DOI 10.
1515/hf-2012-0126      Holzforschung 2013; 67(3): 273–276
Short Note
José A.F. Gamelas*, Gustavo V. Duarte and Paulo J. Ferreira
Inverse gas chromatography and XPS of extracted
kraft pulps
Abstract: Kraft pulps at the κ number level of 15 obtained
from Acer saccharum (sugar maple) and Eucalyptus globu-
lus prepared with and without hot water extraction (HWE)
were analyzed by inverse gas chromatography (IGC) and
X-ray photoelectron spectroscopy (XPS). In the case of
A. saccharum pulps, the dispersive component of the sur-
face energy (γsd) at 40°C determined by IGC was 39.8 mJ m-2
(control pulp without HWE) and 36.7 mJ m-2 (HWE pulp).
Eucalyptus globulus pulps resulted in γsd values of
30.8  mJ  m-2 (control) and 34.9 mJ m-2 (HWE). The higher
values of γsd for sugar maple pulps were interpreted as the
influence of lower amounts of extractives or lignin at their
surface, as revealed by XPS. It is also discussed why the
acid-base character of the sugar maple pulp surface was
slightly reduced with previous HWE, whereas, for E. glob-
ulus, it was greatly enhanced.
Keywords: acid-base character, E. globulus, IGC, sugar
maple, surface properties, XPS
*Corresponding author: José A.F. Gamelas, Chemical Engineering
Department, University of Coimbra, Pólo II, R. Sílvio Lima,
3030-790 Coimbra, Portugal, e-mail: jafgas@eq.uc.pt
Gustavo V. Duarte: Chemical Engineering Department, University
of Coimbra, Coimbra, Portugal
Paulo J. Ferreira: Chemical Engineering Department, University
of Coimbra, Coimbra, Portugal
Introduction
The physicochemical surface properties of lignocellulosic
materials are important in the context of papermaking and
in the production of composites (Gregorova et  al. 2009;
Rocha et al. 2009; Tonoli et al. 2010; Gamelas et al. 2012).
These properties can be evaluated by contact angle meas-
urements (Gindl et al. 2001; Walinder 2002) and even more
effectively by inverse gas chromatography (IGC) or X-ray
photoelectron spectroscopy (XPS). IGC is a highly sensitive
technique for the characterization of the surface properties
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of particulate and fibrous materials, in the course of which
a single gas or vapor (probe molecule) is injected into a
column packed with the solid sample under investigation.
The interaction of several molecular probes with the high-
est-energy sites of the surface of the material is measured,
enabling to obtain important thermodynamic and surface
energy parameters. XPS gives information of the chemi-
cal composition of the surface up to approximately 10 nm
depth, and it is an established method in wood science
(Tuong and Li 2011; Brodin et al. 2012; Rautkari et al. 2012).
Both IGC and XPS were used to evaluate the effects of
cooking, bleaching, and beating processes on pulp surfaces
(Shen et  al. 1998; Shen and Parker 1999; Belgacem 2000;
Carvalho et  al. 2005a,b). Recently, the effect of hot water
extraction (HWE) on red maple (Acer rubrum) wood was
also studied by IGC (Mills et al. 2009; Paredes et al. 2009).
In this work, kraft pulps from Acer saccharum (sugar
maple) and Eucalyptus globulus, which were obtained
with and without HWE before cooking, were analyzed
by IGC and XPS. The results of these analyses will be dis-
cussed in terms of the most relevant surface properties
and surface chemical composition.
Materials and methods
The sugar maple chips were from the Heiberg forest in Tully, NY, and
the E. globulus chips were from a paper mill in Portugal. The extrac-
tions and cooks were carried out in a 4.5 l laboratory digester with
a liquid-to-wood ratio of 4:1 at 160°C. Parameters of HWE: heating
ramp time (until reaching 160°C) of 30 min and extraction time (at
160°C) of 120 min. For kraft cooks, the heating ramp time was 60
min. The white liquor had 16% active alkali and 25% sulfidity and
the H-factor was chosen to achieve κ no. 15. The kraft cook of HWE
chips was done right after the extraction, that is, the chips were never
dried. The control pulps were obtained without previous HWE.
The original woods and the kraft pulps were all analyzed for the
cellulose and hemicelluloses content by 1H nuclear magnetic reso-
nance spectroscopy (Kiemle et al. 2004; Duarte et al. 2012) and for the
total lignin content (Klason lignin plus acid-soluble lignin). Hexe-
nuronic acids (HexA) in the pulps were determined by the method
proposed by Chai et  al. (2001). All analyses were done at least in
duplicate and the duplicated results did not differ by more than 5%.
274      J.A.F. Gamelas et al.: IGC and XPS of kraft pulps

For IGC, the pulps were milled in a laboratory mill (60-mesh 1.E+07 Sugar maple control pulp
screen). The analysis was carried out on a DANI (Milan, Italy) GC1000 Sugar maple extracted pulp
8.E+06
digital pressure control gas chromatography instrument equipped
with a H2 FID at a column temperature of 40°C, injector tempera- 6.E+06
ture of 180°C, and detector temperature of 200°C. He was the carrier
4.E+06
gas and methane was the reference. The probes, n-hexane (C6), n-
heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), trichlo- 2.E+06
romethane (TCM), acetone, tetrahydrofuran (THF), and ethyl acetate
0.E+00
(ETA), were of chromatographic grade (Sigma-Aldrich, St. Louis, MO,

RT In(Vn) (mJ mol-1)

USA). The retention times reported are the average of at least three in- -2.E+06
jections and were determined at the peak maximum for symmetrical
-4.E+06
peaks or by the recommended Conder and Young method for the less
1.E+07
symmetrical peaks. The coefficient of variation between runs was not Eucalypt control pulp
larger than 3%. The theory behind IGC and the values of the physical 1.E+07 Eucalypt extracted pulp
properties (a and γld) of the probes used in this work was described 8.E+06
by Santos and Guthrie (2005). 6.E+06
The XP spectra were obtained by an ESCALAB 200A (VG Scien-
4.E+06
tific, East Sussex, UK) instrument in combination with PISCES soft-
ware (Data Systems, Bristol, UK). An achromatic Al (Kα) X-ray source 2.E+06
operating at 15 kV (300 W) was used. The spectrometer, calibrated 0.E+00
with reference to Ag 3d5/2 (368.27 eV), was operated in constant ana-
-2.E+06
lyzer energy mode with 20 eV pass energy. Spectra analysis was per-
formed based on peak fitting with Gaussian-Lorentzian peak shape -4.E+06
2.E+06 3.E+06 4.E+06 5.E+06
and Shirley-type background subtraction. Samples were analyzed at
least in duplicate with pellets of approximately 1 cm diameter. 2N·a(γId)0.5 [(mJ)0.5 m·mol-1]

Figure 1 Determination of the dispersive component of the surface

Results and discussion
The analysis data on the bulk chemical composition of
the pulps (Table 1) are in agreement with the expectations
concerning the decrease in the hemicelluloses content
(mainly due to xylan loss) after HWE pretreatment (Duarte
et al. 2011, 2012). The pulps with lower amounts of xylan
(HWE pulps) also show lower HexA contents, that is, HexA
decreased from 63–65 to 2–5 mmol kg-1 as a result of HWE.
The dispersive component of the surface energy (γsd)
of the pulps was determined based on the retention times
obtained for a series of n-alkanes (C6, C7, C8, C9, and C10).
From the plots of RTln(Vn) as a function of 2N⋅a(γld)0.5,
as depicted in Figure 1, the values calculated for γsd were
39.8 and 36.7 mJ m-2 for the control and HWE sugar maple
pulps, respectively. These values are higher than those
energy of kraft pulps made of A. saccharum and E. globulus by IGC
at 40°C.
obtained for the corresponding eucalypt pulps (30.8 and
34.9 mJ m-2 for the control and HWE eucalypt, respec-
tively). Besides, the γsd value decreased in the HWE sugar
maple pulp relatively to the control, whereas the opposite
occurred for eucalypt. In this context, it should be noted
that γsd data (at 40°C) of 38–39 mJ m-2 were reported for red
maple wood after extraction at 160°C for 90 min, whereas
those values of the original wood samples were 36–37 mJ
m-2 (Mills et al. 2009; Paredes et al. 2009).
The differences in the dispersive component of the
pulp surface energy, which is connected mainly to London
interactions between molecules, are likely to be related to
the contents of polysaccharides, lignin, and extractives
on the pulp surface. The XPS results with this regard are

Pulp Amount in bulk (%) by wt. XPS resultsa

Cellulose Xylan Other hemicelluloses Lignin HexA (mmol kg-1) O/C ratio C1 C2 C3

A. saccharum control 73.9 16.5 1.0 2.6 65.4 0.62 25.1 59.2 15.6
A. saccharum HWE 88.8 3.5 0.3 2.5 5.1 0.61 27.0 58.5 14.5
E. globulus control 74.8 15.8 0.4 2.2 63.1 0.55 36.2 49.8 14.0
E. globulus HWE 89.9 2.5 0.2 2.1 1.8 0.56 33.6 52.4 14.0

Table 1 Effect of HWE for 120 min on the bulk chemical composition of kraft pulps and their surface characteristics as determined by XPS.
a
C1 represents carbon linked only to hydrogen or to carbon (-C-H, -C-C or C = C), C2 corresponds to carbon linked to a single oxygen (-C-O),
and C3 represents O-C-O or -C = O bonds.

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a b
C2
C1
C3
291 288 285 282 291 288 285
Binding energy (eV) Binding energy (eV)
c d
291 288 285 282 291 288 285
Binding energy (eV) Binding energy (eV)
Figure 2 Deconvolution of the XP spectra in the region of carbon
binding energies for (a) A. saccharum control pulp, (b) A. saccharum
HWE pulp, (c) E. globulus control pulp, and (d) E. globulus HWE pulp.
HWE, chips that were hot water extracted before pulping.
listed in Table 1 and illustrated in Figure 2. Considerably
higher O/C atomic ratios were found for both the control
and the HWE sugar maple pulps in comparison with the
corresponding eucalypt pulps. The deconvolution of the
XP spectra in the region of carbon binding energies (Figure
2) shows that the sugar maple pulps have less C1 groups
and more C2 groups than the eucalypt pulps. Typically, C1
is the major spectral component for lignin and extractives,
whereas C2 is the dominant component for cellulose and
hemicelluloses (Belgacem et al. 1995; Shen et al. 1998; Shen
and Parker 1999). Therefore, a lower amount of extractives
or lignin (or both) can be anticipated at the surface of the
sugar maple pulps in comparison with the eucalypt pulps.
This must be the reason why a higher value of γsd was deter-
mined for sugar maple pulps, once extractives and lignin
have lower γsd than cellulose (Belgacem et al. 1995; Shen
and Parker 1999). The γsd decrement in the case of HWE
sugar maple pulp versus control is in agreement with the
increase of the C1 part of the carbon signal.
The acid-base properties of the pulps’ surfaces were
evaluated based on calculations of the specific component
of the work of adhesion (Was) between the surfaces and
several polar probes, namely, acidic (TCM), basic (THF),
and amphoteric (acetone and ETA) probes (Figure  3). For
all the control and HWE samples, the Was values followed
the order: acetone > ETA, THF > TCM. The greater affinity of
the pulps’ surfaces with a basic probe (THF) than with an
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J.A.F. Gamelas et al.: IGC and XPS of kraft pulps      275
30 Sugar maple control pulp
Sugar maple extracted pulp
25 Eucalypt control pulp
Eucalypt extracted pulp
Was (mJ/m2)
20
15
10
5
282
0
TCM THF ETA Acetone
Figure 3 Work of adhesion of control and HWE A. saccharum and E.
globulus kraft pulps with several polar probes at 40°C as deter-
mined by IGC.
acidic one (TCM) indicates that pulps have a more acidic
character than a basic one. This is in agreement with the
dominant presence of OH groups (and also COOH groups,
282 although to lesser extent) in the macromolecular structure
of the polysaccharide components.
The values of the work of adhesion seem to decrease
slightly in the HWE sugar maple pulp in comparison with
the control, that is, the acid-base properties were not
enhanced in the extracted pulp. Because hemicelluloses
are more hydrophilic (and polar) than cellulose, this result
is not unexpected in view of the large removal of hemi-
celluloses (including HexA) during the HWE stage and,
in addition, due to the slight increase of the extractives
or lignin contents on the pulp surface (Table 1). Eucalypt
pulp behaved differently, as HWE enhanced the acid-base
properties. In this material, the partial removal of extrac-
tives or lignin from the surface, as shown by XPS, could
unblock some high-energy sites, mainly from cellulose
chains, setting free these sites to interact with the polar
probes, thus enhancing the acid-base properties of the
pulp surface. Because IGC is sensitive only to the highest-
energy sites, it can be stated that the amount of those
active sites increased in HWE eucalypt pulp.
Conclusions
The higher γsd values obtained for both unextracted and
HWE sugar maple kraft pulps (39.8 and 36.7 mJ m-2, respec-
tively) in comparison with the corresponding E. globulus
pulps (30.8 and 34.9 mJ m-2) indicate a higher tendency of
the former pulps to undergo London dispersion interac-
tions. Moreover, regarding the effect of HWE, the contri-
bution of the London interactions to the surface energy
was enhanced by the pretreatment in the case of E. globu-
lus. The acid-base character of the different pulps, with
the exception of E. globulus control pulp, was of similar
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276      J.A.F. Gamelas et al.: IGC and XPS of kraft pulps
magnitude as measured by the works of adhesion with
characteristic polar probes. In addition, the acid-base
character of the E. globulus pulp surface was significantly
enhanced with previous HWE in spite of the removal of
high amounts of hemicelluloses from the bulk. Probably,
the extracted E. globulus pulp, which is not well suited
for paper production, could be suited for reinforcement
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