COST E18 Final Seminar A review of interfacial aspects in wood coatings

A review of interfacial aspects in wood coatings:

wetting, surface energy, substrate penetration and adhesion.
Mari de Meijer
SUMMARY This paper gives a review of the state of the art of interfacial aspects in wood coatings research. It firstly covers the topics of penetration of the coatings into the wood pores from both an anatomical and a rheological point of view. Secondly results and methods for the determination of surface energies of wood are briefly reviewed. Thirdly the existing knowledge on adhesion of coatings on wood is described, including the aspects of wet adhesion. Finally the major gaps in knowledge are identified.

1.

PENETRATION OF COATINGS INTO WOOD

The penetration of primers in the wood substrate has been subject of several studies during the last 40 years of wood coatings research. Research work has covered various types of coatings corresponding to the state-of-the-art in wood coating technology. It started with studying solventborne alkyds and drying oils1, followed by a reviewed interest with the introduction of waterborne coatings 2. Especially the introduction of waterborne alkyds have been studied because these types of binders seems to have a better penetrating capacity then acrylic dispersions. Also high-solid alkyds and water soluble linseed oils have been studied more recently3. Most of the work has been done on coating systems intended for exterior applications. For interior (furniture or parquet) coatings hardly any work has been published although penetration might be relevant for esthetical reasons. 1.1 Existing techniques for assessment

Most of the studies on penetration characteristics are based on microscopic studies. One of the most popular techniques is fluorescence microscopy with a fluorescent dye mixed or grafted to the binder or the paint. Alternatively the wood itself can be stained with a fluorochrome or the pores not penetrated with the paint are filled with and additional dye. More recently also confocal laser microscopy has been used4. Another method for detection is the use of autoradiography in combination with a 14C labelled binder. This has the advantage that the binder is chemically hardly changed. The grafting of a fluorescent dye might change the properties of the binder or paint to some extent. Since fluorescence microscopy is limited to magnifications of about 200 x for higher magnifications SEM is the most widely used techniques although a good contrast between coating and wood is not very easily to achieve. For the detection of pigments EDAX analysis can be employed. The majority of the work done in this field is of qualitative nature but some studies also give quantitative data bast on measuring the depth in penetration in axial direction or by image analysis. Some typical examples of fluoresence and SEM images of wood with coating are given below.

Drywood Coatings P.O.Box 3954 7500 DZ Enschede info@drywood.nl Page 1 of 17

COST E18 Final Seminar A review of interfacial aspects in wood coatings

coating

extractive wood

Fig. 1 SEM-image of pigmented coating On softwood

Fig. 2 Fluoresence microscopic image of coating on meranti (black and white print)

The above described analytical tools are quite sufficient to describe the penetration pattern of a dried coating into the pore structure of wood they lack the possibility to study the penetration mechanism of a liquid coating in situ. Also the possible penetration of certain components of the coating into the cell wall n not be assessed. In this respect some more advanced tools might be used in future. Possibilities might be: magnetic resonance imaging (MRI) microscopy with sufficient resolution to study flow patterns at a cellular level; environmental scanning microscopy (ESEM) and TOF-SIMS imaging to study changes in chemical composition during coating penetration. Another approach the study the dynamical uptake of coating material into the wood is to measure the decrease in volume of coating droplets deposited on wood surfaces5. 1.2 Influence of anatomical structure

Softwood If paint is able to flow into the wood cells, three different ways of penetration in softwood can be distinguished as is schematically shown in fig 3. Firstly the outer longitudinal tracheids are filled directly by coating flowing from the open ends on the surface. This predominantly occurs in the earlywood. The angle between length axis of the tracheid and the surface has a strong influence on the importance of this mechanism. A second way of penetration is through the rays, starting also at the open cut ends of the ray cells. In which way transport in the rays proceeds is strongly dependent on the wood species. In pine the major part of the coating flows through the parenchyma cells, transport from cell to cell must therefore be possible. In spruce the coating almost solely penetrates the ray tracheids. A third way of penetration is from ray cells to adjacent longitudinal tracheids in the latewood. The extent of transport from rays to tracheids is strongly dependent on permeability of the cross-field pits and almost totally limited to pine sapwood. The importance of the three penetration mechanisms mentioned above implicates that penetration of the coating can strongly be influenced by the way in which boards are sawn out of a log. This because of the impact on differences in flat and standing growth rings, orientation of grain to the surface, width of early and latewood bands and the number of rays ending in radial and tangential surfaces. The origin of the wood might influence penetration because of differences in early- and latewood portions, conditions of the pits, number of rays and length of longitudinal tracheids. Drying conditions of the wood might also have some influence on coating penetration because of its impact on pit aspiration.

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COST E18 Final Seminar A review of interfacial aspects in wood coatings 1. 2. 3. 4. 5. flow into open end of longitudinal tracheid flow into ray tracheid flow into ray parenchyma flow from ray parenchyma into longitudinal latewood tracheid flow from ray tracheid into longitudinal tracheid

Fig. 3

Schematic overview of possible coating penetration patterns in softwood (source: M. de Meijer, K. Thurich and H. Militz, Wood Sci. Technol. 32, 1998)

Hardwood Penetration in hardwoods, like e.g. dark red meranti is mainly restricted to the filling of vessels and the first cells of rays and very occasionally axial parenchym and sklerenchym. In more permeable hardwood species (e.g. beech) vessels will be filled deeper and penetration in axial parenchym and sklerenchym is more pronounced. The filling of a vessel by the coating is strongly reduced if tyloses are present. Extractives appeared to have none or only a very minor influence on the penetration in all tree wood species studied. Surface preparation can have some influence on coating penetration because sanding reduces the number of open cell capillaries in which paint can flow. 1.3 Influence of coating formulation, rheology and surface energy

The various studies on penetration show fairly consistent results with respect to differences in the depth of penetration. Unpigmented oil based paints show the deepest penetration, especially through rays and adjacent tracheids. This is observed for both formulations that are solventbased, waterbased or solvent free. Unpigmented alkyd resins with organic solvent (mostly white spirit) also show a deep penetration. Emulsions of alkyd resins do penetrate the other cell layers but clearly to a lesser extent. The penetration of waterborne acrylic dispersions is very limited. When pigments are added to the formulations, especially at higher loadings in opaque paints, the penetration of all types of paints is strongly reduced but the rank-order remains the same. It should be noted that the pigments itself are still small enough to flow through the pores, only in cross-fields some clogging might occur.

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COST E18 Final Seminar A review of interfacial aspects in wood coatings

To understand these differences the underlying mechanism of the capillary flow process should be considered. The following two cases should be considered:

L=

2 cos L r L g

(1)

With height of liquid in a In this approach the maximum height of capillary rise is determined by the capillary pressure balanced by the weight of the liquid, and neglecting the effect of viscosity. Equation 1 predicts a deeper penetration in smaller capillaries. For the very deep penetrating oil based and unpigmented alkyd paints this is the case with the deepest penetration in the smaller latewood cells. However for most other products the deepest penetration is found in the wider earlywood cells. This behaviour is predicted by the following equation (known as the Washburn equation):
L= L cos r t 2

(2)

With the time (t) and liquid viscosity (). Please note that equation 1 describes an equilibrium situation whereas equation 2 is a non-equilibrium, time dependent model. Equation 2 states that the depth of capillary penetration is proportional to the square root of: liquid surface tension, cosine of the contact angle between liquid and capillary wall, diameter of the capillary and the reciprocal liquid viscosity. It should also be noted that according to equation 2, lowering the surface tension if wetting is complete ( > 0) will reduce the penetration rate. The actual limiting factor for most penetration processes following the Washburn equation is the increase in viscosity during the capillary penetration process. The micro-pores in the cell wall of the wood capillaries, with a size of 0.1- 1 nm, will only allow the lower molecular weight materials like water and solvent to enter the cell wall. The larger polymeric molecules will remain inside the capillary. The above mentioned process is visualised schematically in fig.4.The selective removal of solvent or water during the penetration process will increase the polymer fraction in the liquid and hence the viscosity of the solution6.

WOODEN CELL WALL

INCREASING FRACTION POLYMER CAPILLARY FLOW OF BINDER

SELECTIVE REMOVAL OF WATER OR SOLVENT

Fig. 4 Schematic overview of the transport processes during penetration of a liquid containing polymeric material into a wood cell capillary6

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COST E18 Final Seminar A review of interfacial aspects in wood coatings

The increase in viscosity with increasing solids content is strongly dependent on the physical nature of the polymer. Dispersions show an almost infinite increase in viscosity at solids contents between 4060 % depending on the nature and the particle size distribution of the dispersion. Emulsions will remain lower in viscosity until phase transition from an oil in water to a water in oil emulsion takes place that corresponds with a very sharp increase in viscosity. True solutions of polymers in either solvent or water retain a low viscosity even at high solids content. In some cases the viscosity might even drop with increasing solids content. A comparison of various types of binders is given in figures 5a and 5b.
15 acrylic dispersion alkyd emulsion
o)

Relative viscosity log ( /

12

6 solventborne alkyd

0 0.3

0.35

0.4

0.45

0.5

0.55

0.6

0.65

mass fraction binder

Fig. 5a Relative viscosity at a shear rate of 0.01 s-1 of an acrylic dispersion, alkyd emulsion and a solventborne alkyd binder as a function of binder content. (Source: M. de Meijer, Adhesion aspects of polymeric coatings 2003)

Fig. 5b Viscosity solids content of a water soluble modified linseed oil. (Source: Worle Technical datasheet)

If it comes to capillary penetration of a coating into wood the most important factor seems the viscosity increase at higher solids content. The rheological behaviour of coatings at increasing solids content or during drying is not very well understood in general and only limited work has been published about it7. This is not only important for substrate penetration but also for properties like flow, levelling and open time which are still issues that require improvement in waterborne decorative coatings. 1.4 Relevance of penetration to performance

Apart from the mechanism of penetration of a coating into wood, its usefulness to the overall performance should be taken into account. The following relevant aspects are here discussed in brief:

Carrier of functional additives like biocides against blue-stain or decay fungi. To be effective these products need to penetrate in the wood and hence a penetrating coating is required. It is for this reason that blue-stain primers are often based on low viscosity, deep penetrating oils. Improvement of adhesion by providing mechanical anchoring, this is discussed in section 3. Improving the exterior durability by applying an impregnating primer. Apart from the blue-stain and adhesion issues some studies have demonstrated that an impregnating primer reduces cracking and flaking of the topcoat8. This might be explained by reducing stresses between coating and wood due to the presence of an intermediate layer 9. Although this aspect has never been described in literature, esthetical aspects like clarity of grains (anfeuerung) and pore wetting might also be improved by a certain degree of coating penetration.

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COST E18 Final Seminar A review of interfacial aspects in wood coatings

2. 2.1

SURFACE ENERGY DETERMINATIONS ON WOOD Existing theories and models for surface energy

Knowledge on the surface energy and surface chemistry of wood might help to understand wetting and adhesion phenomena of coatings on wood. In this section the surface energy of wood is discussed. Specific adhesion issues are discussed in the next section. Measurement of surface energies for wood has received ongoing attention in recent decades, following the general theoretical developments in this field. The earliest research was based on measuring critical surface tensions ( c )10, later followed by measurements of polar (P ) and disperse (D ) or non-polar energy components of the surface energy according to either the geometric or harmonic mean methods 11. More recently, the Lifshitzvan-der-Waals (LW) and (Lewis) acid-base components (AB ) were used to measure the surface free energy12. Here the total surface free energy is the sum of the Lifshitz-van der Waals and the combined acid (+) and base (-) components. In the definition provided by Lewis, the acidity of a surface is determined by the possibility to accept electrons or donate protons. The basicity is controlled by the ability to donate electrons and accept protons. The acid-base interaction does include hydrogen bonding. The methods used to determine surface energies of wood are generally based on static contact angle measurements of sessile drops or dynamic contact angle measurements (Wilhelmy plate). It should also be emphasised that all these methods are based on Youngs equation: s= sl + l cos (3)

where is the surface tension (in mN m-1 or mJ m-2) of the solid (s), the solid-liquid (sl) and the liquid (l) interface respectively. In principle Youngs equation assumes that the entire system is at thermodynamic equilibrium and that the solid surface is chemically homogeneous, flat and not influenced by chemical interaction or adsorption of the liquid to the surface. 2.2 Review of results obtained on wood

An overview of the literature on surface energy data obtained for various wood species and methods is given in table 1. The critical surface tension of most wood species lies within a relatively narrow range of 40 to 55 mJ m-2, although the wood species vary in chemical composition and the different researchers used various sets of test liquids. The total surface free energy based on polar and dispersive components shows a larger variation and is generally higher than the critical surface tensions. The magnitude of the polar and dispersive components is highly variable. None of the components seem to be consistently dominant. Even for one specific wood species, the values are highly variable. For example, the polar surface energy of beech ranges between 19.6 and 53.1 mJ m-2 and the dispersive component ranges between 6.9 and 32.1 mJ m-2. With the Lifshitz-van der Waals approach, the total surface free energy is much lower, generally below or similar to the critical surface tension. The surface free energy is primarily composed of the Lifshitz-van der Waals component, but most wood species also show a significant base parameter with only a very low acidic parameter. Apart from differences in calculation methods, a large part of the variation between different observations might be explained by the complex nature of the wood surface with respect to contact angle measurements. Firstly, wood is porous which causes a continuous decrease in contact angle with sessile drop measurements due to capillary penetration into the wood structure. Secondly the wood structure causes surface roughness. As a consequence liquid spreading is more pronounced perpendicular then parallel to the orientation of the wood cells and the roughness of the surface would affect the measured contact angle data. Differences in spreading between the smoother latewood areas and the more rough and porous earlywood areas were also observed by various authors.

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COST E18 Final Seminar A review of interfacial aspects in wood coatings

Table 1
Wood Species Ash Ash Aspen Beech Beech Beech Cherry Cherry Douglas fir Douglas fir Douglas fir Maple Maple Maple Pine Pine Pine
4 4 5 6

Overview of literature data for the surface free energy of wood (mJ m -2).
Type of measurement Wilhelmy plate Wilhelmy plate Wilhelmy plate sessile drop sessile drop sessile drop Wilhelmy plate Wilhelmy plate Wilhelmy plate sessile drop sessile drop Wilhelmy plate Wilhelmy plate Wilhelmy plate sessile drop Wilhelmy plate sessile drop sessile drop sessile drop sessile drop Wilhelmy plate Wilhelmy plate sessile drop Wilhelmy plate sessile drop sessile drop Wilhelmy plate Wilhelmy plate 57 45 51.8 53.2 46.8 50.9 54.3 53.1 83.4 68.1 28.5 72.7 42.2 31.5 16.5 71.6 41.9 0.4 3 25.2 3.9 10.4 22.7 45 2 13.9 83.8 71.1 53.7 76.6 52.6 51.9 54.2 61.5 73.6 55.8 49.4 0.81 11.35 6.06 55.5 45.5 39.7 0.02 57.01 0.46 37.74 2.14 8.30 47.7 48.0 42 52.8
3

P
13.2

D
41.8

S 1
87.8 74.0 55 50.0 68.8 60 54.3 55.2 48 48 49 64.8 61.1 56.6

LW
42.6 45.0

AB
0.60 0.91

S 2
43.2 45.9

Ref.

42.9 85.16 2.68 60.15 13.87 19.18 31.88 45.53 24.48 50.6 48.1 53.1 6.9 38.1 16.19 35.1 20.09 11.8 19.2 11.5 46.8 56.07 16.4 36.2 28.8 37.5 8.77 40.2

0.00 67.35 0.02 12.64

47.5 38.7

0.42 28.00 2.86 3.29

6.84 6.13

54.3 44.8

45.5 43.2 40.7 38.9

0.46 33.19 0.71 13.29 1.73 8.41 0.05 17.33

7.85 6.15 7.63 1.86

53.3 49.4 48.3 40.8

40.93 20.13

Pine Poplar Red Maple Red oak Red oak Redwood Spruce Spruce
5 6

35.04 16.87

Spruce Walnut White oak

10.8 86.14 31.4 41.65

1.28 5.29

87.4 46.9

37.9 34.0

0.09 58.93 0.39 22.80

4.63 5.98

42.6 40.0

[d] [d] [g]7 [f] [f] [a] [d] [d] [g]7 [c] [b] [d] [d] [g]7 [e] [e] [a] [a] [a] [h] [d] [d] [b] [g]7 [a] [a] [d] [d]

S = P + D 2 S = LW + AB 3 adjusted to ideal surface 4 measured parallel to the grain of the wood 5 earlywood areas 66 latewood areas 7 data calculated from contact angles reported [a] Scheikl, M., Dunky, M. Holzforschung, 1998, 52, 89-94; [b] Nguyen, T., Johns, W.E. Wood Science and Technology, 1979, 13, 29-40; [c] Nguyen, T., Johns, W.E Wood Science and Technology, 1978, 12, 63-74; [d] Gardner, D.J. Wood and Fiber Science, 1996, 28 (4), 422-428; [e] Shen, Q., Nylund, J., Rosenholm J.B. Holzforschung, 1998, 52, 521-529; [f] Liptkov, E., Kdela, J. Holzforschung, 1994, 48, 139-144; [g] Mantanis, G.I., Young, R.A. Wood science and Technology, 1997, 31, 339-353 [h] Maldas, D.C., Kamdem, D.P. Wood and Fiber Science, 1998, 30 (4), 368-373
1

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COST E18 Final Seminar A review of interfacial aspects in wood coatings

Another complicating factor is the chemical heterogeneity of the wood surface. Apart from its major constituents cellulose (40-50%), hemicellulose (15-25%) and lignin (20-35%) wood can also contain 5-15 % of material consisting of a wide range of terpenoid, fatty acid or polyphenolic substances. These so-called extractives can have a strong negative impact on the wettability of wood surfaces 13. Available data on isolated wood components show that for cellulose LW= 44 mJ m-2, AB= 17.2 mJ m-2, += 1.62 mJ m-2, -= 17.2 mJ m-2 and for arabinogalactan (hemicellulose) LW= 37.6 mJ m-2, AB= 12.6 mJ m-2, += 0.75 mJ m-2, -= 53.1 mJ m-2. For extracted lignin it is reported that AB= 10-13 mJ m-2 and D= 45-50 mJ m-2. Because the cell wall components are not distributed evenly within the cell walls, a spreading liquid will encounter differences in the chemical composition of the surface depending whether its on the outside, inside or cross-section of the wooden cell wall. Furthermore water adsorbed onto the cell wall will always be present in significant amounts; the exact amount will, however, differ depending on the wood species and the relative humidity of the environment. Liquids used for the contact angle measurements will also be adsorbed onto the wooden surface and might even diffuse into it. This means that a thin layer of liquid vapour will be present in front of the spreading liquid. 2.3 Wetting by coatings

The wetting of a wood surface of by a coating can also be measured directly by measuring contactangle of a sessile drop of coating on a wooden surface. In order to wet the surface the surface energy of the coating should be lower than that of the wood ( coating < wood). Since most wood surface have a surface energy between 40 and 50 mJ m-2 and most coatings have a surface energy between 30 and 40 mJ m-2 this is generally no a problem. Apart from the surface energy, the spreading of a coating droplet might also be restricted by the viscosity. The shape and contact angle of the spreading contact angle is influenced by capillary penetration under or at the front of the droplet (see fig. 6). The contact angle of a coating decrease rapidly initially reaching an equilibrium after approximately (see fig. 7). In general there is a good correlation between contact angle and degree of penetration of the coating into the wood.

CAPILLARY PENETRATION

140 120 100 80 60 40 20

ac1/EW ac3/EW sba/EW ac1/LW ac3/LW sba/LW ac2/EW hsa/EW wba/EW ac2/LW hsa/LW wba/LW

LATEWOOD EARLYWOOD

contactangle (degress)

0 0 50 100 150 200 250 300 350

Time, s

Fig. 6 Microscopic image (SEM) showing influence of Fig. 7 Contact angles of coatings on early- (EW) and Wood structure on the spreading of the coating latewood (LW) areas of tangential surface of droplet. Insert at higher magnification shows pine sapwood. (Source: M. de Meijer, substrate penetration in the spreading liquid front. Adhesion aspects of polymeric coatings 2003)

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COST E18 Final Seminar A review of interfacial aspects in wood coatings

3. 3.1

ADHESION OF COATINGS TO WOOD Practical versus theoretical adhesion (adherence / adhesion)

Understanding, measuring and predicting the adhesion of coatings on wood is rather complex due to the fact that various mechanisms are involved. Most important topics to take into consideration are: Impact of the measurement technique itself Reduction of the measured adhesion by energy stored in the coating because of internal stress. Work expended in deformation during peeling or torsion of the coating during measurement. Impact of mechanical anchoring an adhesion. Influence of moisture in coating or wood. Molecular forces between coating and wood that determine the interfacial adhesion.

Sometimes the overall or practical adhesion is referred to as adherence, whereas the term adhesion is reserved for the interfacial forces between the two materials.

3.2

Analytical tools

Frequently used techniques to measure the adhesion of a coating on wood are: the axial pull-off test with a dolly glued on the coating (ISO 4624)14, shear measurements in torque mode15 and the semiquantitative x-cut or cross hedge (ISO 2409 or ASTM D3359). The first two methods are often difficult to interpret because cohesional failure can occur in the coating, glue or wood. These are often combined within one fractured surface. Furthermore, the measured force is influenced by the stressdistribution under the dolly and the method of cutting the coating around the dolly. The third method suffers from reduced reproducibility due to manual influences during the application and removal of the tape and the visual assessment of the removed coating area. Adhesion measurements by peeling of coatings with pressure-sensitive tape in a tensile testing machine are successfully applied on metals, glass and wood16. 3.3 Influence of mechanical anchoring

Some workers have suggested that there is no relation between adhesion and penetration. However, there are many studies on both adhesion of glues and coatings, in which differences in adhesion between early- and latewood areas correspond to varying degrees of substrate penetration 17. Normally the adhesion strength is higher in the earlywood, which corresponds with its deeper penetration. Adhesion is only higher in the less penetrated latewood cells, if the wood is preweathered before application of the coating. This can be explained by the fact the unprotected earlywood degraded faster during weathering which lead to a weaker bond strength. A very clear example of the importance of penetration / mechanical anchoring is given in fig. 8a and 8b. In a peel test the work increases at penetrated earlywood and decreases on latewood. Also microscopic analysis of the fractured surfaces after a peel or dolly pull-off adhesion show the importance of mechanical anchoring. Two examples of these are given in fig. 9a and 9b showing that both the penetrated part of the coating can break cohesively or can be pulled out of the wood.

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COST E18 Final Seminar A review of interfacial aspects in wood coatings

200 175 150 peel force, N/mm 125 100 75 50 25 0 0 10 20 30 40 50 peeled distance, mm
wood structure under coating which is peeled valley corresponding to latewood bands peak corresponding to earlywood bands adhesion strength J/m 2

350

300

earlywood (higher penetration) latewood (lower penetration)

250

200

150

100

50

0
acrylic1 acrylic2 acrylic3 alkyd-emulsion high solid alkyd solvent alkyd

coating type

Fig. 8a Adhesion as a function of peeled distance on pine sapwood with early- and latewood.

Fig. 8b Peel adhesion strength of various coatings on pine sapwood after exposure to liquid water.

to rn out co ati ng m at eria l

coating

Fig 9a SEM image of a pigmented alkyd emulsion Paint peeled from wood in a wet adhesion test

Fig. 9b SEM image of wood with part of a high solid alkyd paint that has failed cohesively

3.4

Influence of moisture

It is well known from both practical experiences at scientific research that adhesion of coatings on wood is much weaker under moist conditions and on wood with a high moisture content (this will be further referred to as wet adhesion). The difference between wet and dry adhesion is most pronounced with paints based on acrylic dispersions, but also waterborne alkyd paints have a lower wet adhesion than solventborne alkyds (see fig. 8b). Although the reasons for the weaker wet adhesion is not fully understood some factors can be identified as responsible for lowering the adhesion under wet conditions. An important factor is the uptake of moisture in the coating, the swelling of the coating as a consequence of this and the following build-up of hygroscopic stress. The relations between stress and adhesion and the level of hygroscopic stress are given by the following equations:

=c . E .

coating

wood

(4)

Wp = WaCW + Wd -

(5)

With the elastic energy () due to stored hygroscopic strain, thickness (c) ,elasticity (E) and Poisson ratio () of the coating and hygroscopic expansion (swelling) of coating or wood for a given change in environmental conditions. The measured peel work of adhesion (W p) is a function of: interfacial

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COST E18 Final Seminar A review of interfacial aspects in wood coatings

work of adhesion (WaCW), work expanded in plastic deformation during peeling (Wd) and elastic energy stored in the coating because of strain ( ). This means that is the swelling of the coating is much higher than that of wood, the stress will be high and might exceed the interfacial adhesion. In some studies16 this has been clearly demonstrated experimentally. It should also be noted that in such cases a high film thickness and a high elastic modulus of the coating will reduce that adhesion. The difference in adhesion after exposure to vapour and liquid water, as is shown in figure 10 can also be explained by the differences in swelling between exposure to water (which can be very high, see fig. 11) and water vapour were swelling is much lower.
500 450 adhesion strength 2 J/m 400 350 300 250 200 150 100 50 0 Ac1 liquid Ac2 liquid Ac3 liquid Ac1 vapour Ac2 vapour Ac3 vapour
140 53 58 55 116 78 76 71 298 232 195 473

pine sapwood SBA HSA WBA Ac3 Ac2 Ac1

earlywood latewood

7 2.7 2.7 2.6 46 78 11

20

40

60

80

100

volumetric swelling %

Fig. 10 Differences in peel adhesion strength of 3 acrylic paints on pine sapwood exposed to liquid water and vapour (98 % RH)

Fig. 11 Volumetric swelling of different solvent (SBA, HSA) and waterborne (WBA, Ac1-3) coatings after immersion in water.

In addition to the adhesion reduced by internal stress there might be other factor leading to a lower wet adhesion. The weak boundary layer theory explains the loss of adhesion as a failure in an intermediate molecular layer between adhesive and adherent. This molecular layer consists of low molecular weight impurities of various origins, including water. This theory has never been verified for wood, but it is known that low molecular weight extractives can easily migrate to the surface and might reduce adhesion. Also lower molecular weight fractions in the coating (e.g. surfactants, thickeners or coalescing agents) can influence wet adhesion because they might cause a weak boundary layer 18. Another reason for a decrease in adhesion can come from depletion at the polymer (coating) surface interface since a random coil of a polymer is repelled, entropically from an impenetrable surface. The depletion effect has to be overcome by adsorption of the polymer to the surface 19. 3.5 Calculated measured adhesion

From the surface free energies of both coating ( c) and wood ( w), the work of adhesion (Wacw) between the two phases can be calculated according to the following equation [73] using Lifshitz-van der Waals-acid-base parameters: Wacw = c + w - cw (6)
a Wcw =2

LW LW + + c w + c w + c w

(7)

The interfacial work of adhesion after exposure to water (W awet) can be obtained from the interfacial energies between coating-water (CL), wood - water (WL) and coating wood (CW) as follows: Wawet = CL + WL - CW (8)

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COST E18 Final Seminar A review of interfacial aspects in wood coatings

Table 2 shows results for various types of coatings with the interfacial work of adhesion between coating and wood calculated according to this equation. The measured differences in interfacial energy did not reflect the adhesion differences between the coatings. Table 2 Measured work of peel adhesion (WP) and calculated interfacial work of adhesion (Wa) under wet and dry conditions, all expressed in J m -2
Coating EW Ac1 Ac2 Ac3 WBA HSA SBA 152 142 156 238 682 580 Wp LW 107 115 110 126 200 255 WaCW
dry

Wa LW-ABwet 0.087 0.096 0.094 0.098 0.093 0.093 0.020 0.010 0.050 0.019 0.014 0.030

EW: earlywood LW: latewood CW: coating-wood LW-AB: Lifshitz-van der Waal acid-base

3.6

Adhesion promoting technologies

Several attempts can be made to improve the adhesion of coatings on wood but most important seems to improve the adhesion under wet conditions. The following approaches are described below: Pretreatment of the wood by flame-ionisation or plasma- treatment. These techniques are aiming to increase the surface energy of the wood and to change the ratio between polar and dispersive components. The improvements in adhesion with such techniques are limited which seems logical keeping in mind that substrate wetting is generally not the limiting factor in getting good adhesion. And even if the wetting of the wood by the coating is incomplete this is more likely to be due to viscosity effects. Incorporation of adhesion promoting monomers in acrylic dispersions. The monomers used are usually based on (meth)acrylates, maleates, alkyl or vinyl ester compounds which carry amino, acetoacetate, cyanoacetae, urea, thiourea or cyclic urea groups. The working principle of these monomers on wood is not described in literature but for adhesion on old alkyd paints (with similar poor adhesion) it might work by the virtue of formation of hydrogen bounds or acid-base interactions.20 Reducing the wateruptake and / or swelling of the coating by crosslinking of the polymer or reducing the hydrophilicity. Chemical crosslinking between coating and wood. In principle various types of reactive groups in two component coatings like isocyanate or expoxides could also react with the hydroxylgroups of the wood. So far no commercial products based on this principle are available but some are claiming formulations based on this principle21.

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COST E18 Final Seminar A review of interfacial aspects in wood coatings

4.

WOOD SURFACE PREPARATION

The wood surface preparation prior to application of a coating has usually received little attention but might have an important impact on the performance of a coating. The various types of surface preparation studied are: planing, sanding and rough sawn surfaces. Sanding reduces or even complete prevents the penetration of the coating due to cell deformation and clogging of capillaries with dust. Rough sawn surface generally show a higher uptake of paint material and an improved performance because of that22. Following several damage complaints about early cracking of solventborne paints on softwood studies has been done on the influence of planing conditions on durability of wood coatings. It was shown that sharp planing knifes are essential to prevent compression of wood cells during planing 23. An example of compressed cells is shown in fig. 12. If the compressed cells are coated with a solventborne paint the cells remain initially compressed but expand during weathering. Because of the extreme expansion taking place than, most coatings will crack. With waterborne paints the cells will expand during application of the paint. This will lead to grain raising and an uneven surface but cracking during service will be prevented. A comparison of grain raising with water- and solventborne paints is shown in fig. 13.

Deformed cell layer

Fig. 12 Compressed spruce wood due to poor planing

Exposed to water

Coated with solventborne paint

Coated with waterborne alkyd paint

Source fig. 12 & 13: SHR report 1.157 Wood Machining and cell deformation (in dutch), 2002.

a ronde kant + celdeformatie onafgewerkt

Fig. 13 Response of compressed wood to water and paints c ronde kant b ronde kant + celdeformatie Figuur 9
oplosmiddelhoudende alkyd spuit verf

+ celdeformatie watergedragen alkyd dompel verf

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COST E18 Final Seminar A review of interfacial aspects in wood coatings

5.

CONCLUSION AND DIRECTIONS FOR FUTURE RESEARCH

The current state of the art in the field of penetration, adhesion and surface chemistry of wood coatings has been described in the previous sections. The following main conclusions can be made: 1. A combination of the anatomical wood structure and the ability of the coating to flow into the wood capillaries govern the degree of coating penetration. Differences in penetration capacity of coatings are mainly determined by the increase in viscosity with solid content due to selective uptake of water or solvent in the cell wall. Wetting and surface tension of the coating seem to play a minor role and insufficient wetting is often due to a limitation by viscosity. 2. Surface energy determinations in terms of polar dispersive parts or lifshitz vander waals acid base components has been made for many wood species but are of hardly any use in understanding the adhesion of coatings. In general the surface energy of wood is equal or higher than the surface energy of a liquid coating which means that wetting is not a limiting factor. 3. Penetration of coatings into the outer pores of wood certainly contributes to improving the adhesion of a coating, especially under wet conditions. A very deep penetration will not directly contribute to adhesion but might reduce the differences in dimensional change between coating and wood and reduce stress in the coating. 4. The adhesion of a coating to wood is particularly critical under wet conditions. Waterborne coatings (both acrylic and alkyd based) have a lower wet adhesion than solventborne ones. One reason might be the higher swelling by moisture but other unknown factors seem to play a role too. 5. The surface preparation can have a major impact on the coating performance if wood cells are strongly compressed during planing. The subsequent expansion of the cells can lead to high grain raising or premature cracking of the coating. From the current state of the art the following gaps in knowledge can be identified: The rheology of coatings at increasing solid content or during drying is hardly known but is essential to understand differences in penetrating capacity. However, a better knowledge in this field will also contribute in understanding differences between waterborne and solventborne coatings with respect to flow, levelling and open time. Impact of a penetrating primer on the weathering performance. Some work suggests a clear improvement but the importance and reasons behind it are not known. Reduction of coating adhesion under wet conditions. Although major improvements have been made by adjusting binder properties, the wet adhesion of waterborne coatings is still not at the level of solventborne ones. These differences seem to come from differences in penetration and coating swelling alone. Existing surface energy concepts can not explain observed differences. Improved knowledge in this field is required to understand why adhesion is sometimes insufficient.

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COST E18 Final Seminar A review of interfacial aspects in wood coatings

6.

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Page 15 of 17

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