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Progress in Organic Coatings xxx (2016) xxx–xxx

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Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Esterified organosolv lignin as hydrophobic agent for use on wood

products
Oihana Gordobil, René Herrera, Rodrigo Llano-Ponte, Jalel Labidi ∗
Chemical and Environmental Engineering Department, University of the Basque Country UPV/EHU, Plaza Europa, 1, 20018, Donostia-San Sebastián, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Lignin from Spruce and Eucalyptus wood was isolated by organosolv process, and subsequently was
Received 27 December 2015 chemically modified using a long aliphatic chain (12C) of dodecanoyl chloride as reagent, to obtain a
Received in revised form hydrophobic lignin derivative to be used as protective agent on wood products. Each esterified lignin was
22 September 2016
applied on wood by two different methods In the first method, the lignin was applied as coating using for
Accepted 23 October 2016
that a press moulding (current industrial processing technology) at two different conditions. The other
Available online xxx
method consisted in impregnation using acetone as solvent and immersing the samples during different
periods of time. The chemical modification of lignins was confirmed by FTIR, GPC and DSC resulting
Keywords:
Esterified lignin
in an increase of its molecular weight and great reduction of glass transition temperature, allowing to
Coating process lignin by press moulding besides improving the solubility in acetone. The wood hydrophobicity
Impregnation (WCA ≈ 140◦ ), oleophobicity (OCA ≈ 120◦ ) and stability against water and oil dramatically increase after
Artificial aging treatments observed by dynamic contact angle analysis. Furthermore, the efficiency of treatments over
Contact angle time was confirmed by accelerated aging test. Aesthetical assessments, by meaning of color analysis
Color (CIEL*a*b* system) showed significant differences between application methods, being more pronounced
in case of coating treatments. Additionally, after aging test the color was quite stable.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Wood is an incredibly essential raw material that has been used
extensively throughout human history and is employed in a great
variety of applications such as building materials or indoor-outdoor
products [1]. Although wood is a versatile material some of its
intrinsic properties represent disadvantages in some applications.
Its hydrophilic nature, instability against moisture and degrada-
tion due to microorganism or ultraviolet radiation are the main
drawbacks that require improvements [1,2]. On these grounds,
wood treatments are required to deal with its natural features and
enhance its durability in order to increase the service life of wood
products [3].
Achieving wood protection from external factors to prevent its
deterioration involves different protective methods such as chemi-
cal modifications of wood [4–8], thermal treatments [9,10] and the
use of additives or chemicals as coatings or penetrating finishes
[11–14]. However, the use of toxic products [8] as wood preserva-
tive represents diverse risks to humans and other life forms which
∗ Corresponding author.
E-mail address: jalel.labidi@ehu.eus (J. Labidi).
should be avoided and that involves the desire to develop new
biobased products for wood preservation.
Lignin, one of the most available natural polymers on the
earth, presents significant potential as raw material to be used as
hydrophobic agent for wood protection. Depending on the origin,
growing conditions and the used isolation process, the chemical
structures of lignins have distinctive characteristics [15,16]. Lignin
backbone is based on three phenylpropane units (p-hydroxyphenyl
(H), guaiacyl (G) and syringyl (S)) which are bound to each other via
ether and C C linkages and are substituted with numerous func-
tional groups like methoxyl groups, phenolic and aliphatic hydroxyl
groups principally [17].
However, to increase its hydrophobicity and solubility in organic
solvents [18], chemical modification of its functional groups is often
carried out. Esterification is one of the easiest reactions to perform
considering the reaction parameters and used reactants [17]. More-
over, when lignin is modified by esterification, hydroxyl groups are
replaced by ester substituent [19] and thus, reduce the number
of hydrogen bonding and generate an increased free volume in
the molecule, providing mobility of the chains [20] reducing the
glass transition point of lignin and increasing its thermoplasticity
[6,21,22]. These gained thermal properties are highly desirable for
current industrial processing technology like press moulding.

http://dx.doi.org/10.1016/j.porgcoat.2016.10.030
0300-9440/© 2016 Elsevier B.V. All rights reserved.

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Fig. 1. General schemes of esterified lignins synthesis.

On the other hand, the introduction of vegetable oils composed
by different fatty acids has a long tradition in the coatings industry
for wood protection [6,23]. Therefore, the synthesis of lignin deriva-
tives using a long aliphatic chain as reactive (with 12 carbons) could
be a good choice to develop a hydrophobic natural product with a
possible protective action on timber, besides providing a new added
value for lignin.
In general, long aliphatic alkyl-lignin derivatives or esterified
lignin, consist of two domains, lignin can be considered as pol-
yaromatic domain, and the introduced aliphatic chain could be
polyaliphatic domain linked by ester bonds. In nature already exists
a macromolecule with similar structure called suberin which is
present in most of plants and acts as a barrier between the plants
and the environment [23].
The aim of this study was to synthesize long aliphatic alkyl-
lignin derivatives from hardwood and softwood organosolv lignins
and investigate their possible use in wood treatments as protective
agent as well as the influence of lignin derivates on water and oil
affinity, their resistance to artificial aging and appearance on wood
veneers. Esterified lignins were applied on the veneers by two dif-
ferent methods. First method was a coating by press moulding at
two different conditions; the second one was impregnation using
acetone as solvent and immersing the samples at different periods
of time.
2. Experimental methods
2.1. Materials
stirrer, pyridine (2.75 mL) was used as a catalyst and dodecanoyl
chloride was added (0.9 mL), the reaction was conducted at 20 ◦ C for
2 h. After that, the solution was poured into 650 mL of 2% ice-cold
hydrochloric acid. The precipitate was filtered and washed with
excess distilled water and ethanol. The samples were then dried
in vacuum at 35 ◦ C overnight. Fig. 1 shows the general schemes
of esterified lignins synthesis. The obtained modified lignins were
called OS12C and OE12C for Spruce and Eucalyptus lignins respec-
tively.
2.4. Wood veneers treatments
Samples prepared for finishing with lignin derivative products
were sanded using silicon carbide (SiC) sandpaper with 280-grit
(Beech) and 180-grit (poplar). These wood veneers samples were
treated with esterified lignins using two different methods; first
method was coating by press moulding at two different condi-
tions (90 ◦ C/100 bar and 100 ◦ C/200 bar). Final experimental design
was set at 2 min and a dosage of 0.002 g of product per cm2 . The
treatment time assigned was the most suitable time where the
product was coated to the substrate without visual defects as well
as the quantity of product. The second method was impregnation
by immersion of veneers at room temperature in a prepared solu-
tion of acetone and esterified lignins (0.5 wt%) at different times (2,
4, 8, 12, 24, 48 and 72 h). Prior to immersion wood veneers were
dried at 105 ◦ C in an oven during 2 days and then samples were put
under vacuum for 1 h.

For lignin extraction two different raw materials were used;
Spruce and Eucalyptus wood, provided by KTH University in
Sweden. Ethanol absolute (99.9%), N,Nı́-Dimethylformamide (99%),
pyridine (99%), dodecanoyl chloride (98%) and hydrochloric acid
(37%) were used as supplied by Panreac and Sigma Aldrich. Veneers
were obtained from Poplar and Beech wood.
2.2. Lignin isolation
Organosolv extraction process was performed for both raw
materials with small differences between them. The extractions
were carried out in a 4 L pressure (20 bar) stainless steel batch reac-
tor with constant stirring (EL0723 Iberfluid) with electronic control
unit for pressure and temperature control. Spruce lignin (OS) was
extracted with a mixture of ethanol-water (50/50 w/w), H2 SO4 was
used as catalyst (1.2% w/w), and the treatment was carried out at
180 ◦ C for 60 min. The solid to liquid ratio was 1:7 (w/w) [24];
dissolved lignin was isolated by precipitation with four volumes
of cold water. For Eucalyptus lignin extraction (OE) a mixture of
ethanol water (60/40 w/w) without catalyst was used, the treat-
ment was carried out at 180 ◦ C for 90 min. Solid to liquid ratio was
1:10 (w/w) [25]. Dissolved eucalyptus lignin was isolated by pre-
cipitation from the obtained liquor with two portions of acidified
water (pH = 2). Both lignins were recovered by filtration, washed
until neutral pH and then dried at 50 ◦ C.
2.3. Lignin esterification
Esterification procedure was performed with 0.5 g of lignin dis-
solved into 15 mL of DMF in a two-necked flask with a magnetic
2.5. Characterization of lignin ester derivates
2.5.1. FTIR
The FT-IR analysis of unmodified and esterified lignins was
performed on a PerkinElmer Spectrum Two FT-IR Spectrometer
equipped with a Universal Attenuated Total Reflectance accessory
with internal reflection diamond crystal lens. A total of 8 scans were
accumulated in transmission mode with a resolution of 4 cm−1 . The
spectrum was obtained from a range of 4000–700 cm−1 .
2.5.2. GPC
Size exclusion chromatography analysis was used to evaluate
the average molecular weight (Mw) and polydispersity (Mw/Mn) of
the obtained lignin samples. N,N-Dimethylformamide (ethylDMF)
eluent was used as GPC mobile phase, at a flow rate of 0.7 mL/min
and 35 ◦ C, using a Jasco Inc. chromatograph provided with an LC-
NetII/ACD interface, a column oven CO-2065Plus and a RI-2031Plus
Intelligent Refractive Index Detector. A guard column and two
columns PolarGel-M (Varian Inc.) were employed. Calibration was
made using polystyrene standards provided by Fluka, ranging from
250 to 70,000.
2.5.3. DSC
The glass transition temperature of unmodified and esterified
lignins was determined by METTLER TOLEDO DSC 822 differential
scanning calorimetry. Samples about 5–10 mg were tested under
nitrogen atmosphere at a heating rate of 10 ◦ C/min. The isolated
and were heated from 25 ◦ C to 200 ◦ C. However, chemical modified
lignins were analyzed from −60 ◦ C to 200 ◦ C.

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Fig. 2. FTIR spectra of isolated and esterified lignins, (a) organosolv spruce lignin (OS) and (b) organosolv eucalyptus lignin (OE).
2.6. Characterization of treated wood veneers
2.6.1. Weight percent gain (WPG), moisture content, thickness
and roughness
The weight percent gain (WPG) after immersion of woods at
different times was calculated according to Eq. (1), in order to know
the relations between immersion time and WPG (%).
 
WPG (%) = (Wt − W0 ) /W0 x100%
where Wt = weight of sample after the treatment; W0 = weight of
sample before the treatment. The moisture content and thickness of
the control samples and treated wood samples were also analyzed.
In order to follow the change in the surface veneer roughness, a
profilometer (Mitutoyo Surftest SJ-301) was used to measure the
average roughness Ra (ISO 428714) selected and calculated as an
average of ten consecutive cut-off lengths for each pick-up travel
length. The length of scanning line and cut-off were set to 15 mm
and 2.5 mm, respectively, and the measurements were performed
at 0.5 mm/s stylus speed.
2.6.2. Water and oil repellence
To examine water and oil repellence of treated wood veneers
surfaces, water (WCA) and ethylene glycol (OCA) were used.
Samples were stabilized at 25 ◦ C temperature and 50% relative
humidity. Measurements were carried out using a Dataphysics
Contact angle system OCA 20. The dynamic contact angle was
determined by the placement of a droplet (3 ␮L) and at different
times (1, 10, 20, 30, 40, 50, 60, 90, 120 s). The average value
of five measurements per sample was calculated. In addition
of WCA and OCA, contact angles of diiodomethane (DCA) were
measured in order to complete the calculations using three liquids
of diverse polarity: deionized water ␥T = 72.8 mJm−2 , ␥L d = 21.8
(mJm−2 , ␥L p = 51.0 mJm−2 ), ethylene glycol (␥T = 48.0 mJm−2 ,
␥L d = 29.0 mJm−2 , ␥L p = 19.0 mJm−2 ) and diiodomethane
(␥T = 50.8 mJm−2 , ␥L d = 50.8 mJm−2 , ␥L p = 0.0 mJm−2 ) and then
were calculated the free surface energy according to Owens and
Wendt and Rabel and Kaelble from the contributions of the liquid
and the solid [26,27].
2.6.3. Optical properties
The color of the coated and immersed woods surfaces was mea-
sured by a Konica Minolta CM-2600d device and expressed using
the CIE-Lab color space coordinate system L*, a*, and b* (lightness,
red-green-axis, and yellow-blue axis). The overall color change
(E*) was also calculated from the L*, a*, and b* values for each
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3
coating system (Eq. (2)). Measurements were taken in triplicate for
each sample.

E = L∗2 + a∗2 + b∗2 (2)
where: L, a, b denote differences in parameters of compared
colors. L* axis defining lightness (values from 0 to 100%), a* − axis
running from the red color (+a*) to the green color (−a*) and b* –
(1) axis running from the yellow color (+b*) to the blue color (−b*).
2.6.4. Accelerated aging
Wood veneers were artificially aged based on a modified ASTM
D2559 technique [28]. To complete an aging cycle, samples were
dried, weighted, placed in a sealed container and submerged in
water (approx. 27 ◦ C), at 20 kPa for 15 h; then placed in a con-
vection oven at 75 ◦ C for 9 h. Once removed from the oven, each
specimen was checked for delamination or cracks and the cycle
was repeated five times. Afterwards, samples were weighted and
stored at 25 ◦ C and 50% relative humidity until they were tested to
know the changes in water and oil repellence and color changes.
3. Results and discussion
3.1. Esterification of isolated lignins
FTIR spectra (Fig. 2) of esterified lignins confirmed that the
esterification process was successful at studied conditions. This
modification is highlighted for its short period of time with-
out using temperature. Modified lignins showed that the signal
around 3400 cm−1 which corresponds to O H stretching vibra-
tions in aromatic and aliphatic hydroxyl groups was reduced and
the appearance of two new peaks at 1740 cm−1 and 1760 cm−1
are clearly seen. They are assigned to aliphatic and aromatic ester
bonds, respectively. The intense increase of peaks at 2930 cm−1
and 2840 cm−1 are assigned to long chain alkyl groups (aliphatic
carbon) which are present in fatty acid chloride [22,29].
Moreover, the thermal behaviour and visual appearance of
lignin derivatives was totally different from the original lignins.
Modified lignins have different properties such as molecular weight
and thermal properties like glass transition temperature which is
important parameter to process the lignin by hot pressing. Table 1
shows the changes on molecular weight properties of isolated and
chemically modified lignins. As can be observed, isolated lignins
are a brown thin powder while modified lignins become a soft and
sticky dark resin. As expected, after lignins esterification with dode-
canoyl chloride a significant increase in Mw can be observed. It is
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Table 1 to obtain a clearer information to identify this parameter. Both

Appearance, weight average (Mw), number average (Mn), polydispersity index
isolated lignins had a relatively high glass transition tempera-
(Mw/Mn) and glass transition temperature (Tg ) of isolated and esterified lignins (For
interpretation of the references to color in this table legend, the reader is referred ture (115–125 ◦ C) due to strong intermolecular hydrogen bonding
to the web version of this article.). interactions which restrict the thermal mobility of original lignin
molecules and result in high Tg [31]. However, lignin derivatives
Lignin sample Appearance Mn Mw PDI
presented a great reduction of glass transition temperature (Tg )
[32]. This phenomenon occurs because the replacement of hydrox-
OS 896 3124 3.5
yls groups by ester substituent produced the reduction of the
number of hydrogen bonding in lignin molecule and implied an
OS12C 2774 10300 3.7 increase free volume in the molecule and thus the mobility of the
chains.
So, the use of esterification to elaborate lignin derivative prod-
OE 1498 9490 6.3 ucts by attaching long aliphatic chains proved that it is a suitable
method to obtain lignin derivatives with suitable glass transitions
temperatures to use them in current industrial techniques.
OE12C 3192 25837 8.1

3.2. Treatments on wood veneers

known that the weight average should increase when lignin is mod-
ified with ester groups; also the molecular weight increase with the
increase in the length of the ester substituent [30]. No direct rela-
tion between the molecular weight of modified lignins and their
properties as hydrophobic product was found.
On the other hand, DSC diagrams of different lignin samples
are shown in Fig. 3. However, the glass transition temperature (Tg )
of lignin samples is often very difficult to determine due to the
heterogeneity of the lignin chemistry, as well as the broad molec-
ular weight distributions. Therefore, based on the glass transition
temperature is defined as the midpoint of the lineal variation of
the polymer heat capacity, and taking into account this inflexion
point is a maximum of the first derivative curve, it was possible
The applied systems used for wood veneers showed certain dif-
ferences. The press moulding technique did not generate a film
on wood veneers, but the esterified lignins were homogeneously
extended over woods surfaces. Despite the fact that the Tg of both
products is below 18 ◦ C, there is necessary to provide additional
energy in the form of heat to form homogeneous treatment. In
order to obtain the most uniform product the temperature was
gradually increased from room temperature up to 100 ◦ C, check-
ing that the initial product was melted-merged with the substrate
to finally solidify on the cooling stage. Table 2 shows the differ-
ences of the moisture content and thickness of veneers control
and treated veneers. As it can be observed, after treatments the
moisture content substantially decreased in all treated veneers,

Fig. 3. Differential scanning calorimetry (DSC) of (a) isolated and chemically modified Spruce lignin and (b) isolated and chemically modified Eucalyptus lignin.

Table 2
Moisture content and thickness of control veneers and treated veneres.

Sample Product Treatment Moisture contenta (105 ◦ C) Thicknessb (␮m)

Beech Control Control 6.47 ± 0.58 1120 ± 230

Poplar Control Control 7.29 ± 0.45 1360 ± 350
Beech OS12C Coating 2.44 ± 0.18 250 ± 100
Beech OS12C Immersionb 2.82 ± 0.34 10 ± 10
Beech OE12C Coating 2.19 ± 0.21 180 ± 90
Beech OE12C Immersionb 2.88 ± 0.48 18 ± 10
Poplar OS12C Coating 2.46 ± 0.22 230 ± 80
Poplar OS12C Immersionb 4.56 ± 0.86 10 ± 10
Poplar OE12C Coating 2.30 ± 0.41 210 ± 50
Poplar OE12C Immersionb 3.16 ± 0.61 10 ± 10
a
Measured with a Denver instrument IR60Q; 2 Thickness of veneers (control) and film thickness (thickness gauge PCE-CT 25).

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Table 3 The dynamic contact angle with water and ethylene gly-
Percentage of weight gained due to the product retention for impregnated wood
col of coated and impregnated wooden surfaces are shown in
samples.
Figs. 4–6. The analyses of contact angle exhibited important dif-
Sample Impregnation Retentions (%)a ferences between treated and original woods veneers. The original
time (h)
wooden veneers presented hydrophilic and oleophilic character
Beech Poplar [34]. However, wetting properties of treated wood displayed a great
2 0.38 ± 0.11 0.26 ± 0.05 improvement against water and oil. Coated wood veneers pre-
OS12C 4 0.39 ± 0.09 0.29 ± 0.07 sented values between 90–120◦ for water and 70–100◦ for ethylene
8 0.77 ± 0.12 0.44 ± 0.11 glycol. In the case of impregnated wood veneers, the contact angles
12 1.02 ± 0.17 0.54 ± 0.09 were higher and more stable than coated woods and remained
24 1.22 ± 0.22 0.88 ± 0.18
48 1.33 ± 0.28 0.97 ± 0.38
practically unchanged during the test period with 120–140◦ for
72 1.40 ± 0.19 1.01 ± 0.21 water and between 110–130◦ for oil. So, the general tendency of
2 0.48 ± 0.10 0.27 ± 0.10 the OCA with the press moulding treatment was the stability over
OE12C 4 0.54 ± 0.29 0.42 ± 0.08 time, showing with higher values in the beech veneers treated but
8 0.57 ± 0.10 0.66 ± 0.20
slightly lower in the poplar veneer treatments. With respect to
12 0.65 ± 0.13 0.73 ± 0.07
24 0.82 ± 0.22 0.74 ± 0.10 the results with poplar veneers, it was found that it surface was
48 0.85 ± 0.15 0.81 ± 0.15 slightly apolar initially (without treatment) with WCA higher than
72 1.05 ± 0.27 0.96 ± 0.14 beech veneers and with a total free surface energy lower than that
a
Percentage of weight gained due to the product retention. found in press moulding treatments and specifically with lower dis-
perse shares (leading to a better behaviour with ethylene glycol).
Table 4
It seems that the pretreatment of poplar veneers (180-grit sanded)
Roughness average of veneer samples. was crucial to activate the free surface energy, showing an equi-
table distribution of shares; while in the treated poplar veneers
Sample Treatment Roughness Ra(um)a
the free surface energy was practically disperse with lower polar
Beech Poplar shares. The study of the contact angles of three different liquids and
Control – 19.89 ± 2.82 11.65 ± 4.62 the free surface energy of the veneers treated and control was stud-
OS12C Coating 32.78 ± 9.41 28.10 ± 6.54 ied, in order to complete the study of liquid-substrate interactions
Immersionb 22.14 ± 3.32 12.49 ± 5.63 (Table 5).
OE12C Coating 36.77 ± 11.32 24.17 ± 6.97
The hydrophobic character of synthesized lignin derivates pro-
Immersionb 21.24 ± 2.14 13.27 ± 3.79
vides the high contact angle values which are stable over time.
a
Ra was measured across the grain orientation. Although used lignins come from different origin (hardwood and
b
72 h of immersion treated wood veneers.
softwood) and have different chemical structure [35]; there was not
significant differences between them regarding their hydrophobic
probably due to saturation of veneer pores after the products behaviour, thus proving that esterified lignin is an appropri-
application avoiding thus moisture absorption. Besides, the veneer ate agent to increase the wood durability. However, there can
thickness increased by 15–22% when the products were applied be observed few differences depending on the selected appli-
as coating and when products were impregnated the changes in cation methods, being more hydrophobic and oleophobic when
thickness were below 1%. On the other hand, the impregnation impregnation method was used. Nowadays, the modification and
method of veneers-lignin products was carried out at different hydrophobization of wooden surfaces by using silanes is being
immersion times in order to obtain the adequate set-time where studied and several results are already presented in the literature
the maximum quantity of product was retained. The product reten- with lower values than presented values [36,37]. Other authors
tion was calculated by weighing the veneers before impregnation obtained values below 90◦ using commercial coatings [14,38].
and after impregnation under the same conditions (65%RH and
25 ◦ C). The immersion method did not greatly affect on the gain 3.4. Optical properties
weight (0.2–1.4%) of the treated wood samples. Higher retention
of the product at higher time was observed, being almost constant The optical characterization of untreated beech wood veneers
from 24 h to 72 h (Table 3). Table 4 shows the roughness average presented color values in the meaning of lightness L* (65.51),
of veneer samples. The average roughness (Ra) of veneers before red/green hue a* (11.44), yellow/blue hue b* (24.73), chroma C*
treatments were influenced by the sanded-pretreatment, and in (27.26) and hue angle (65.08). For untreated poplar veneers the
general, were lower than on treated veneers; however the control results were lightness L* (84.28), red/green hue a* (3.35), yel-
veneers presented significant differences between species (about low/blue hue b* (24.47), chroma value C* (22.72) and hue angle
41%). After treatments all veneers increased the roughness value, (81.51). The color change in both woods after each treatment
nevertheless the immersed samples presented similar values to is visually appreciable, especially in the case of coated woods
that found in control (difference <12%). On the other hand, the (Fig. 7). The total color difference (E) of coated beech wood varies
roughness of coated samples was rather higher than in control with between 30 and 40 while poplar woods presented higher values
a difference above 65%. The roughness was influenced by the layer between 50 and 60.
formed due to the coating (0.18–0.25 mm of thickness), but in gen- In general, the lightness (L*) decreased around 50% in coated
eral the values were acceptable and the visual assessment did not beech and 60% in coated poplar. a*, b* C* and h parameters var-
show remarkable defects. ied respect to the original woods in all cases, decreasing all these
parameters in the case of coated beech but increasing the red-green
3.3. Water and oil repellence coordinate (a*) in coated poplar, with both type of lignin derivates.
On the other hand, impregnated woods presented less color
The contact angle of liquids on solid surfaces provides direct change (E) than coated woods with values between 2 and 12
information about the wetting behaviour of the surface. Kalnins for impregnated beech and 3–22 for impregnated poplar. The gen-
et al. [33] suggested the usage of a video-type technique to measure eral trend was that OS12C lignin provided greater color changes
the dynamic contact angle of liquids on wood over time. on woods than OE12C as can be observed in Fig. 7 where sam-

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Fig. 4. Water and ethylenglicol dynamic contact angle of coated beech (a, aı́) and coated poplar (b, bı́).

ples treated with OS12C presented darker color. The lightness (L*) 3.5. Accelerated weathering
decreased around 5–15% for impregnated beech and 5–20% for
impregnated poplar. Following the initial successful results, it was necessary to ana-
lyze its effectiveness through material service life. For this purpose,

Fig. 5. Water dynamic contact angle of impregnated beech and poplar with OS12C and OE12C .

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Fig. 6. Ethylenglicol dynamic contact angle of impregnated beech and poplar with OS12C and OE12C .

an accelerated aging test on treated wood veneers was performed
to know how could affect on the obtained wetting properties and
also comparing with aged control samples.
In order to know the changes during the aging cycles, the weight
loss of samples was measured. Although a clear trend was not
found, controls and treated wood samples showed comparable
weight loss with values between 1 and 3%.
Another way to follow the changes due to aging was the evalu-
ation of color by the meaning of E. In the case of coated samples
there is remarkable the stability of the samples treated at lower
conditions (90 ◦ C/100 bar) for both esterified lignins recording val-
ues below controls (E = 2–6) and being OS12C lignin at process
conditions of 90 ◦ C and 100 bar the most stable treatment. Regard-
ing impregnated wood samples, all presented similar color changes
compared with controls samples. However, the impregnated poplar
samples slightly more stable.
Finally, dynamic contact angle was again measured. As expected
aged controls presented higher affinity for water (Fig. 8). In the case
of ethylene glycol, it was not possible to measure the trend over
time after aging due to its high affinity.
On the other hand, aged coated surfaces exhibited a great
improvement against oil and water compared to the aged controls
(Fig. 9). In the case of hydrophobicity, all wood samples showed
WCA of water > 60◦ after two minutes of test. However, the effec-
tiveness of the esterified lignins against ethylene glycol after aging
was lower than the previous values presented in Section 3.3. For this
reason, it was taken as reference time 20 s which allow recording
the contact angle in all samples. Thus, less stability with an impor-

Table 5
Contact angles of three liquids with different polarity and free surface energy of veneers.

Sample Testa Control OS12C OE12C

b c
Coating Immersion Coatingb Immersionc

Beech WCA 24.54 ± 3.71 96.95 ± 1.36 132.51 ± 3.21 88.65 ± 3.18 133.24 ± 2.74
OCA 40.01 ± 18.34 91.34 ± 4.11 120.01 ± 2.69 86.45 ± 4.06 117.54 ± 5.12
DCA 3.51 ± 2.11 56.67 ± 4.38 7.01 ± 5.87 55.51 ± 1.12 7.61 ± 3.66
␥p 24.59 0.47 9.31 2.29 9.55
␥d 36.72 26.13 40.09 24.18 40.87
␥T 61.31 26.60 49.40 26.48 50.42

Poplar WCA 67.31 ± 5.25 111.25 ± 8.64 131.66 ± 4.69 99.61 ± 1.02 131.06 ± 3.77
OCA 80.40 ± 8.11 66.31 ± 3.78 123.51 ± 6.39 62.91 ± 3.65 121.04 ± 4.44
DCA 62.61 ± 6.03 40.48 ± 2.55 62.62 ± 4.62 42.01 ± 1.02 4.65 ± 1.03
␥p 12.98 0.69 3.03 0.04 8.82
␥d 18.31 42.92 21.42 39.07 39.67
␥T 31.29 43.61 24.45 39.11 48.49
a
Values derived of average contact angle at time 60 s.
b
Average contact angle of both press moulding treatments at time 60 s.
c
Average contact angle at time 60 s of all veneers immersed at different times.

Please cite this article in press as: O. Gordobil, et al., Esterified organosolv lignin as hydrophobic agent for use on wood products, Prog.
Org. Coat. (2016), http://dx.doi.org/10.1016/j.porgcoat.2016.10.030
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Fig. 7. RGB color space calculated for wood samples (a) untreated beech, (b) beech coated with OE12C at 90 ◦ C/100Ba, (c) impregnated beech d with OS12C (72 h), (d) untreated
poplar, (e) poplar coated with OS12C at 90 ◦ C/100Ba and (f) impregnated poplar with OS12C (72 h).

case of WCA the values were higher than 80◦ after two minutes of
test. On the other hand, greatest differences were observed during
dynamic contact angle with ethylene glycol on aged impregnated
veneers. At the reference time (20 s) was observed a reduction of
OCA between 25 and 100% for beech-OS12C , 25–70% for beech-
OE12C , 25–40% for poplar-OS12C and 10–30% for poplar-OE12C .
The obtained WCA and OCA values after artificial aging were
positive proving the resistance of the synthesized hydrophobic
agent and thus improving the wood products service life. These
hydrophobic values are comparable with commercial products and
with those found in literature.

4. Conclusions

The esterification process at short time and room tempera-

Fig. 8. Differences on WCA between unaged controls and aged controls.
tant decrease of contact angle (OCA) at that time was observed,
being the results between 40 and 80% for OS12C coatings and about
20–30% for OE12C coatings.
Concerning impregnated aged samples there was found higher
stability against water and oil than in coated aged veneers. In the
ture was successful to synthesize lignin ester derivatives to use as
hydrophobic agent on wood products. Esterified lignins presented
a significant decrease on glass transition temperature making them
suitable to use by industrial processing such as press mould-
ing. Regarding the application methods performed, a stable and
high hydrophobic and oleophobic behaviour on wood veneers was
observed. However, the immersion method provided the highest
and more stable dynamic contact angle for water and oil which
remained practically unchanged over time. The color change on
treated veneers was visually appreciable, especially in the case of
coated woods. The dark shades generated by these products can

Fig. 9. Wetting of a wood surfaces by liquid: (a) aged poplar at 30 s with water, (b) impregnated aged poplar with OS12C (2 h) at 120 s with water, (c) impregnated aged poplar
with OE12C (4 h) at 120 s with water and (d) impregnated aged poplar with OE12C (2 h) at 120 s with ethylenglicol.

Please cite this article in press as: O. Gordobil, et al., Esterified organosolv lignin as hydrophobic agent for use on wood products, Prog.
Org. Coat. (2016), http://dx.doi.org/10.1016/j.porgcoat.2016.10.030
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be an advantage for undervaluated woods by adding an aesthetic
contribution. Furthermore, the efficiency of treatments over time
was confirmed by the means of color analysis and dynamic contact
angle. The color change was quite stable after aging test. Also, WCA
and OCA values were acceptable decreasing about 40% and thus
the resistance of the synthesized hydrophobic agent was proved
improving the wood products service life.
Acknowledgements
The authors are grateful for the financial support received from
the University of the Basque Country (doctoral grant of Ms. Gordobil
grant no. PIF13/050) and to theBasque Government (scholarship of
young researchers training and project IT672-13).
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