Adhesion de Recubrimientos en Madera

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Adhesion of coating materials to wood
Jozef Kdela & Eva Liptkov
Version of record first published: 02 Apr 2012.
To cite this article: Jozef Kdela & Eva Liptkov (2006): Adhesion of coating materials to wood,
Journal of Adhesion Science and Technology, 20:8, 875-895
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J. Adhesion Sci. Technol., Vol. 20, No. 8, pp. 875895 (2006)
VSP 2006.
Also available online - www.vsppub.com
Adhesion of coating materials to wood
JOZEF KDELA
1,
and EVA LIPTKOV
2
1
Technical University in Zvolen, Faculty of Wood Sciences and Technology, Department of Wood
Science, Masarykova 24, 960 53 Zvolen, Slovak Republic
2
M. R. tefnika 9, 960 01 Zvolen, Slovak Republic
Received in nal form 20 March 2006
AbstractThis study analyses the work of adhesion calculated according to the YoungDupr
equation and the work of adhesion calculated based on the interactions at the interface between the
coating material in the liquid phase and the wood. It has been shown that the adhesion of coating
materials to wood and their ability to spread over the substrate surface are primarily controlled by
interactions between the surface forces at the interface. The values of these interactions conrmed
that the tested materials should spread spontaneously over the wood surface. There are also discussed
the secondary factors that can signicantly inuence the interactions between the surface forces and,
consequently, the nal stability of the examined system.
The values of surface free energy for the hardened coating materials were considerably higher than
the original values of surface free energy for the corresponding liquid coatings especially due to
the several times higher polar component. We also observed a considerable increase of the work of
adhesion of the coating materials to the wood due to the hardening process. This increase resulted
mainly from interactions between the polar components of surface free energy of the adjacent phases.
The increase in adhesion of the coating materials during the hardening process was accompanied by
a decrease in the interfacial free energy at the interface with the substrate.
Mechanical testing of the stability of the coating materialwood system showed that the failure
in the system always occurred in accordance with the calculated values of the work of adhesion of
the coating material to the wood and the work of cohesion of the coating material and of the wood
substrate.
Keywords: Coating materials; wetting; contact angle; surface free energy; spreading coefcient;
adhesion; cohesion; tensile strength; wood.
1. INTRODUCTION
The nal surface quality of wood coated with synthetic or natural paint (coating)
materials is a result of the chemical composition of the paint materials, properties
To whom correspondence should be addressed. E-mail: kudela@vsld.tuzvo.sk

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876 J Kdela and E. Liptkov
of the substrate and interactions between the two materials. The interaction between
the coating and wood materials comprises:
interactions between the coating material and the wood at their interface,
secondary inuences arising from specic properties of the coating material and
the wood substrate.
Examination of the interactions across the interface between the wood and a coating
material requires focusing on two basic systems:
solid materialliquid,
two solid materials with different physical and chemical properties.
The rst case is considered when we study the interface between wood and coating
material during its application. Interactions between surfaces occurring across the
interface in such a case are primarily reected in the wetting and spreading of the
coating material over the substrate surface. This determines, together with wood
substrate morphology, the area of contact interface (coatingwood) and the nal
smoothness of the coating layer. Consequently, the study of wood wetting with
coating materials is necessary for understanding adhesion of these materials to the
wood substrate.
The solid coatingwood system is formed after the hardening (drying) of the
coating material on the substrate surface. Our hypothesis is that the development
and stability of this system is primarily controlled by the interactions between the
unsaturated active zones at the interface between the solid coating and wood and by
the cohesion within the particular constituents of the system.
The purpose of this study was to explore the interactions between the surface
forces at the interface of coating and wood material in both liquid and solid phases,
and, based on the results obtained, to elucidate the mechanism of adhesion of
coating materials in both liquid and solid phases to wood.
2. WOODCOATING MATERIAL SYSTEM
2.1. Wood
Wood is a heterogeneous, anisotropic, porous and hydrophillic natural material.
Variously shaped and variously arranged anatomical elements of wood constitute
a heterogeneous porous structure (Fig. 1). The pores with radii r 100 nm are,
in general, present in the cell walls. The pores with r > 100 nm correspond to the
lumens of cell elements and the intercellular space. The latter represents a major
part of wood porosity. At the same time, it is necessary to consider the specic
features of individual wood species (shape and size of the pores, their mutual
linking and spatial arrangement). The heterogeneity of wood porous structure is
naturally reected in a higher variability of the wood surface roughness and uneven
penetration of the liquid coating materials into wood. The result is the formation of
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Adhesion of coating materials to wood 877
Figure 1. Distribution of pores in beech wood as determined using mercury porosimetry.
a wood layer pre-impregnated with the coating material [1, 2]. The thickness of the
pre-impregnated layer is dependent on several factors.
The wood porosity related to penetration of a lm-forming material into wood
has a twofold effect: it increases the contact area between the wood and the coating
material, and can cause defects in the nal coating quality.
Chemical properties of wood depend on its chemical composition (cellulose,
hemicelluloses, lignin and extractives). The quality of wood surface with applied
coating is also inuenced by the extractives [38] that can cause:
migration of wood extractives into the coating,
undesired changes in the substrate colour,
inhibition of coating material hardening.
Chemical composition of wood is also reected in its hydrophilic nature. The
sorption capacity of wood is dependent on the density of functional groups con-
stituting the adsorption grid. The equilibrium moisture content in the wood also
depends on the ambient environment (relative air humidity and temperature). Wood
moisture is necessary to consider both at the application stage of lm-forming ma-
terials as well as after the lm hardening because with varying wood moisture con-
tent, the dimensions (swelling, shrinking) also change, which causes development
of stresses in the solid coating. Excessive moisture content in wood can result in
poor adhesion properties of the coating material.
Chemical composition of wood also determines the thermodynamic properties
of its surface (surface free energy, dispersion and polar components, etc.). We
measured the values of surface free energy ranging from 60 to 70 mJ m
2
depending
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Table 1.
Surface free energy of selected wood species , with dispersion and polar components
d
and
p
(microtomed surface)
Wood species
d
p
[mJ m
2
]
Spruce 60.3 27.8 32.5
Pine 66.9 25.0 42.0
Birch 67.8 24.6 43.2
Aspen 68.3 24.4 43.9
Beech 68.1 24.5 43.6
Walnut sapwood 67.8 24.6 43.2
Walnut heartwood 65.0 26.0 39.0
Oak 63.9 26.5 37.3
Elm 65.4 25.7 39.7
on the wood species (Table 1) and on mechanical treatment of the wood surface
[912].
Surface free energy is of an additive nature and consists of dispersion, i.e. non-
polar and a polar component that determine the polar/non-polar character of the
wood surface. As seen in Table 1, the polar component of surface free energy
is signicantly higher than the non-polar component. Several authors [1316],
however, have reported that the non-polar component is higher. However, this value
can be considerably inuenced by the method of measurement of the equilibrium
contact angle discussed in the following text.
Both physical and mechanical properties of wood inuence a wide range of
characteristics (density, moisture content, swelling and shrinkage, permeability,
strength, elasticity, hardness. . .) and have an indirect impact on the quality of
surface treatment and on the stability of the woodsolid coating system.
2.2. Coating materials
The basic characteristics of coating materials primarily depend on the chemical
composition of the lm-forming constituent. In the drying process, both physical
and chemical events occur leading to the formation of thermoplastic or thermoset-
ting lms with specic physical and chemical properties. Today, the production of
such lms can be well controlled and their properties adjusted precisely according
to the requirements.
The values of surface free energy for the selected types of coating materials
in their liquid form and the separate values for dispersion and polar components
are summarized in Table 2. The surface free energy for all organic solvent-
borne coatings is virtually the same and ranges from 27.01 to 27.61 mJ m
2
. The
dispersion component of surface free energy is highly dominant (the ratio of the
dispersion to polar component is about 9 : 1). The surface free energy of the water-
based acrylate lacquer is considerably higher than the organic solvent-borne types,
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Table 2.
Basic statistical characteristics of cumulative values of surface free energy for selected coating
materials in the liquid phase
L
and separate values for dispersion and polar components
d
L
and
p
L
[17]
Coating material
L
s
d
L
s
p
L
s Number of
measurements
[mJ m
2
] n
Nitrocellulose lacquer 27.61 0.65 24.76 0.41 2.85 0.23 20
Acid-hardened lacquer 27.22 0.50 24.51 0.30 2.71 0.18 20
Polyurethane lacquer 27.14 0.64 24.39 0.42 2.65 0.22 20
Polyester lacquer 27.01 0.59 24.37 0.39 2.64 0.21 20
Water-based acrylate lacquer 34.69 1.89 28.54 0.82 6.15 1.08 20
s standard deviation.
and this can be attributed to the higher proportion of polar component. In the case
of water-based acrylate lacquer, the value of surface free energy is dependent on the
amount of water contained in the coating.
The values of surface free energy of coating materials are approximately 2.5-times
lower than the values of surface free energy of wood. The values
d
L
are nearly
equivalent to the values of the dispersion component of the surface free energy of
wood; on the other hand, the values of polar component of surface free energy of
coating materials are several times lower in comparison to the values of the polar
component of surface free energy of wood.
We examined the wood wetting with coating materials. In most cases we observed
that the wetting of wood substrate with the coating material was incomplete [17].
3. INTERACTIONS OF WOOD WITH COATING MATERIALS IN THE LIQUID
PHASE
Application of coating materials onto the wood surface entails creation of an
interface between the coating material and the wood.
The process of wetting and adhesion at the interface between the coating and the
wood material in the liquid phase will be inuenced by the chemical constitution
of the wood substance as well as morphology of the wood surface. There exist
a number of properties of these two contacting phases: geometry of the substrate
surface, viscosity of coating materials, wood moisture content, various stress states
in the system, etc. [2, 9, 11, 1821] which must to be considered when studying
coating-wood systems because they also may cause a considerable distortion of the
pattern of interactions among the surface forces, and inuence the conditions at the
interface between the wood and the liquid coating material. They can also have a
negative impact on the stability of the nal solid coatingwood system.
The wetting process was evaluated by using the Youngs concept of energy
equilibrium at the interfaces between the solid, liquid and gaseous phases, according
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to the equation
LV
cos =
SV

SL
, (1)
where
SV
is the interfacialfree energy at the solid materialgas interface,
LV
is the
interfacial free energy at the liquidgas interface,
SL
is the interfacial free energy
at the solidliquid interface and is the equilibrium contact angle.
The capacity of a liquid to wet the surface of a specic solid material is assessed
based on the experimentally measured contact angle .
As we can see in the literature [2228], there are a number of ways to determine
the contact angle, because the actual wetting process always occurs in conditions
more or less different from the ideal equilibrium state.
The penetration of the liquid into the substrate at the interface between the coating
and wood material is, in general, characterized by changing contact angle. This
change depends on time and, to a considerable extent, also on wood morphology
and geometry of the wood external surface [17, 29].
The problem of changing contact angle has been discussed in detail in [30, 31].
In these works we suggest that for the calculation of thermodynamic characteristics
the most suitable angle is the one corresponding to an ideally smooth wood surface
w
.
The wood surface is more or less rough as a result of the wood morphology
and the way of treatment and at the moment of the contact between the drop
and wood surface, the void spaces on the surface under the drop remain partially
lled with air. In case when the substrate surface in the contact spot with the liquid
consists of two different components with surface free energy values
S1
and
S2
,
the equilibrium contact angle is expressed as:
cos = f
1
S1V

S1L
LV
+ f
2
S2V

S2L
LV
, (2)
where f
1
and f
2
represent the proportions of the separate components at the site
occupied by the liquid.
Modifying equation (2) we obtain
cos = f
1
cos
1
+ f
2
cos
2
, (3)
where
1
and
2
are values of contact angles corresponding to the separate substrate
components.
If one of the components is the wood substance and the other is the air, then the
value of
S2V
on the right side of equation (2) is equal to zero,
SL
is identical to the
surface stress of the liquid
LV
and equation (3) can be arranged in the following
way:
cos
0
= f
1
cos
w
f
2
, (4)
where
0
is the contact angle at zero time, i.e. at the moment the drop just
contacts the substrate,
w
is the contact angle on ideal smooth surface, in our case
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corresponding to the surface of wood substance with molecular-sized roughness, f
1
is the proportion of wood substance and f
2
is the proportion of air-lled unevenness
under the liquid.
The continually spreading drop at the same time inltrates the substrate, and,
consequently, the unevenness on the surface is lled with the liquid, the drop
diameter gets larger, and the height of the drop decreases. Just at the moment when
all the unevenness under the drop is lled with the liquid, there occurs a change
in the nature of the interface. At this time the advancing contact angle is reversed
to a receding one, the value
S2V
on the right side of equation (2) is equal to the
surface tension of the liquid
LV
, and
SL
is equal to zero. We consider this state
as equilibrated. Consequently, the equilibrium contact angle
u
at the woodliquid
interface can be expressed as:
cos
u
= f
1
cos
w
+ f
2
. (5)
The meanings of the other symbols in equation (5) are the same as in equation (4).
Having reached this point, the liquid starts to recede from the already-wetted
surface, and, as a result of progressive penetration, the liquid gradually penetrates
the substrate. The drop diameter starts decreasing, the height and contact angle keep
decreasing too.
As
f
1
+ f
2
= 1, (6)
it is possible to calculate the values of contact angle
w
by substituting the
experimentally obtained values of
0
and
u
in equations (4), (5) and (6).
In such a way, we eliminate the inuence of wood surface morphology, because
now the values of the wetting angle
w
are only dependent on the wood surface
chemical constitution. The same is true for the values of surface free energy and
for other thermodynamic characteristics. The contact angle
w
is more suitable
for calculation of surface free energy values and also for the values of other
characteristics describing the thermodynamic conditions at the interface than either
the contact angle
0
or another contact angle measured at a specied time [31].
The conditions at the interface between the wood and liquid coating materials
can also be evaluated through the reversible work of adhesion W
a
, according to the
following equation:
W
a
=
SV
+
LV

SL
. (7)
Rearranging equations (1) and (7) we obtain the YoungDupr equation
W
a
=
LV
(1 + cos ). (8)
Equation (8) enables us to calculate the values of adhesion of a liquid material to
a solid substrate, because the values of
LV
and on the right side can be obtained
experimentally.
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Table 3.
Work of adhesion of coating materials to wood W
a
, work of cohesion of coating materials W
c
and
spreading coefcient S
Wood Coating material
w
W
a
W
c
S
species
[degree] [mJ m
2
]
Spruce Nitrocellulose lacquer 11.8 54.64 55.22 0.58
Acid-hardened lacquer 15.2 53.48 54.44 0.96
Polyurethane lacquer 13.1 53.57 54.08 0.51
Polyester lacquer 14.4 53.17 54.02 0.85
Water-based acrylate lacquer 16.7 67.91 69.38 1.47
Beech Nitrocellulose lacquer 15.4 54.23 55.22 0.99
Oak Nitrocellulose lacquer 14.6 54.32 55.22 0.90
Both the cohesion of a coating material and its adhesion to wood also affect the
spreading capacity of the coating material on the wood surface as expressed through
the spreading coefcient S [32] according to the relation
S = W
a
W
c
, (9)
where W
c
is work of cohesion which is
W
c
= 2
LV
. (10)
Equation (9) means that the coating material will spontaneously spread on the
wood surface in the case when S > 0, i.e., when W
a
> W
c
.
Substituting the mean values of surface free energy of wood (Table 1) and the
mean values of contact angle
w
(Table 3) into equations (7)(9), we obtained
the values of the work of adhesion of coating materials to wood W
a
, the values
of cohesion of the coating materials W
c
and the values of spreading coefcient S
(Table 3).
The values of the work of adhesion W
a
are lower than the values of the work
of cohesion. This fact is also reected in the negative values of the spreading
coefcient S. Wetting and spreading of coating materials decrease with increasing
viscosity (Fig. 2).
A different method for evaluation of the interface between the wood and the
coating material is derived from the works dealing with studies of intermolecular
forces occurring at interfaces [3335]. These authors show that it is possible to
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Figure 2. Inuence of dynamic viscosity of nitrocellulose lacquer on values of contact angle
w
measured on spruce, beech and oak wood substrates.
determine the values of interfacial free energy for the solid materialliquid interface
SL
, according to the relation
SL
=
d
S

d
L
2
+
p
S

p
L
2
(11)
by knowing the values of the dispersion (non-polar) and polar components of the
surface free energy of the substrate
d
S
and
p
S
and of the non-polar and polar
components of the surface free energy of the liquid material
d
L
and
p
L
.
The work of adhesion W
a
and the spreading coefcient S can be expressed as:
W
a
= 2
d
S
d
L
+ 2
p
S
p
L
, (12)
S = 2
d
S
d
L
+ 2
p
S
p
L
2
d
L
+
p
L
. (13)
The term 2(
d
L
+
p
L
) on the right side of equation (13) corresponds to the term
representing the work of cohesion of the liquid in equation (10).
The work of adhesion of coating materials to wood, the work of cohesion of
coating materials and spreading coefcient were also calculated from equations (12)
and (13) (Table 4). The table also contains the values of non-polar and polar
components of the work of adhesion W
d
a
and W
p
a
.
As it follows from the results in Table 4, the adhesion of a coating material in
the liquid phase to wood is a result of interactions between non-polar and polar
forces at the interface between the wood and the coating material. Except for the
water-based acrylate lacquer, there were found signicant interactions between the
non-polar components of the surface free energy of the neighbouring phases.
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Table 4.
Work of adhesion of coating materials to wood W
a
, work of cohesion of coating materials W
c
and
spreading coefcient S [17]
Wood Coating material W
a
W
d
a
W
p
a
W
c
S
species
[mJ m
2
]
Spruce Nitrocellulose lacquer 71.74 52.52 19.22 55.22 16.52
Acid-hardened lacquer 71.00 52.25 18.75 54.44 16.56
Polyurethane lacquer 70.66 52.12 18.54 54.08 16.58
Polyester lacquer 70.60 52.10 18.50 54.02 16.59
Water-based acrylate lacquer 84.63 56.39 28.24 69.38 15.25
Beech Nitrocellulose lacquer 71.53 49.24 22.29 55.22 16.31
Oak Nitrocellulose lacquer 71.89 51.26 20.63 55.22 16.67
The interactions between the non-polar and polar forces at the interface between
the wood and an organic solvent-soluble coating material result in rather high values
of interfacial free energy at the interface between the wood and the coating material
SL
, resulting from high proportion of the polar component (Table 5). In the case of
the interface between the wood and the water-based acrylate lacquer, the values of
interfacial free energy are lower than in solvent-soluble lacquers, and the difference
between non-polar and polar components is also lower.
The work of adhesion of coating materials to wood as calculated according
to equation (12) is signicantly higher than the work of cohesion of coating
materials W
c
. Consequently, all the values of spreading coefcient S are greater
than zero (Table 4). This means that the coating materials have intrinsic ability to
spontaneously spread over the wood surface. This fact has been conrmed also by
Pecina and Paprzycki [20].
The values of the work of adhesion of coating materials to wood determined
using equation (12) are evidently higher (Table 4) compared to those obtained
using equation (8)(Table 3). From the viewpoint of thermodynamic equilibrium,
however, equivalence of equations (8) and (12) is to be expected. According to
Liptkov et al. [17], these differences stem from the secondary inuences due to
rheological properties of coating materials because in the case of ideal liquids, the
validity of this equivalence has been conrmed.
Experimental results demonstrate that the values of the work of adhesion and
spreading coefcient obtained using equations (8) and (9) and the corresponding
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Table 5.
Values of interfacial free energy between the coating materials and wood,
SL
and its non-polar and
polar components
d
SL
and
p
SL
[17]
SL

d
SL

p
SL
species
[mJ m
2
]
Spruce Nitrocellulose lacquer 16.14 0.10 16.04
Acid-hardened lacquer 16.49 0.11 16.38
Polyurethane lacquer 16.64 0.11 16.53
Polyester lacquer 16.67 0.11 16.56
Water-soluble acrylate lacquer 10.33 0.01 10.32
Beech Nitrocellulose lacquer 24.14 0.00 24.14
Oak Nitrocellulose lacquer 19.59 0.03 19.56
values obtained using contact angles measured for woodcoating material in the
liquid state do not correspond to the thermodynamic conditions at the interface
between a solid and a liquid, as a result of the inuence of secondary factors.
The values of the work of adhesion W
a
and of the spreading coefcient S resulting
from interactions between surface forces at the interface between the wood and a
coating material can only be determined using equations (12) and (13), i.e., from
the experimentally determined values of the dispersion and polar components of the
surface free energy of the neighbouring phases.
However, a comparison of the effects of surface force interactions at the solid-
liquid interface determined using equations (8) and (9) and those determined using
equations (12) and (13) allows us to evaluate the actual state at the interface.
The results obtained in such a manner point out the necessity to eliminate the
secondary inuence of rheological properties of coating materials on their wetting
and spreading over the wood surface in the process of application. One possible
way to address this issue is to decrease the viscosity of the coating material before
the application and choose a suitable application technique.
4. INTERACTIONS OF WOOD WITH COATING MATERIALS IN THE SOLID
PHASE
The process of drying a coating material on a substrate surface encompasses several
mechanical and physical events resulting in changes in the chemical composition of
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the solid coating. These changes occurring at the interface of the coating and wood
are reected in the values of surface free energy of the coating, values of adhesion
of the solid coating to wood and the values of cohesion of the coating material itself.
Our evaluation of the solid coatingwood system was focussed on the work of
adhesion at the solid coatingwood interface and the work of cohesion of the
components of the studied system. The primary basis for this study were the results
obtained in the preceding work of Liptkov and Kdela [36].
Interactions in the solid coatingwood system can be studied using the principles
of a solidliquid system. Analogous to equations (11) and (12), for the values of
interfacial free energy at the solid coatingwood interface
S1S2
and for the values
of the work of adhesion of the solid coating to the wood W
a
we obtain the equations
S1S2
=
d
S1

d
S2
2
+
p
S1

p
S2
2
, (14)
W
a
= 2
d
S1
d
S2
+ 2
p
S1
p
S2
, (15)
where
d
S1
and
p
S1
are the dispersion and polar components of surface free energy
of wood and
d
S2
and
p
S2
are the dispersion and polar components of surface free
energy of the solid coating.
The work of wood cohesion W
C1
was determined from experimentally obtained
values of surface free energy of wood
S1
, according to the following equation
W
C1
= 2
S1
. (16)
The work of cohesion of the solid coating W
C2
was calculated fromthe experimen-
tally obtained values of the surface free energy of the solid coating
S2
, according
to the equation
W
C2
= 2
S2
. (17)
To obtain a realistic idea about the existing state in the examined solid coating
wood system and to identify the impacts of the secondary factors on the given
system, it is necessary to verify the calculated values of the work of adhesion W
a
and the work of cohesion W
C1
and W
C2
by mechanical loading in tension of the
studied system (pull-off test).
The values of surface free energy obtained for hardened or dried coating materials
were substantially higher compared to the corresponding materials in the liquid
state. In the case of organic-solvent-based coating materials, the surface free energy
for the hardened materials was approximately two times higher (Fig. 3). In the case
of the water-based acrylate lacquer, the increase was 1.5 times. Such increases in the
surface free energy are primarily a result of increased polar component; on the other
hand, the change in the dispersion component is rather small. Moreover, in the case
of solid coatings, we also observed signicant differences between the individual
types of coating materials caused by the differences in their chemical composition.
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Figure 3. Average values of surface free energy of wood and of coating materials in solid and
liquid phases, together with their dispersion and polar components (white columns: liquid phase,
grey columns: solid phase, dark grey columns: wood, 1 nitrocellulose lacquer, 2 acid-hardened
lacquer, 3 polyurethane lacquer, 4 polyester lacquer, 5 water-based acrylate lacquer) [36].
Table 6.
Equilibrium contact angle at solid coating water interface
u
, surface free energy values of solid
coatings
S2
, their dispersion and polar components
d
S2
and
p
S2
[36]
Coating material
u
s
S2
s
d
S2
s
p
S2
s n
[
] [mJ m
2
]
Nitrocellulose lacquer 61.3 7.1 46.57 4.17 31.32 0.59 15.25 4.55 60
Acid-hardened lacquer 43.5 11.0 57.37 5.62 28.99 1.69 28.38 7.21 60
Polyurethane lacquer 48.3 5.1 54.13 3.06 30.25 0.66 23.88 3.56 60
Polyester lacquer 53.9 8.0 50.87 4.62 30.82 1.05 20.05 5.61 60
Water-based lacquer 48.1 5.8 54.27 3.34 30.20 1.00 24.07 4.32 60
s standard deviation, n number of measurements.
On the other hand, the values of surface free energy of the solid coatings were
lower than the values of surface free energy of wood and were, depending on the
wood species and the type of the coating, 6895% of the original surface free energy
value
S1
(Fig. 3). The smallest differences are for systems based on spruce wood.
The ratio between the dispersion components
d
S2
/
d
S1
was in all cases greater than
one; on the other hand, the polar component ratio
p
S2
/
p
S1
was smaller than one.
From the mean values of surface free energy of wood (Table 1) and the mean
values of surface free energy of the solid coatings (Table 6) we calculated, using
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Table 7.
Work of adhesion at the interface of wood with a solid coating W
a
, and its dispersion and polar
components W
d
a
and W
p
a
[36]
a
W
d
a
W
p
a
species
[mJ m
2
]
Water-based acrylate lacquer 113.94 58.00 55.94
equation (10), the values of the work of adhesion of coating materials to wood W
a
after their hardening or drying ( Table 7). In this table we also present the values
of interactions between non-polar and polar components W
d
a
and W
p
a
at the solid
coatingwood interface.
The values of W
a
for the wood species decreased from beech, through oak to
spruce. The results of the work of adhesion summarised in Table 7 show that the
adhesion of coating materials to wood is a result of interactions between non-polar
and polar components at the interface between the wood and the coating materials,
and the magnitudes of these components are dependent on chemical composition of
the substrate and the solid coating applied.
Comparison of the values of the work of adhesion determined at the interface
between coating materials in the liquid phase and the wood substrate (Table 4)
with the values given in Table 7 revealed that the work of adhesion of the
coating materials to wood increased after drying. This increase primarily follows
from interactions between polar components of the surface free energy of the
neighbouring phases.
The increase in the work of adhesion of coating materials during drying is
accompanied by a drop in interfacial free energy at the interface with the substrate
S1S2
(Table 8). The values of
S1S2
are relatively low, and they have mostly
polar character. The dispersion component
d
S1S2
, resulting from the non-saturated
dispersion component of surface free energy of the solid coating is lower by an order
of magnitude and, consequently, can be neglected.
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Table 8.
Interfacial free energy of wood with solid coating
S1S2
and its dispersion and polar components
d
S1S2
and
p
S1S2
[36]
S1S2

d
S1S2

p
S1S2
species
[mJ m
2
]
Table 9 shows the values of the work of adhesion of solid coatings to wood W
a
,
the values of the work of cohesion for wood W
C1
and the work of cohesion of the
solid coatings W
C2
. In all cases shown in Table 9 the following holds:
W
C1
> W
a
> W
C2
. (18)
If we suppose that the stability of the solid coatingwood system results only
from the cohesion forces within the principal components and from the adhesion at
their interface, the results obtained indicate that the coatings are the weakest link in
the system. Under mechanical loading of the system, the failure will occur in the
coating. However, it is necessary to emphasize that the term wood cohesion means
cohesion of the ideal compact wood substance, i.e., the wood substance without
pores; and the cohesion of the coating material means the cohesion of free solid
lms of the corresponding material.
In the case of wood, it is necessary to consider its porous structure, containing
certain types of defects. In such cases, the strength of wood is considerably lower
than the strength of the corresponding solid wood substance. The higher is the wood
porosity, the lower is its density and the lower is also its strength.
The strength of solid coating lms applied onto wood can also be lower than the
theoretical value, because the lm structure may be changed to some extent [20]
and, moreover, there may be defects in the coating lms with negative inuence
on the lm strength [37, 38]. The impact of these factors on the stability of a specic
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Table 9.
Mean values of the work of adhesion of solid coating materials to wood W
a
, the work of cohesion of
wood W
C1
and the work of cohesion of solid coating W
C2
[36]
a
W
C1
W
C2
species
[mJ m
2
]
Acid-hardened lacquer 117.57 114.74
Polyurethane lacquer 113.81 108.26
Polyester lacquer 109.64 101.74
Water-based acrylate lacquer 113.94 108.54
solid coatingwood system can be veried by mechanical loading of the system in
tension (pull-off test). This method of testing the stability of the solid coatingwood
system is frequently used in practice. Such testing is often considered as a test of
the coating practical adhesion to the substrate.
The results of analysis of the failure sides of coating and wood surface after the
coating detachment, performed using scanning electron microscopy, allow us to
conclude that the failure was most frequently in the coating (i.e., cohesive failure,
Fig. 4). Consequently, the study into interactions between intermolecular forces at
the solid coatingwood interface conrmed that the weakest link occurred just in
the coating. If we evaluate such failures only visually, they can be misinterpreted as
adhesion failures, particularly in the case of transparent coating materials.
In the case of oak and spruce wood, we observed partial wood failure as evidenced
by the presence of wood bres on the coating lm (Fig. 5a). However, it was
not always a typical cohesive failure over the whole substrate surface, with a few
exceptions when the wood substrate contained early wood (Fig. 5b). In such cases,
the work of cohesion of the wood was smaller than the work of cohesion of the
coating material.
However, it is important and necessary to emphasize that not even in a single case
adhesion failure was observed, which is consistent with the results of the work of
adhesion and the work of cohesion of coating materials and wood.
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(a)
(b)
Figure 4. Cohesive failure in the coating, following mechanical loading of the polyester lacquer
beech wood system. (a) backside of the coating pulled apart from wood; (b) wood surface after the
coating was torn away the wood remains covered with a lacquer layer.
In case of ground specimens, the bres can also be torn away from the coated
substrate (Fig. 6). In common practical evaluation, such a case is considered as
a cohesive failure in the substrate which is not correct and is in contradiction
with the results of thermodynamics at the interface. The phenomenon, occurring
in grinding, is caused by broken wood bres, pre-impregnated with the coating
material [9, 12]. If a wood specimen with a hardened coating material is subjected to
tension, the bres are picked up from the wood; however, this cannot be considered
a cohesive failure in the substrate. The conclusion that this is not a cohesive failure
in the substrate follows also from the strength values which are signicantly lower
than the tensile strength of the wood in the direction considered.
Mechanical tests have conrmed that the results of the work of adhesion of solid
coatings to wood and their work of cohesion calculated using equations (15), (16)
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(a)
(b)
Figure 5. Backside of the coating lm of water-based acrylate lacquer torn away from (a) oak wood
tangential surface, (b) spruce wood tangential surface (with visible wood debris).
and (17) provide us with information on the stability at the interface between the
coating material and wood and on the weakest link in solid coatingwood system.
The condition for an adhesion failure is
W
C1
> W
a
< W
C2
. (19)
Such cases were observed when there was high moisture content in the substrate
or in the case of contamination of the wood surface before the surface treatment
itself.
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Figure 6. Backside of the detached polyester lm covered with bres torn from tangential beech
wood surface treated by grinding.
5. CONCLUSIONS
The analysis of the results discussed in this study allows us to draw the following
conclusions.
Adhesion of coating materials to wood and their ability to spread over the wood
surface primarily result from interactions between the surface forces at the solid
liquid interface. The values of these interactions showed that the materials tested
should spread spontaneously over the wood surface.
The secondary inuence of the rheological properties of coating materials causes
a limited wetting abilitiy on the wood surface. Negative inuence of coating
rheological properties on the wood surface wetting with the coating materials
and the spreading of these materials over the surface is possible to overcome by
applying appropriate mechanical force during the wetting process (suitable method
of application).
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Comparison between the effects of interactions among surface forces at the solid
liquid interface calculated using equations (8) and (9) and those calculated using
equations (12) and (13) provide an actual pattern of the interface.
The values of surface free energy for the hardened coating materials are consid-
erably higher than original surface free energy values for the corresponding liquid
coatings especially due to the higher polar component. At the same time, the
change in the dispersion component is comparatively small. The value of surface
free energy is also signicantly inuenced by the chemical composition of the coat-
ing material.
It has been shown that the adhesion of coating materials to wood increases during
the drying process. This increase was primarily controlled by interactions between
the polar components of the surface free energies of the neighbouring phases. An
increase in adhesion of coating materials during the drying process is accompanied
by a drop in interfacial free energy at the interface with the substrate.
Mechanical testing of the stability of the coating materialwood system showed
that the failure in the system always occurred in accordance with the calculated
values of the work of adhesion of the coating material to wood and the work of
cohesion of the coating material and the wood substrate.
Acknowledgements
We thank Professor Douglas J. Gardner for helpful comments on the manuscript.
This work was supported by the Slovak Grant Agency for Science (Grant No.
1/0558/03).
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Adhesion de Recubrimientos en Madera

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This article was downloaded by: [Universidad Nacional Colombia]

On: 11 October 2012, At: 06:39

To whom correspondence should be addressed. E-mail: kudela@vsld.tuzvo.sk

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