
OH H O O O H HO H H OH
H H OH H H O O
OH H OH H OH H H O
OH OH H OHH H
H OH OH
H OH H H H H OH OH
HO O OH H H H
H
H HO H O H
O
HO O OH H H
OH H
HO O H HO H H O H H O
O O HO H H O H HO H OH
OH H O O H HO H O
H H OH OHH H O O
H OH H OH H H OHH
OH H H
O OH
H H H
H H H O
O O O
O H H OH
H H H H
H H OH OH H
H H O OH H H
OH OH H H HO HO H OH
H H H O
H OH
H O
HO H OHO O H OHO H O O
OH H OH H O H
O H O H H H
HO H HO H H OH OH OHH OH
HO H O H OHO OH OH
H
O H OHH H
OH H H OH H
H OH H O OH H H OH H
H OH OH H H HO HO H OH
H H H O
H OH
H O
HO H OHO O H OHO H O
O
OH H OH H O H
O H O H H H
HO H HO H H OH OH OHH OH
HO H O H OHO OH H H OH
O OHH H OH H
OH H H H H O OHH H OH H
H H OH OH OH H HO H OH
H OH H HO H OHO H OHO H
H H
O
O
H O O OHO H O
OHH H O H OH H H
HO O HO H H OH
H H OH OH OHH
HO H O H OHO OH H
O H OHH
H OH H OH
H

123
1200 Cellulose (2010) 17:1193–1202

Effect of high pressure treatment on pulp strength 100

properties Untreated pulp
HP-treated pulp
95
Since HP treatment diminished the hornification of
sulphite pulp, a brief study was done to assess the 90
associated changes in its strength properties. Hand-

Yield, %
sheets produced from oven dried unbeaten ASP 85
before and after the HP treatment were subjected to
a series of physical tests. These results are summa- 80
rised in Fig. 8. Noteworthy, the drainability of pulps
was very similar (15° SR for ASP and 14°SR for 75
ASP-HP), though the HP treated pulp was more bulky
than the untreated one (1.97 and 2.15 cm3/g, respec- 70
tively). This, however, did not deteriorate the strength 0 1 2 3 4 5 6
properties of HP treated pulp as could be expected. In Time, h
contrast, all evaluated physical properties were
Fig. 6 Kinetics of sulphite pulp hydrolysis by 1.8 M H2SO4
significantly improved, especially for the tear under reflux. The yield of non-hydrolysed residue decreased
remarkably while pulp was pre-treated at high pressure
100 (400 MPa during 10 min)
90
80
Table 3 Effects of different drying conditions and high
Weight (%)

70
pressure treatment on ASP hornification
60
50
Pulp sample WRV Hornification
(%) (%)
40
30 Never dried 95 0
20
Air dried (20 °C) 60 37
Oven dried (140 °C) 54 43
10
Oven dried (140 °C) treated at 61 36
0
0 100 200 300 400 500 600 700 800
400 MPa
Temperature (°C)
100
resistance. Since the tear resistance is associated to
90
interfibre bonding capacity (Clark 1985), it may be
80 considered that HP treatment remarkably improved
70 this pulp property.
Weight (%)

60 Some increase of zero span tensile strength for

50
HP-treated pulp (Fig. 8) reflect the increased intrinsic
strength of fibres due to the favourable cellulose
40
fibrils rearrangement leading to crystallites aggrega-
30
tion/accretion and diminishing the distortion of their
20 surfaces. Highly probable positive correlations
10 between the amount of ordered cellulose in pulp
0 and the pulp strength characteristics (tensile strength
0 100 200 300 400 500 600 700 800 and work of rupture among others) have been
Temperature (°C) previously reported (Komarov et al. 1994). Interest-
ingly the tensile energy absorption index, as well as
Fig. 5 Thermogravimetric curves of sulphite (upper figure)
and sulphate (bottom figure) pulps before (solid lines) and after the stretch, was increased almost five times in
(dashed lines) high pressure processing handsheets produced from ASP-HP evidencing the

123
Cellulose (2010) 17:1193–1202 1201

Fig. 7 Optic microscopy images (9400 zoom) of oven dried sulphite pulp fibres (a and b) and those after high pressure processing at
400 MPa during 10 min (c and d)

14 Conclusions
12
Oven dried pulp Results of this work demonstrated that high pressure
HP-treated oven dried pulp
10 processing has promoted the hydration of pulps and
affected the structural features of cellulose. In
8
particular, the crystallites of elementary fibrils suffer
6 partial cocrystallization and recrystallyzation leading
to increment of the average crystallite width and the
4 degree of cellulose crystallinity in pulp. Simulta-
neously, the hyperbaric treatment provides the pen-
2
etration of water molecules into inaccessible
0 cellulose surfaces thus favouring the internal fibre
Tensile Tear Resistance, Burst Zero span
Strength, mN.m2/g Resistance, tensile strength,
swelling and the increment of strongly bound water in
N.m/g kPa.m2/g km pulp. This causes a decrease of hornification of dried
pulp, improving fibre flexibility and elasticity.
Fig. 8 Strength properties of bleached sulphite pulps oven
dried at 140 °C, before and after the high pressure treatment Despite more bulky handsheets have been obtained
with unbeaten HP pre-treated pulp, this did not cause
deterioration of its physical properties, but, in con-
trast, improved them, when compared to properties of
impressive enhancement of the elasticity of fibre untreated pulp. This was assigned to improved fibre
network. These results evidence the significant bonding capacity and increased intrinsic fibre
changes of papermaking properties of dried pulps, strength, due to the favourable ordering and the
when subjected to HP treatment. Hence, HP treatment increment of cellulose domains. Overall high pres-
may be advantageous to fibre materials which sure processing may be considered as an interesting
papermaking properties are drastically deteriorated tool for the modification of chemical pulps for
upon drying due to the hornification (recycled fibres, different purposes.
acidic sulphite, organosolv pulps, etc.). Since the
effect of HP treatment on papermaking properties of
pulps might depend on the particular conditions of References
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1202
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