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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- Keywords Cellulose  High pressure processing 
lyptus globulus pulps were subjected to treatment at Swelling  Hornification
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- Introduction
inantly via lateral aggregation (cocrystallization) and,
to some extent, due to the accretion of cellulose from The physical and chemical properties of cellulose are
noncrystalline domains (recrystallization). The trea- strongly affected by its swelling ability in water
ted pulps exhibited increment of the amount of (Warwicker 1971; Clark 1985). Being a fibrillar polar
strongly bound water and improved accessibility to polymer cellulose properties are vulnerable to moist-
amorphous domains. The high pressure treatment of ening-drying cycles. During drying of cellulose
dried sulphite pulp led to restoration, at least materials the rearrangement of cellulose molecules
partially, of its swelling capacity thus diminishing and interfibril aggregation in virgin (never-dried)
the hornification features. Pressure treated dried fibres takes place leading to irreversible structural
sulphite pulp showed improved fibre bonding capac- changes (Hult et al. 2001a; Newman 2004). This
ity at simultaneously increased bulk of the produced phenomenon is known as hornification and was
handsheets. The results obtained clearly showed the widely discussed for chemical pulps (Minor 1994;
potential of high pressure treatments for the modifi- Weise 1998). The fibres of dried pulp become less
cation of cellulosic fibres in different applications. 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
A. Figueiredo  D. Evtuguin (&)
CICECO, Chemistry Department, University of Aveiro, et al. 1996). Hornification is responsible for the
Campus de Santiago, 3810-193 Aveiro, Portugal drastic decrease in papermaking properties of chem-
e-mail: Dmitrye@ua.pt ical pulps and, especially, of recycled fibres thus
limiting their reutilization (Nazhad and Paszner 1994;
J. Saraiva
QOPNA, Chemistry Department, University of Aveiro, Kato and Cameron 1999). The extent of cellulose
Campus de Santiago, 3810-193 Aveiro, Portugal hornification in pulp depends on the pulping method

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1194 Cellulose (2010) 17:1193–1202

applied and decreases with the increase of amount of Materials and methods
residual hemicelluloses that impede the fibrils aggre-
gation (Oksanen et al. 1997; Rebuzzi and Evtuguin Cellulosic pulps
2006).
One way to overcome the problems of rewetting of Cellulosic pulps used in this work were never-dried
cellulosic materials and to introduce structurally industrial eucalypt pulps: (1) acidic sulphite pulp of 89%
associated water may be the treatment at high ISO brightness and intrinsic viscosity of 950 cm3/g
hydrostatic pressures (hyperbaric treatment). High supplied by CAIMA Companhia de Celulose (Portu-
pressure (HP) technology was applied for many years gal); (2) kraft pulp of 91% ISO brightness and intrinsic
in the production of ceramics, composite materials, viscosity of 920 cm3/g supplied by PORTUCEL (Por-
plastics and artificial diamond and is now an tugal). The sulphite pulp contained 6.5% of pentosans
expanding technology that has attracted increased and 0.7% of residual lignin and kraft pulp contained
attention for food preservation and processing, 16.5% of pentosans and 0.1% of residual lignin. Pulps
mainly due to the advantages that it offers in were analysed for pentosans and residual lignin as
comparison to thermal processing. The application described previously (Rebuzzi and Evtuguin 2006). The
of HP to foods causes microbial destruction, leading pulps were dried on air at 20 °C to humidity of around
to food pasteurization, while keeping their nutritional 8% or, alternatively at 140 °C for 1 h to ca. 2% humidity.
value and organoleptic properties (Ramirez et al.
2009; Oey et al. 2008; Rastogi et al. 2007; Torrecilla High pressure treatment
et al. 2004). A broad range of pressure processed/
pasteurized food products are now commercially Dried chemical pulps were swollen in distilled water
available worldwide (Ramirez et al. 2009). In these for 12 h under moderate agitation before the high
processes pressures of up to 600 MPa are usually pressure processing (hydromodulus about 60). About
used (Oey et al. 2008; Rastogi et al. 2007). Apart 20.0 mL of pulp suspension, containing 0.33 g (dry
from these food preservation applications, high weight) of pulp were closed into a heat-sealed plastic
pressure is being increasingly studied for modifying bag that was introduced in a second plastic bag,
food texture as a technological basis for innovative which was heat-sealed under vacuum and submitted
foods with modified functional properties or struc- to 400 MPa during 10 min at room temperature (ca
tures (Rademacher and Hinrichs 2006) and for 20 °C). HP processing was carried out in a High
biotechnological applications (Salvador et al. 2010). Pressure U33 device (Institute of High Pressure
Moreover, high pressure can cause protein and Physics, Poland), with a high pressure vessel of
enzyme denaturation (Castro et al. 2006) and change approximately 100 cm3 capacity, filled with a pressure
the structure and functionality of biomacromolecules, transmitting medium (propylene glycol:water, 1:1,
such as starch (Gomes et al. 1998; Oh et al. 2008). It v/v). After HP treatment, the sample was dried in an
has been shown that starch is gelatinized by a oven for 3 h at 105 °C, and stored in a desiccator. For
two-step mechanism while applying a hydrostatic comparison reasons, a sample of oven-dried pulp at
pressure of 450 MPa at room temperature (Gomes 140 °C was swelled in distilled water and HP-treated
et al. 1998; Oh et al. 2008). In the first step, hydration under the same conditions as described above.
of amorphous parts of the starch granules occurs,
which leads to swelling of the granules and distortion Analyses
of the crystalline regions. In the second step, the
crystalline regions become accessible to water (Oh Pulp hornification was assessed by comparison
et al. 2008). between water retention value (WRV) of never-dried
High pressure has never been applied before on (WRV0) and dried (WRV1) pulps (Weise 1998):
cellulosic pulps and was the main challenge of this WRV0  WRV1
study. The effect of a high pressure of 400 MPa Hornification; % ¼  100 ð1Þ
WRV0
during 10 min on structure and some physical and
chemical properties of cellulose in chemical pulps WRV was determined according to a commonly used
was evaluated. procedure (Jayme 1958).

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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

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1196 Cellulose (2010) 17:1193–1202

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

Table 1 Crystalline
Sample b (±0.02 nm) a (±0.02 nm) c (±0.02 nm) c (±0.1 deg.) D200 (±0.1 nm)
parameters of cellulose in
pulps ASP 0.801 0.790 1.033 93.3 4.9
ASP-HP 0.800 0.788 1.033 93.6 5.2
KP 0.800 0.787 1.034 93.0 5.3
KP-HP 0.797 0.787 1.034 93.2 5.9

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

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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

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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
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