Materials Chemistry and Physics 263 (2021) 124358

Contents lists available at ScienceDirect

Materials Chemistry and Physics

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

Surface properties of coated MDF pre-treated with atmospheric plasma and

the influence of artificial weathering
Jure Žigon *, Matjaž Pavlič , Marko Petrič , Sebastian Dahle
University of Ljubljana, Biotechnical Faculty, Department of Wood Science and Technology, Jamnikarjeva Ulica 101, 1000, Ljubljana, Slovenia

H I G H L I G H T S

• Enhanced wettability of MDF substrate with coating achieved with air discharge.
• Introduction of standard and non-standard surface evaluation methods.
• Plasma treatment reduced surfaces color and gloss changes during weathering.
• No influence of plasma treatment on mechanical properties of surface system.

A R T I C L E I N F O A B S T R A C T

Keywords: A non-thermal plasma treatment generated in air at atmospheric pressure was used for surface modification of
Coating medium density fiberboard (MDF) substrate. Untreated and plasma-treated substrates were coated with a
Medium density fiberboard waterborne acrylic coating and exposed to accelerated artificial weathering (AAW) in interior mode. Plasma
Plasma
treatment increased the surface free energy of MDF by about 50%, which positively influenced on the wettability
Surface
Weathering
of the MDF with the coating. Weathering of the coated MDF caused a decrease in surface gloss and color changes,
which were less pronounced for plasma-treated samples. Attenuated total reflection Fourier transform infrared
spectra and microscopic analysis revealed degradation of the acrylic resin on the coated MDF due to light
irradiation during weathering. After 250 h of weathering, the surface roughness of the coated MDF increased by
about 3 μm. The coated MDF surfaces started to lose their hydrophobic character after 50 h of weathering.
Finally, the determination of mechanical properties showed that coated MDF became more resistant to scratching
during AAW, while the adhesion of the coating film to the MDF substrate was not affected in a significant trend
with time of AAW. In both cases, no influence of plasma treatment was detected.

1. Introduction objective of surface treatments with coatings. With the application of

Medium density fiberboard (MDF) is a widely used wood-based
engineered composite material for construction and furniture [1,2].
Physical and mechanical properties, easy workability, and ready avail­
ability make MDF favorable for the production of interior fittings, office
furniture, or kitchen cabinets [3,4]. The smoothness, non-porosity, and
homogeneity of the MDF surface also enables application of different
types of coating materials [5–7].
Apart from providing a specific visual characteristics of all wood-
based materials, protection against degradation due to the weathering
process, including physical and chemical influences, is the main
varnishes, stains and paints it is also possible to improve the appearance
and extend service life of MDF [6,8]. Waterborne coating systems
represent a promising alternative for the surface treatment of MDF [9].
The selection of a particular coating depends on the environmental
conditions [10]. Coatings for interior use have to withstand different
degradation factors due to the daily activities in our living spaces. The
response of the coated product to light irradiation, climatic variations,
mechanical damage (scratching, abrasion, impacts) and chemical dam­
age [2,8] are of prime importance in indoor areas [8,11,12]. Poly­
acrylates and polyurethanes are considered the most important binders
in the formulation of transparent, waterborne coating materials for

Abbreviations: MDF, Medium density fiberboard; AAW, Accelerated artificial weathering.

* Corresponding author.
E-mail addresses: jure.zigon@bf.uni-lj.si (J. Žigon), matjaz.pavlic@bf.uni-lj.si (M. Pavlič), marko.petric@bf.uni-lj.si (M. Petrič), sebastian.dahle@bf.uni-lj.si
(S. Dahle).

https://doi.org/10.1016/j.matchemphys.2021.124358
Received 9 August 2020; Received in revised form 4 January 2021; Accepted 3 February 2021
Available online 9 February 2021
0254-0584/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
J. Žigon et al.
Fig. 1. The sketch of the plasma setup and photos of generated different plasma discharges: (a) without substrate, (b) treatment of beech wood substrate, (c)
treatment of MDF substrate. The photos were taken by Nikon D5600 photo camera (f/6.3, 0.1 s, ISO 1600).
wood-based products in indoor applications [12,13]. However, a pre­
requisite for adequate surface protection of wood-based substrates with
coatings is good wettability of surfaces with a liquid coating [14].
Wettability can be evaluated by a contact angle (CA) measured between
a horizontal surface of a solid and the surface of a coating droplet. A
lower coating CA indicates better and more desirable wettability [15].
From the perspective of the substrate, besides the higher polar character
of the surface free energy (SFE), better wettability is associated with
higher surface roughness [15,16].
It is common practice to machine wooden surfaces before applying
coatings. Alternatively, the wettability and other surface properties of
any wood-based material can be modified by the use of plasmas in air or
other gasses, which can be done at atmospheric or reduced pressures
[17]. In particular, as reported in the literature, dielectric barrier
discharge (DBD) plasmas are most commonly used for the treatment of
MDF. For instance, Wolkenhauer and co-workers [18] reported
increased hydrophilicity of plasma-treated (PT) MDF. This was the
reason for enhanced adhesion performance of PT MDF with waterborne
polyvinyl acetate adhesive. In a recent study, Hazir and co-workers [19]
reported up to 22% improvement in adhesion strength of coating system
composing of waterborne coatings on plasma pre-treated MDF. Appli­
cations of other types of plasmas on MDF were also investigated. The
main process parameters when using a plasma torch to modify MDF
surfaces were investigated by Perisse and co-authors [20]. De Cade­
martori and co-workers [21] reported an increased oxygen content on
MDF surfaces and their improved wettability after helium-DBD treat­
ment. In another study, improved adhesion of acrylic coating was found
when argon was used as a working gas [22]. MDF was also used as a
substrate for the deposition of a macroscopic coating layer of polyester
with a plasma jet [23].
Exposure of uncoated or coated wood-based materials to weathering,
including light irradiation, elevated relative humidity (RH), and tem­
perature [24], results in various changes in the properties of the bulk
material [1] or its surface [25–27]. Long-term natural weathering can be
substituted with accelerated artificial weathering (AAW [28]). Through
the exposure of a particular material to AAW, the performance of the
material can be evaluated much more quickly. In an AAW chamber,
environmental conditions are controlled according to defined test pro­
tocols. Irradiation of natural sunlight to tested material can be imitated
with a xenon-arc lamp [29].
Combinations of structural and chemical changes in the irradiated
2
Materials Chemistry and Physics 263 (2021) 124358
material are reflected in changes in surface wettability, roughness, color,
and gloss [30,31]. Considering only coated surfaces, weathering affects
the mechanical properties of the coating, such as adhesion and hardness
[32–35].
The physical and mechanical properties of coated materials are
influenced by the roles of the coating film, underlying substrate, and the
interface, which together form the surface system [36]. External in­
fluences on coated materials are reflected in damage at different levels.
Deformation responses of the coating film or the entire surface system
can be analyzed on a microscopic level [37].
The present study aims to quantify the possible influence of plasma
pre-treatment on the properties of MDF coated with a waterborne
coating and on the performance during a subsequent exposure to AAW.
Pre-treatment of the MDF substrate was performed using a recently
developed DBD plasma in a floating electrode configuration generated in
air at atmospheric pressure. The influence of PT was first investigated in
terms of surface morphology and wettability of MDF with water and
coating. The performance of the coated MDF samples, both untreated
and PT, was evaluated during 250 h of AAW in interior mode in terms of
color, gloss, chemical properties, wettability with water, microstructure,
and morphology. Finally, the influences of PT and AAW on the me­
chanical properties of the coated MDF were determined by analyzing the
response of the surfaces to scratching and by measuring the peel force of
the coating films.
2. Materials and methods
2.1. Materials
From 3 mm thick MDF boards, specimens with dimensions of 300
mm × 75 mm were divided in untreated (UT) and plasma-treated (PTd)
series. Prior to experiments, the material was stored in a chamber with a
temperature of 20 ◦ C and RH of 65%. Under these conditions, the MDF
reached a density of (802 ± 10) kg/m3 and an equilibrium moisture
content of 10.4%, as determined gravimetrically.
As a coating material, a pigmented commercial acrylic waterborne
coating (Belinka Interier, Belinka Belles, d.o.o., Ljubljana, Slovenia)
with a solid content of 37.8% was used.
J. Žigon et al.
2.2. Plasma treatment process
MDF samples were treated with non–thermal DBD plasma in floating
electrode configuration (FE-DBD) in air at atmospheric pressure. The
details of the setup are described in previous studies [38,39]. Alter­
nating high voltage (frequency 5 kHz, 15 kV peak voltage) was supplied
by high voltage power source into two parallel brass electrodes, each
insulated by an alumina ceramic dielectric. The distance between the
insulated electrodes was set to 5 mm, and the distance between the di­
electrics and the surface of the workpiece was 1 mm. Fig. 1 shows the
sketch of the plasma setup and example photos of the plasma discharges.
The MDF, or any other lignocellulosic substrate (e.g. wood), represents
opposite counter electrode on a floating potential. PT of individual MDF
workpiece was performed at the samples’ moving rates of 2 mm/s
(sample series designated PTd-2) and 3 mm/s (sample series designated
PTd-3) in a room with a temperature of 20 ◦ C and a RH of 35%.
2.3. Surface roughness measurements
The influence of PT on the surface morphology of MDF was examined
with a LEXT OLS5000 confocal laser scanning microscope (CLSM,
Olympus, Tokyo, Japan). Morphology analysis was performed on 5 spots
of MDF surfaces before and after PT (PTd-2 and PTd-3, 3 samples each),
as well as during AAW (c.f. Section 2.6), and for analyzing the scratching
traces (c.f. Section 2.11). To ensure repeatability, the measurements
were recorded each time at the same spots of each individual sample at 5
– fold magnification with the scanned area of 2560 μm × 2560 μm. Non-
contact 3-dimensional (3D) laser microscopy was performed using a
laser light source with a wavelength of 405 nm, with a maximum lateral
resolution of 0.12 μm. The OLS50-S-AA software (Olympus, Tokyo,
Japan) was used to calculate the average absolute deviation of the
roughness irregularities from the mean sample surface over the sam­
pling area Sa [40].
2.4. Determination of surface free energy (SFE) and wettability with
coating
Surface wetting properties and surface free energies on UT and PTd
MDF were determined on the basis of contact angle (CA) measurements
of three liquids: deionized water (surface tension: polar part γP = 51.0
mN/m, dispersive part γD = 21.9 mN/m), diiodomethane (γP = 0.0 mN/
m, γ D = 50.8 mN/m) and formamide (γP = 39.0 mN/m, γ D = 19.0 mN/m)
[34]. Twelve 5 μL droplets of each liquid were applied to 3 (100 mm ×
75 mm) samples of the UT series and each PTd series with Theta optical
goniometer (Biolin Scientific Oy, Espoo, Finland). The corresponding
goniometer software was used to measure the CA between the surface of
the substrates and the tangent line fitting the shape of droplet. The SFE
was calculated using the Lifshitz-van der Waals acid-base method
[41–44]. The same procedure was used to measure the CA of the coating
on 3 MDF samples per series, where the volume of the applied droplets
was 10 μL. After 24 h, the top-view photos of cured coating droplets
were taken using photo camera (f/5.6, 0.02 s, ISO 1250) and the areas of
the droplets were measured using Fiji software (ImageJ 1.46d, Madison,
WI, USA).
2.5. Coating film formation
The UT and PTd MDF samples (5 per series) with the initial di­
mensions were manually coated using a quadruple coating applicator.
At the rate of applicator movement of approximately 30 mm/s, coating
films with a wet film thickness of 240 μm (approximately 130 g/m2)
were created. The determination of the dry film thickness is explained in
Section 2.10. Before further analyses, the samples were stored for 21
days in a dark room at a temperature of 20 ◦ C and a RH of 35%.
3
Materials Chemistry and Physics 263 (2021) 124358
2.6. Accelerated artificial weathering (AAW) process
The coated MDF samples, either UT, PTd-2 or PTd-3, were cut in two
halves and exposed to AAW in the Atlas SUNTEST XXL + chamber (Atlas
Material Testing Technology, Mount Prospect, IL, USA) according to the
EN ISO 11341 [45] standard in the interior mode. The xenon-arc lamp
behind a 3 mm glass filter produced a light spectrum equivalent to
sunlight entering through the window glass [28,46]. Settings of the
AAW device established the following conditions in the chamber: a light
irradiance of 340 nm, irradiation power of 0.35 W m− 2, a RH of 65%, a
chamber temperature of 35 ◦ C and the temperature at the black panel
sensor of 55 ◦ C. The samples were exposed to weathering for 10 h, 50 h,
100 h, and 250 h. As reported in the literature, the selected durations of
irradiation to xenon-arc light lead to detectable changes in various
properties of materials similar to those used in this study [28,30,47].
After completion of each weathering interval, three samples from each
series were taken out of the chamber for further work and analyses.
2.7. Determination of visual properties
The changes in visual properties, gloss, and color of the surfaces of
the samples were monitored during the AAW intervals in 10 measure­
ments of each property on each sample. Gloss, as a property related to
the intensity of light reflected in the specular direction [8], was
measured with a gloss meter AcuGloss TRI (X-Rite, Grand Rapids, MI,
USA) at the angle between the light source and the observed plane of
60◦ . CIELAB color space components (L*, a* and b*) were measured
using the spectrophotometer SP62 (X-Rite) with the D65 light type.
Color changes of the sample surfaces (ΔE*) were calculated according to
equation (1):
[ ]
ΔE* = √ (ΔL* )2 + (Δa* )2 + (Δb* )2 , (1)
where the parameters ΔL*, Δa* and Δb* represent the changes between
the initial value of L*, a* and b* and the value of L*, a* and b* at the end
of each AAW interval.
2.8. Attenuated total reflection Fourier transform infrared (ATR-FTIR)
spectroscopy
Forsthuber and Grüll [45] reported the usability of ATR-FTIR to
quantify the photo oxidation rates of coatings due to the exposure to
xenon-arc light. In this study, ATR-FTIR was used to evaluate the
changes in chemical bonds in the coating films due to photochemical
degradation during AAW. The spectra were recorded using the Perki­
nElmer Spectrum Two (PerkinElmer Inc., Waltham, MA, USA) ATR-FTIR
spectrometer, with a LiTaO3 detector type in the transmittance mode.
Spectra were corrected for background and measured in 3 spots (16
scans per spot) on individual sample, in a wavelength region from 600
cm− 1 to 4000 cm− 1 at a resolution of 0.5 cm− 1. Relevant absorption
bands were then interpreted using the corresponding software (Spec­
trum V.10.5.3, PerkinElmer Inc.).
2.9. Wettability of coated samples with water during AAW
In order to detect the influence of AAW on the in hydrophobic
characteristics of the coating film, the CAs of deionized water were
measured after each weathering period. Optical goniometer Theta was
used to measure the angle of 10 5 μL water droplets deposited on the
surface of each sample of coated MDF. The lower the CA was, the lower
the ability of a coating film to protect the surface from water [48].
2.10. Scanning electron microscopy (SEM) analysis
SEM was used to analyze the microscopic changes on the sample
surfaces due to AAW. The spots of interest were observed with a
J. Žigon et al.
scanning electron microscope FEI Quanta 250 (FEI, Hillsboro, OR, USA).
Prior to observations, samples were coated with a gold conductive layer.
Images were acquired with the backscatter detector at 1000 × magni­
fication in high vacuum (0.085 Pa) with an electron source voltage of
5.0 kV, at a working distance of 10 mm, and a spot size of 3.0 nm. During
the acquisition of each image, the time of beam passage through the
sample was 60 μs. SEM was also used to determine the dry coating film
thickness and to analyze the scratch traces (Section 2.11).
2.11. Determination of response to scratching
The response of the coated surfaces to scratching was determined
during AAW according to the modified circular method described in EN
15186 [49] with a scratch hardness tester (model 413, Erichsen GmbH &
Co. KG, Hemer, Germany) as presented in Fig. 2. The specimen of 100
Fig. 3. The principle of coating peeling force determination: (a) schematic representation of removal of the glued cotton strip from the coated MDF sample (di­
mensions in mm) and (b) the detected peeling force as a function of the measurement time (red line represents the mean detected force). (For interpretation of the
references to color in this figure legend, the reader is referred to the Web version of this article.)
4
Materials Chemistry and Physics 263 (2021) 124358
Fig. 2. Methodology of determination of the sur­
face response to scratching. (a) Schematic repre­
sentation of the deformations in a coating film and
MDF substrate (marked area) caused by the loaded
advancing tip. (b) Morphological picture of the
sample surface with the scratch trace, obtained with
CLSM. The arrows are pointing the pile-up forma­
tions at the border of the scratch. The dimensions of
the analyzed spot are 2560 μm × 2560 μm. (c) Top
view of the scratched sample surface, obtained with
CLSM. The length of the scale bar is 0.5 mm. The
area of the scratch is marked. 5 height profiles were
measured, as shown by the vertical line in the
middle of the picture. (d) The height profile ob­
tained along the analyzed distance, obtained with
CLSM. The marked » V « shape area, defined by the
area (A) and depth (d), represents the cross section
of the calculated scratch volume.
mm × 100 mm in size was clamped on a turntable. The 90◦ angled
diamond test tip with the radius at the tip of 90 μm was attached to a
load arm, which applied the test load to the specimen. After one full
rotation of the specimen (30◦ /s), circular traces with diameters of 45
mm (applied force 5 N) or 55 mm (applied force 7 N) were induced on
the specimen surface (Fig. 2a). Morphological studies of the residual
patterns were performed by CLSM on 5 sections of the individual scratch
to obtain representative results of the response to scratching on the
wider surface. Generalized 3D scratch maps were created (Fig. 2b), in an
attempt to model material contact behavior. Similarly to what was re­
ported by Barletta and co-authors [11], the 3D reconstruction of the
scratch patterns using the profiler enabled the analysis of the deforma­
tion response. As shown in Fig. 2c, the surface area of the scratch and the
average depth of the scratch were determined. An example of the height
profile (mean of 5 profiles measured per length of individual scratch
J. Žigon et al. Materials Chemistry and Physics 263 (2021) 124358

Table 1
The calculated components of surface free energy on MDF substrate.
MDF substrate Surface free energy components [mJ/m]

γLW γAB γ+ γ– γtot

UT 34.9 0.3 3.2 0.0 35.2

PT, 2 mm/s 44.1 9.1 1.6 12.7 53.2
PT, 3 mm/s 42.0 7.3 1.4 9.2 49.3

section) obtained perpendicular to the scratch is shown in Fig. 2d. The

volume of the caused scratch trace was evaluated as follows:
A×l×d
V= , (2)
2

where V is the volume of the scratch [μm3], A is the measured area of the
scratch [μm2], l is the length of the analyzed scratch [1275 μm], and d is
the average depth of the scratch [μm].
The top views and cross sections of the scratch traces and their sur­
roundings were analyzed with SEM. Images were acquired with the large
field detector at 300 × and 1000 × magnification in low vacuum (50 Pa)
with an electron source voltage of 5.0 kV, at a working distance of 10
mm, and a spot size of 3.0 nm. During the acquisition of the image, the
time of beam passage through the sample was 60 μs.

2.12. Determination of coating peeling force

The peeling force test was applied to determine the adhesion of the
coating to UT and PTd MDF samples with respect to time of AAW. The
200 mm × 20 mm cotton tissue strips were glued on the coated MDF
samples with a 2-component epoxy glue (UHU plus endfest, UHU, Bühl,
Germany). After 24 h, the boundaries of the glued strips were carefully
cut down to the substrate to prevent propagation of defects outside of
the test area. The bonded cotton strips were peeled using a Z100 tensile
testing machine (Zwick GmbH & Co. KG, Ulm, Germany) as presented in
Fig. 3. The strips were pulled at a peel angle of 15◦ at a testing machine
crosshead speed of 100 mm/min. The recording of the peeling force
started when it firstly exceeded 10 N. From this point on, the force was
recorded every 0.01 s of measurement. After the test, the share of the
coating adhesion failure was visually estimated. The reported peeling
force and percentage of adhesion failure represent the average of 3
measurements for each type of a sample.
3. Results and discussion
3.1. Surface free energy
PT of MDF caused an increase of both the non-polar dispersive
Lifshitz-van der Waals (γLW) and polar acid-base (γ AB) components of
SFE, as shown in Table 1. Compared with UT MDF, the γ LW of PTd MDF
was found to be about 1.2-times higher for both PTd-2 and PTd-3.
However, PT of MDF significantly increased γ AB: 30.3-times for PTd-2
and 24.3-times for PTd-3, compared to the γ AB values of UT MDF. It
was also shown that PT decreased the electron-donating part of γAB (γ− )
but greatly increased the γAB electron-accepting (γ+) part. Finally, as
calculated according to Lifshitz-van der Waals acid-base method, the
total SFE (γtot) of MDF was the lowest on UT samples (32.5 mJ/m),
higher on PTd-3 samples (49.3 mJ/m), and the highest on PTd-2 samples
(53.2 mJ/m). These results indicate that MDF was likely oxidized and
thus activated and was significantly more hydrophilic after PT. The
lower feed speed of the MDF workpiece through the plasma discharge
increased the SFE of MDF more than higher feed speed.
The improvement of hydrophilicity of MDF by PT is most likely
influenced by the dielectric properties of MDF. Higher moisture content
in the treated substrate makes MDF more electrically conductive, which
also affects the effect of PT to enhanced hydrophilicity [4]. However,
Fig. 4. Evolution of coating CAs applied to different MDF substrates and areas
of cured coating droplets. The top row of images shows the corresponding side-
view photos of the droplets 1 s after deposition. The bottom row of images
shows the top-view photos of the droplets 24 h after deposition. The length of
the yellow scale bars is 2 mm. (For interpretation of the references to color in
this figure legend, the reader is referred to the Web version of this article.)
this assumption was not part of this study.
3.2. Coating CAs
Fig. 4 shows the evolution of the coating CAs on UT, PTd-2, and PTd-
3 MDF substrates as well as the areas of the cured coating droplets 24 h
after deposition. The initial CAs decreased rapidly on all three samples
in the first 10 s after droplet deposition due to penetration of the liquid
into the substrate and due to the spreading of the liquid over the surface
of the solid [50,51]. The increase in SFE of MDF after PT contributed to
improved surface wettability of MDF with a waterborne acrylic coating.
As presented in Fig. 4, the formed CAs of coating droplets were signifi­
cantly lower when applied to PTd MDF than to UT MDF. However, the
difference in coating CAs observed on PTd-2 and PTd-3 samples after 60
s of measurement of 39.6◦ and 40.1◦ , respectively, is only minor and
does not reflect the larger difference in SFE between PTd-2 and PTd-3.
Perisse and co-authors [19] found that the longer PT applies more en­
ergy to the MDF surface and therefore a greater decrease in CAs is
achieved than with a faster treatment. The reason for this is due to
surface oxidation, including the formation of C–O, C– – O and O–C– –O
bonds.
The lower CAs of the coating are reflected in a larger area of MDF
covered by the droplets. 24 h after deposition, the droplets on UT
samples covered in average 16.9 mm2 of MDF, on PTd-2 samples 23.9
mm2, and on PTd-3 samples 21.5 mm2.
3.3. Changes of color and gloss
According to the measured gloss values, detected at 60◦ angle of
incidence, the analyzed surfaces were denoted as matt glossy [52]. A
reduction of gloss with time of AAW was related to the degradation of
the coating during weathering [27,53] and the associated increased
surface roughness of a coating [54,55]. Similar to what was reported by

5
J. Žigon et al.
Fig. 5. Changes of gloss of UT, PTd-2 and PTd-3 coated MDF during the time
of AAW.
Custódio and Eusébio [27], the largest changes in gloss of wood coated
with waterborne acrylic coating and exposed to AAW were detected at
the beginning of weathering (Fig. 5). The highest initial gloss was
detected on PTd-2 samples (16.2), followed by PTd-3 samples (14.5),
and on UT samples (12.0). The initial gloss values indicated that PT
contributed to the increase in gloss. This could be related to enhanced
wettability of the MDF by the coating, but definitely with the reduced
roughness of the coating film surface. With the exposure of samples to
AAW the gloss decreased. The greatest decrease in gloss was detected
after the first 10 h of weathering and was very similar for all three
sample types. With further weathering, the gloss decreased at a slower
rate. After 250 h of weathering, the gloss of PTd samples remained
higher than that of UT samples. The gloss of PTd-2 samples decreased to
15.2 (− 6.5%), of PTd-3 samples to 13.6 (− 6.2%) and of UT samples to
11.1 (− 7.1%). In conclusion, PT seems to reduce the influence of AAW
on the gloss changes.
Fig. 6 shows the color changes of UT, PTd-2 and PTd-3 coated MDF
during the period of AAW. At the beginning of AAW, the dynamics of
color changes was well related with the gloss changes. As indicated by
the calculated values of ΔE*, the color changes of the coating films were
the fastest during the first 10 h of weathering. During further irradiation
Fig. 6. Color changes of UT, PTd-2 and PTd-3 coated MDF during the time of AAW (left) and the pictures of the samples during the time of AAW (right). (For
interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)
6
Materials Chemistry and Physics 263 (2021) 124358
with xenon light and increased RH in the chamber, the color changes of
the samples slowed down slightly. For all three sample types, the color
changes were visible to the naked eye (ie. ΔE ≥ 1) during the interval
between 100 h and 250 h of AAW. During the whole period of AAW, the
most pronounced color changes were present on the UT samples, less on
PTd-3 and PTd-2 samples. This is again in good agreement with the
results of gloss changes and could be the consequence of the improved
wettability of the MDF surface with the coating and other properties of
the coated MDF [56]. At the end of the AAW, the ΔE* for UT samples
was 1.62, for PTd-3 samples 1.46 and for PTd-2 samples 1.32.
3.4. ATR-FTIR spectra
ATR-FTIR experiments were performed in order to study the chem­
ical degradation of the coating acrylic systems caused by the AAW. As
shown in Fig. 7, the only and constantly noticeable spectral changes
were detected in a broad band between 2800 cm− 1 and 3000 cm− 1, in
the alkyl region [57–60], with the bands at 2850 cm− 1 and 2920 cm− 1
denoting stretching in methyl and methylene groups, including hydro­
carbon (C–H) chains [30,61]. The transmittance signal of these bands
became remarkably larger after 50 h of AAW, indicating the formation
of hydroxyl bonds during the degradation of the acrylic resin [45,46].
However, no additional changes were detected in the spectra during
further weathering process. Regardless of the feed speed, the PT had no
effect on the detected spectra throughout the spectral entire wavelength
span, which dataset is provided in the supplementary material (Fig. S1).
Chemical degradation of the polymer matrix involves the formation
of species that are readily ablated from the surface, leading to loss of
gloss, increase in hardness, and rougher morphology [52].
3.5. Wettability of coated MDF
The behavior of water droplets deposited on coated MDF over the
time of AAW was a good indicator of the ability of the coating film to
protect the substrate from water ingress. During the first 50 h of
weathering, the initial low wetting character of the coating film seemed
to be unaffected. Additional 50 h of AAW caused a slight decrease in the
formed CAs of water droplets. After 250 h of weathering, the wettability
of the coating film with water increased significantly (Fig. 8). With
further AAW, an additional loss of coating film wettability would be
expected [62]. However, the influence of PT on coating films wettability
character was not detected during the entire period of AAW.
J. Žigon et al.
Fig. 7. ATR-FTIR spectra of coated samples in the wavelength region between
2750 cm− 1 and 3050 cm− 1, recorded after different intervals of AAW. Bands at
2850 cm− 1 and 2920 cm− 1 are marked.
Fig. 8. Initial (2 s after deposition) water CAs detected on differently pre-
treated, coated samples as measured after different intervals of AAW.
Fig. 9. SEM micrographs of the coated UT MDF surface: (a) non-weathered sample and (b) sample after 250 h of AAW. Black arrows point to deformations in the
coating film, which appeared during weathering. The length of the scale bars is 50 μm.
7
Materials Chemistry and Physics 263 (2021) 124358
3.6. Changes in coating films microstructure and surface morphology
When comparing coated MDF before AAW and after AAW, weath­
ering caused changes in the microstructure of the coating film (Fig. 9).
Such structural changes were detected on both UT and PTd samples.
Apparently, the surface microstructure of the unexposed sample was
relatively homogenous. After 250 h of weathering, semi-circular de­
formations appeared in the coating film, which were attributed to the
photo-degradation of the coating polymer induced by light transmission
[63]. These physical changes are most likely consistent with chemical
changes detected with ATR-FTIR analysis [51]. However, no blistering
or cracking was detected, which would possibly occur after prolonged
weathering [64].
The roughness of MDF depended on many variables, such as the type
of raw material, the type and amount of resin used, the moisture content
of the boards, the sanding process during manufacture, etc. [65].
Treatment of the MDF substrate with plasma caused a reduction of
surface roughness. On average, the arithmetic mean surface roughness
(Sa) of PTd-2 MDF decreased by 0.17 (±0.06) μm, while Sa of PTd-3 MDF
decreased by 0.13 (±0.03) μm. This reduced surface roughness of MDF
after PT could be the consequence of surface cleaning [39], but not
surface etching, as often reported when the PT process was carried out
with other types of setups and by different treatment parameters [66].
The relative changes of Sa of the coated MDF with respect to the pre-
Fig. 10. Relative changes of surface roughness of coated MDF after particular
interval of AAW.
J. Žigon et al.
treatment method and time of AAW are presented in Fig. 10. The results
showed an increase in surface roughness with weathering. This behavior
had a relevant influence on the decrease of gloss and consequently on
the appearance of the polymer coating [67]. Scalarone and co-workers
[68] reported that the most relevant morphological changes, which
occur with time to waterborne acrylic coatings, are primarily related to
the exudation of surfactants. In addition, the photo degradation of
coating during weathering was accompanied by oxidation, hydrolysis
and scissions of the polymer chains. This lead to the removal of low
molecular weight compounds, thus generating micro-cavities and
micro-holes on the surface [58]. Pre-treatment of MDF with plasma did
not seem to have any effect on the changes in surface roughness of the
coating film for the examined time of AAW. The images of the coated UT
and PTd MDF before AAW and after 250 h of AAW, showing the surface
morphology detected by CLSM, can be found in the supplementary
material (Fig. S2).
3.7. Response of surfaces to scratching
Exemplary SEM images of the samples’ surfaces after scratching with
a tip loaded with a force of 5 N are shown in Fig. 11. The advancing tip
caused deformations in the entire surface system, i.e. in the coating film
and underlying MDF substrate, regardless of the load applied to the tip.
The ploughing phenomenon of flat surfaces caused the appearance of
fractures in the form of pile-ups at the scratch pattern surface [69]. The
pile-up formations were the result of the deformation induced in the
material by the compressive and tensile stress fields that develop in front
of and behind the advancing tip during the progressive scratching load
[70]. For the sample cross section shown in Fig. 11a, the scratch was
approximately 170.8 μm wide and 46.2 μm deep. The thickness of the
coating dry film was measured at different spots of the micrographs as
shown in Fig. 11b, and was estimated to be 37.7 ± 5 μm. No obvious
differences in the coating film thickness were detected on UT MDF and
PTd MDF. Top-view SEM analysis of the scratches revealed the differ­
ences in the deformations caused on the non-weathered sample
(Fig. 11c) and on the sample exposed to AAW for 250 h (Fig. 11d). For
the non-weathered sample, the longer deformations of the coating film
and larger pile-up formations in the scratch surroundings indicated a
8
Materials Chemistry and Physics 263 (2021) 124358
Fig. 11. SEM analysis of scratching traces and the
surrounding on coated MDF, induced by a scratch
tip loaded with 5 N. The length of the scale bars is
50 μm. The top images show the obtained cross
sections of the non-weathered samples: (a) Black
arrows point the boundary of the scratch. The
formed pile-up of out-scratched coating and sub­
strate material is encircled by red dashed line. (b)
The black arrows point to the interface between the
MDF substrate (bottom) and coating film (above).
Here the thickness of the coating dry film can be
estimated. The bottom images show the top-views
of the scratched surfaces: (c) non-weathered sam­
ple and (d) the sample after 250 of AAW. In both
images the red dashed arrows show the direction of
the advancing tip causing scratching traces and the
revealed MDF substrate. Black arrows point to the
deformed coating film in the scratches’ surround­
ing. The formed pile-ups are encircled with a red
dashed line. (For interpretation of the references to
color in this figure legend, the reader is referred to
the Web version of this article.)
higher elasticity of the coating film. Exposure of coated material to AAW
with light irradiation (including ultra-violet light) and elevated tem­
perature, appeared to make the coating film harder [2] or more resistant
to scratching [71]. This is assumed to be due to the shorter deformations
of the coating film and smaller pile-up formations in the scratch sur­
roundings. As supported by the findings of ATR-FTIR analysis, the
coating polymer became more crosslinked, but more brittle [36,72].
Determination of the mechanical properties (e.g. tensile strength) of
non-weathered and weathered free film of the coating might addition­
ally support this assumption [12,13].
The representative 2D cross sectional profiles of the scratch patterns
and their surroundings, as obtained by the CLSM investigation and
extracted by 3D morphology, are shown in Fig. 12. The width and depth
of the scratch profile depended on the force applied to the scratch tip.
The larger the force, the wider and deeper the scratch becomes.
Morphological 3D images of coated and scratched UT and PTd MDF
before AAW and after 250 h of AAW, are provided in the supplementary
material (Fig. S3).
From the scratch and morphological data, including scratch area and
average depth of each scratch, the volume of the material scratched out
was calculated (Fig. 13). As expected, and with a similar trend for the 2D
cross sectional profiles of the scratch patterns, the volume scratched out
was greater when the surfaces were scratched with greater (7 N) than
lower (5 N) force. A large dissipation of the calculated volumes indicates
large differences in the areas and depths of the analyzed scratching
traces at the selected spots. Although the error bars partially overlap
between the filled or hatched columns, the trend of decreasing volume
with time of AAW was visible. Again, the reason for this behavior can be
found in the increasing crosslinking of the coating polymer with time
and the increased resistance of the coating to mechanical damage [61].
However, an influence of the pre-treatment method of the MDF substrate
was again not found.
3.8. Coating peeling force
The scratch resistance of polymer films is generally related to the
adhesion strength of the films to the substrate [65,66,73]. The results of
the coating peeling force measurements did not show a continuous trend
J. Žigon et al. Materials Chemistry and Physics 263 (2021) 124358

Fig. 12. Examples of 2D cross sectional profiles extracted from the visualized 3D morphology of the scratches and their surroundings. Depending on the MDF pre-
treatment method, the time of AAW and the force applied by the scratching tip, the figures follow as: (a) UT, 0 h of AAW, 5 N, (b) UT, 250 h of AAW, 7 N, (c) PT, 2
mm/s, 0 h of AAW, 5 N, (d) PT, 2 mm/s, 250 h of AAW, 7 N, (e) PT, 3 mm/s, 0 h of AAW, 5 N, and (f) PT, 3 mm/s, 250 h of AAW, 7 N.

with time of AAW, neither with the pre-treatment method of the MDF
before coating application (Table 2). For the time of AAW used in this
study, the adhesion force of the coating films showed no trend of change,
neither negative nor positive. Pre-treatment of the MDF substrate with
plasma did not increase the adhesion of the waterborne coating to the
substrate, as could be expected from the reports in the literature (e.g. ref.
[18]). Although the PT increased the SFE of the MDF surface, this pos­
itive influence did not reflect in the increased coating adhesion strength
determined with peeling force measurements. The reason for this could
be due to the method used. A different result could be obtained by using
a different method for determination of coating adhesion strength (e.g.
by determination of coating pull-off adhesion strength) or by performing
the measurements on more sample replicates. However, the influence of
weathering or pre-treatment of MDF with plasma on coating adherence
to the substrate could be more pronounced with longer exposure to
weathering than used in this study.

4. Conclusions

A non-thermal DBD plasma in a floating electrode configuration (FE-

Fig. 13. Calculated volumes of scratched traces on coated UT and PTd MDF DBD) was shown to be a viable technique for modifying the surface of
samples, with respect to the applied scratching force (5 N – filled columns, 7 N – medium density fiberboards (MDF). The treatment with plasma
hatched columns) and the time of AAW. increased the surface free energy (SFE) of MDF, which had a positive

9
J. Žigon et al.
Table 2
The results of determination of coating peeling force on UT and PTd coated MDF.
Type of coated MDF Time of AAW [h]
0 10
Fa [N] AFb [%] Fa [N] AFb [%]
UT 11.21 (2.16) 80 10.91 (3.1) 70
PT, 2 mm/s 10.88 (2.09) 75 15.76 (2.3) 75
PT, 3 mm/s 15.64 (3.70) 75 13.62 (2.1) 75
a
–Peeling force, standard deviation shown in parentheses.
b
– Share of coating adhesion failure.
effect on the wettability of MDF with a waterborne commercial acrylic
coating. Both the increased SFE and improved wettability could be
related to the reduced surface roughness and surface oxidation after
treatment with plasma. Exposure of the coated MDF to an accelerated
artificial weathering (AAW) process resulted in changes in the visual and
mechanical properties of the coating films. Surface gloss decreased with
AAW, but, higher overall gloss values were found on plasma-treated
samples. Plasma treatment (PT) also reduced the color changes of the
surfaces that occurred during the whole period of AAW. The recorded
ATR-FTIR spectra revealed the formation of hydroxyl bonds in the
coating films during AAW, indicating the degradation of the acrylic resin
by the light irradiation. The coated MDF started to lose its hydrophobic
character after 50 h of AAW. PT of MDF had no influence on the
chemical changes in the coating films nor on the hydrophobic behavior
before, during, or after AAW. As shown by the microscopic analyses,
irradiation of the samples with xenon-arc led to the formation of semi-
circular deformations in the coating film. The changes in the micro­
structure of the coating film reflected also in the increasing surface
roughness with the time of AAW. Finally, the determination of me­
chanical properties showed that the coated MDF became more resistant
to scratching during AAW, while the adhesion of the coating film to the
MDF substrate was not significantly affected over the time of AAW. In
both cases, no influence of PT was detected.
We can conclude that the pre-treatment of MDF with atmospheric
FE-DBD plasma enhanced the ability of MDF to interact with the
waterborne acrylic coating. During AAW, the positive effect of PT was
confirmed in reduced changes in gloss and color. However, the me­
chanical properties of the surfaces of the coated MDF were not improved
by the plasma pre-treatment.
CRediT authorship contribution statement
Jure Žigon: Investigation, Methodology, Data curation, Writing -
original draft, Writing - review & editing. Matjaž Pavlič: Writing - re­
view & editing. Marko Petrič: Supervision, Writing - review & editing.
Sebastian Dahle: Supervision, Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
The authors acknowledge the financial support from the Slovenian
Research Agency (research program funding no. P4-0015, “Wood and
lignocellulosic composites”).
This project has received funding from the European Union’s Hori­
zon 2020 research and innovation program under grant agreement No
745936.
10
Materials Chemistry and Physics 263 (2021) 124358
50 100 250
Fa [N] AFb [%] Fa [N] AFb [%] Fa [N] AFb [%]
17.69 (4.1) 65 16.43 (3.2) 85 13.37 (2.3) 80
14.87 (3.7) 70 15.17 (2.0) 55 18.77 (3.0) 80
14.21 (3.4) 85 15.14 (3.2) 70 13.85 (2.8) 60
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.matchemphys.2021.124358.
References
[1] Y. Kojima, T. Shimoda, S. Suzuki, Evaluation of the weathering intensity of wood-
based panels under outdoor exposure, J. Wood Sci. 57 (2011) 408–414.
[2] M. Yalcin, H. Pelit, C. Akcay, N. Cakicier, Surface properties of tannin-impregnated
and varnished beech wood after exposure to accelerated weathering, Color,
Technol. 133 (2017) 334–340, https://doi.org/10.1111/cote.12287.
[3] D.J. Gardner, C. Tascioglu, E.P. Wålinder, Wood composite protection, in:
B. Goodell, et al. (Eds.), Wood Deterioration and Preservation, ACS Symposium
Series, American Chemical Society, Washington, DC, 2003, pp. 399–419.
[4] J. Zhou, H. Zhou, C. Hu, S. Hu, Measurements of thermal and dielectric properties
of medium density fiberboard with different moisture content, Bioresources 8 (3)
(2013) 4185–4192.
[5] M. Wulf, P. Netuschil, G. Hora, P. Schmich, H.K. Cammenga, Investigation of the
wetting characteristics of medium density fibreboards (MDF) by means of contact
angle measurements, Holz Roh- Werkst. 55 (1997) 331–335, https://doi.org/
10.1007/s001070050241.
[6] T. Dilik, S. Erdinler, E. Hazır, H. Koҫ, S. Hiziroglu, Adhesion strength of wood
based composites coated with cellulosic and polyurethane paints, Ann. Mater. Sci.
Eng. (2015) 745675, https://doi.org/10.1155/2015/745675.
[7] E.S. Erdinler, K.H. Koc, T. Dilik, E. Hazir, Layer thickness performances of coatings
on MDF: polyurethane and cellulosic paints, Maderas Cienc. Tecnol. 21 (3) (2019)
317–326, https://doi.org/10.4067/S0718-221X2019005000304.
[8] E. Scrinzi, S. Rossi, F. Deflorian, C. Zanella, Evaluation of aesthetic durability of
waterborne polyurethane coatings applied on wood for interior applications, Prog.
Org. Coating 72 (2011) 81–87, https://doi.org/10.1016/j.porgcoat.2011.03.013.
[9] C. Jocham, T.W. Schmidt, G. Wuzella, A. Teischinger, A. Kandelbauer, Adhesion
improvement of powder coating on medium density fibreboard (MDF) by thermal
pre-treatment, J. Adhes. Sci. Technol. 25 (15) (2011) 1937–1946, https://doi.org/
10.1163/016942410X537189.
[10] A.P. Singh, B.S.W. Dawson, Microscopic assessment of the effect of saw-textured
pinus radiata plywood surface on the distribution of a film-forming acrylic stain,
J. Coating Technol. Res. 3 (3) (2006) 193–201, https://doi.org/10.1007/
BF02774508.
[11] M. Barletta, S. Guarino, G. Rubino, F. Trovalusci, V. Tagliaferri, Environmentally
friendly wooden-based coatings for thermalinsulation: design, manufacturing and
performances, Prog. Org. Coating 77 (2014) 701–711, https://doi.org/10.1016/j.
porgcoat.2013.12.008.
[12] S. Veigel, G. Grüll, S. Pinkl, M. Obersriebnig, U. Müller, W. Gindl-Altmutter,
Improving the mechanical resistance of waterborne wood coatings by adding
cellulose nanofibers, React. Funct. Polym. 85 (2014) 214–220, https://doi.org/
10.1016/j.reactfunctpolym.2014.07.020.
[13] M. Deka, M. Petrič, Photo-degradation of water borne acrylic coated modified and
non-modified wood during artificial light exposure, Bioresources 3 (2) (2008)
346–362.
[14] R.J. Good, Contact angle, wetting, and adhesion: a critical review, J. Adhes. Sci.
Technol. 6 (12) (1992) 1269–1302, https://doi.org/10.1163/156856192x00629.
[15] L.F. De Moura, R.E. Hernández, Evaluation of varnish coating performance for two
surfacing methods on sugar maple wood, Wood Fiber Sci. 37 (2) (2005) 355–366.
[16] A. Rolleri, E. Roffael, Influence of climatic conditions and surface roughness on the
wettability of medium density fiberboards (MDF), Holz Roh- Werkst 66 (2008)
465–466, https://doi.org/10.1007/s00107-008-0274-0.
[17] J. Žigon, M. Petrič, S. Dahle, Dielectric barrier discharge (DBD) plasma
pretreatment of lignocellulosic materials in air at atmospheric pressure for their
improved wettability: a literature review, Holzforschung 72 (11) (2018) 979–991,
https://doi.org/10.1515/hf-2017-0207.
[18] A. Wolkenhauer, H. Militz, W. Viöl, Increased PVA-glue adhesion on particle board
and fibre board by plasma treatment, Holz Roh- Werkst. 66 (2008) 143–145,
https://doi.org/10.1007/s00107-007-0217-1.
[19] E. Hazir, S. Sedanur, K.H. Koc, T. Dilik, E.S. Erdinler, E. Ozturk, Optimization of
plasma treatment parameters to improve the wood-coating adhesion strength using
Taguchi integrated desirability function approach, J. Adhes. Sci. Technol. aop. 17
(2020), https://doi.org/10.1080/01694243.2020.1816668.
J. Žigon et al.
[20] F. Perisse, S. Menecier, E. Duffour, D. Vacher, G. Monier, J.-F. Destrebecq,
P. Czarniak, J. Górski, J. Wilkowski, MDF treatment with a dielectric barrier
discharge (DBD) torch, Int. J. Adhesion Adhes. 79 (2017) 18–22, https://doi.org/
10.1016/j.ijadhadh.2017.09.006.
[21] P.H.G. De Cademartori, G.I.B. De Muniz, W.L.E. Magalhãez, Changes of wettability
of medium density fiberboard (MDF) treated with He-DBD plasma, Holzforschung
69 (2) (2015) 187–192, https://doi.org/10.1515/hf-2014-0017.
[22] P.H.G. De Cademartori, A.R. De Carvalho, P.R.D. Marangoni, M.A.C. Berton,
P. Blanchet, G.I.B. De Muniz, W.L.E. Magalhãez, Adhesion performance and film
formation of acrylic emulsion coating on medium density fibreboard treated with
Ar plasma, Int. J. Adhesion Adhes. 70 (2016) 322–328, https://doi.org/10.1016/j.
ijadhadh.2016.08.002.
[23] R. Köhler, P. Sauerbier, H. Militz, W. Viöl, Atmospheric pressure plasma coating of
wood and MDF with polyester powder, Coatings 7 (2017) 171, https://doi.org/
10.3390/coatings7100171.
[24] S. Yildiz, E.D. Tomak, U.C. Yildiz, D. Ustaomer, Effect of artificial weathering on
the properties of heat treated wood, Polym. Degrad. Stabil. 98 (2013) 1419–1427,
https://doi.org/10.1016/j.polymdegradstab.2013.05.004.
[25] M.A. Kalnins, W.C. Feist, Increase in wettability of wood with weathering, For.
Prod. J. 43 (2) (1993) 55–57.
[26] Y. Bai, Z. Gao, The ambient aging of wood fiber and its effect on mechanical
properties of MDF panels, Wood Sci. Technol. 45 (2011) 501–510, https://doi.org/
10.1007/s00226-010-0336-4.
[27] P. Nzokou, D.P. Kamdem, A. Temiz, Effect of accelerated weathering on
discoloration and roughness of finished ash wood surfaces in comparison with red
oak and hard maple, Prog. Org. Coating 71 (2011) 350–354, https://doi.org/
10.1016/j.porgcoat.2011.03.028.
[28] J.E.P. Custódio, M.I. Eusébio, Waterborne acrylic varnishes durability on wood
surfaces for exterior exposure, Prog. Org. Coating 56 (2006) 59–67, https://doi.
org/10.1016/j.porgcoat.2006.02.008.
[29] B.A. Horn, J. Qiu, N.L. Owen, W.C. Feist, FT-IR studies of weathering effects in
western redcedar and southern pine, Appl. Spectrosc. 48 (6) (1994) 662–668,
https://doi.org/10.1366/000370294774369072.
[30] X. Colom, F. Carrillo, F. Nogués, P. Garriga, Structural analysis of photodegraded
wood by means of FTIR spectroscopy, Polym. Degrad. Stabil. 80 (2003) 543–549,
https://doi.org/10.1016/S0141-3910(03)00051-X.
[31] X. Huang, D. Kocaefe, Y. Kocaefe, Y. Boluk, A. Pichette, Changes in wettability of
heat-treated wood due to artificial weathering, Wood Sci. Technol. 46 (2012)
1215–1237, https://doi.org/10.1007/s00226-012-0479-6.
[32] P. Ahola, Adhesion between paints and wooden substrates: effects of pre-
treatments and weathering of wood, Mater. Struct. 28 (6) (1995) 350–356, https://
doi.org/10.1007/BF02473151.
[33] P.D. Thay, P.D. Evans, The adhesion of an acrylic primer to weathered radiata pine
surfaces, Wood Fiber Sci. 30 (2) (1998) 198–204.
[34] M. Gindl, A. Reiterer, G. Sinn, S.E. Stanzl-Tschegg, Effects of surface ageing on
wettability, surface chemistry, and adhesion of wood, Holz Roh- Werkst. 62 (2004)
273–280, https://doi.org/10.1007/s00107-004-0471-4.
[35] M. Gindl, G. Sinn, S.E. Stanzl-Tschegg, The effects of ultraviolet light exposure on
the wetting properties of wood, J. Adhes. Sci. Technol. 20 (8) (2006) 817–828,
https://doi.org/10.1163/156856106777638653.
[36] X. Ma, Z. Qiao, Z. Huang, X. Jing, The dependence of pendulum hardness on the
thickness of acrylic coating, J. Coating Technol. Res. 10 (3) (2013) 433–439,
https://doi.org/10.1007/s11998-013-9477-3.
[37] M. Barletta, S. Vesco, F. Trovalusci, Effect of the substrate and interface on micro-
scratch deformation of epoxy-polyester powder coatings, Prog. Org. Coating 74
(2012) 712–718, https://doi.org/10.1016/j.porgcoat.2011.07.017.
[38] J. Žigon, M. Petrič, S. Dahle, Artificially aged spruce and beech wood surfaces
reactivated using FE-DBD atmospheric plasma, Holzforschung 73 (12) (2019)
1069–1081, https://doi.org/10.1515/hf-2019-0005.
[39] J. Žigon, J. Kovač, R. Zaplotnik, J. Saražin, M. Šernek, M. Petrič, S. Dahle,
Enhancement of strength of adhesive bond between wood and metal using
atmospheric plasma treatment, Cellulose 7 (2020) 6411–6424, https://doi.org/
10.1007/s10570-020-03212-8.
[40] E.S. Gadelmawla, M.M. Koura, T.M.A. Maksoud, I.M. Elewa, H.H. Soliman,
Roughness parameters, J. Mater. Process. Technol. 123 (2002) 133–145, https://
doi.org/10.1016/S0924-0136(02)00060-2.
[41] C.J. Van Oss, M.J. Chaudhury, R.J. Good, Interfacial Lifshitz-van der Waals and
polar interactions in macroscopic systems, Chem. Rev. 88 (1988) 927–941, https://
doi.org/10.1021/cr00088a006.
[42] D.Y. Kwok, D. Li, A.W. Neumann, Evaluation of the Lifshitz-van der Waals/Acid-
Base approach to determine interfacial tensions, Langmuir 10 (1994) 1323–1328,
https://doi.org/10.1021/la970460e.
[43] D.J. Gardner, Application of the Lifshitz-Van der Waals acid-base approach to
determine wood surface tension components, Wood Fiber Sci. 28 (4) (1996)
422–428.
[44] C.J. Van Oss, Use of the combined Lifshitz–van der Waals and Lewis acid–base
approaches in determining the apolar and polar contributions to surface and
interfacial tensions and free energies, J. Adhes. Sci. Technol. 16 (6) (2002)
669–677, https://doi.org/10.1163/156856102760099870.
[45] EN ISO 11341, Paints and Varnishes — Artificial Weathering and Exposure to
Artificial Radiation — Exposure to Filtered Xenon-Arc Radiation, European
Committee for Standardisation, Brussels, Belgium, 2004.
[46] M. McGreer, Weathering Testing Guidebook, Atlas Electric Devices Company,
Chicago, IL, USA, 2001. ISBN: 9780971032200.
11
Materials Chemistry and Physics 263 (2021) 124358
[47] B. Forsthuber, G. Grüll, The effects of HALS in the prevention of photo-degradation
of acrylic clear topcoats and wooden surfaces, Polym. Degrad. Stabil. 95 (5) (2010)
746–755, https://doi.org/10.1016/j.polymdegradstab.2010.02.016.
[48] V. Landry, P. Blanchet, Weathering resistance of opaque PVDF-acrylic coatings
applied on wood substrates, Prog. Org. Coating 75 (2012) 494–501, https://doi.
org/10.1016/j.porgcoat.2012.06.004.
[49] En 15186, Furniture, Assessment of the Surface Resistance to Scratching, European
Committee for Standardisation, Brussels, Belgium, 2012.
[50] M. De Meijer, S. Haemers, W. Cobben, H. Militz, Surface energy determinations of
wood: comparison of methods and wood species, Langmuir 16 (2000) 9352–9359,
https://doi.org/10.1021/la001080n.
[51] P.H.G. De Cademartori, W.H. Schreiner, W.L.E. Magalhãez, Facile one-step
fabrication of highly hydrophobic medium density fiberboard (MDF) surfaces via
spray coating, Prog. Org. Coating 125 (2018) 153–159, https://doi.org/10.1016/j.
porgcoat.2018.08.032.
[52] U. Zorll, New aspects of gloss of paint film and its measurement, Prog. Org. Coating
1 (2) (1972) 113–155, https://doi.org/10.1016/0300-9440(72)85006-9.
[53] J. Hu, X. Li, J. Gao, Q. Zhao, Ageing behavior of acrylic polyurethane varnish
coating in artificial weathering environments, Prog. Org. Coating 65 (2009)
504–509, https://doi.org/10.1016/j.porgcoat.2009.05.002.
[54] C. Merlatti, F.X. Perrin, E. Aragon, A. Margaillan, Natural and artificial weathering
characteristics of stabilized acrylic-urethane paints, Polym. Degrad. Stabil. 93
(2008) 896–903, https://doi.org/10.1016/j.polymdegradstab.2008.02.008.
[55] T.V. Nguyen, X.H. Le, P.H. Dao, C. Decker, P. Nguyen-Tri, Stability of acrylic
polyurethane coatings under accelerated aging tests and natural outdoor exposure:
the critical role of the used photo-stabilizers, Prog. Org. Coating 124 (2018)
137–146, https://doi.org/10.1016/j.porgcoat.2018.08.013.
[56] M. Pavlič, M. Petrič, Comparison of visual and instrumental assessment of colour
differences on finished wooden surfaces, Drv. Ind. 71 (2) (2020) 201–207, https://
doi.org/10.5552/drvind.2020.1954.
[57] N.S. Allen, M.J. Parker, C.J. Regan, R.B. McIntyre, W.A.E. Dunk, The durability of
water-borne acrylic coatings, Polym. Degrad. Stabil. 47 (1) (1995) 117–127,
https://doi.org/10.1016/0141-3910(94)00103-f.
[58] M.R. Alexander, S. Payan, T.M. Duc, Interfacial interactions of plasma-polymerized
acrylic acid and an oxidized aluminium surface investigated using and XPS, FTIR
poly(acrylic acid) as a model compound, Surf. Interface Anal. 26 (1998) 961–973,
https://doi.org/10.1002/(SICI)1096-9918(199812)26:13<961::AID-SIA432>3.0.
CO;2-7.
[59] N.S. Allen, M. Edge, A. Ortega, C.M. Liauw, J. Stratton, R.B. McIntyre, Behaviour of
nanoparticle (ultrafine) titanium dioxide pigments and stabilisers on the
photooxidative stability of water based acrylic and isocyanate based acrylic
coatings, Polym. Degrad. Stabil. 78 (3) (2002) 467–478, https://doi.org/10.1016/
S0141-3910(02)00189-1.
[60] O.R. Pardini, J.I. Amalvy, FTIR, 1H-NMR spectra, and thermal characterization of
water-based polyurethane/acrylic hybrids, J. Appl. Polym. Sci. 107 (2008)
1207–1214, https://doi.org/10.1002/app.27188.
[61] T.V. Nguyen, P. Nguyen Tri, T.D. Nguyen, R. El Aidani, V.T. Trinh, C. Decker,
Accelerated degradation of water borne acrylic nanocomposites used in outdoor
protective coatings, Polym. Degrad. Stabil. 128 (2016) 65–76, https://doi.org/
10.1016/j.polymdegradstab.2016.03.002.
[62] S. Saha, D. Kocaefe, C. Krause, T. Larouche, Effect of titania and zinc oxide particles
on acrylic polyurethane coating performance, Prog. Org. Coating 70 (2011)
170–177, https://doi.org/10.1016/j.porgcoat.2010.09.021.
[63] S.-T. Chang, P.-L. Chou, Photo-discoloration of UV-curable acrylic coatings and the
underlying wood, Polym. Degrad. Stabil. 63 (1999) 435–439, https://doi.org/
10.1016/S0141-3910(98)00124-4.
[64] M. Vlad-Cristea, B. Riedl, P. Blanchet, E. Jimenez-Pique, Nanocharacterization
techniques for investigating the durability of wood coatings, Eur. Polym. J. 4
(2012) 441–453, https://doi.org/10.1016/j.eurpolymj.2011.12.002.
[65] A. Rolleri, E. Roffael, Influence of different climatic conditions on the roughness of
uncoated medium density fiberboards (MDF), Holz Roh- Werkst 65 (2007)
239–244, https://doi.org/10.1007/s00107-006-0165-1.
[66] L. Xie, Z. Tang, L. Jiang, V. Breedveld, D.W. Hess, Creation of superhydrophobic
wood surfaces by plasma etching and thin-film deposition, Surf. Coating. Technol.
281 (2015) 125–132, https://doi.org/10.1016/j.surfcoat.2015.09.052.
[67] E.D. Tomak, F. Arican, O. Gonultas, E.D.S. Parmak, Influence of tannin containing
coatings on weathering resistance of wood: water based transparent and opaque
coatings, Polym. Degrad. Stabil. 151 (2018) 152–159, https://doi.org/10.1016/j.
polymdegradstab.2018.03.011.
[68] D. Scalarone, M. Lazzari, V. Castelvetro, O. Chiantore, Surface monitoring of
surfactant phase separation and stability in waterborne acrylic coatings, Chem.
Mater. 19 (2007) 6107–6113, https://doi.org/10.1021/cm0714077.
[69] M. Barletta, L. Lusvarghi, F. Pighetti Mantini, G. Rubino, Epoxy-based
thermosetting powder coatings: surface appearance, scratch adhesion and wear
resistance, Surf. Coating. Technol. 201 (2007) 7479–7504, https://doi.org/
10.1016/j.surfcoat.2007.02.017.
[70] S.J. Bull, Failure modes in scratch adhesion testing, Surf. Coating. Technol. 50 (1)
(1991) 25–32, https://doi.org/10.1016/0257-8972(91)90188-3.
J. Žigon et al.
[71] T.-W. Seo, J.-I. Weon, Influence of weathering and substrate roughness on the
interfacial adhesion of acrylic coating based on an increasing load scratch test,
J. Mater. Sci. 47 (2012) 2234–2240, https://doi.org/10.1007/s10853-011-6034-2.
[72] C.-M. Popescu, B.C. Simionescu, Structural study of photodegraded acrylic-coated
lime wood using fourier transform infrared and two-dimensional infrared
12
Materials Chemistry and Physics 263 (2021) 124358
correlation spectroscopy, Appl. Spectrosc. 67 (6) (2013) 606–613, https://doi.org/
10.1366/12-06628.
[73] M. Akkuş, T. Akbulut, Z. Candan, Application of electrostatic powder coating on
wood composite panels using a cooling method. Part 1: investigation of water
intake, abrasion, scratch resistance, and adhesion strength, Bioresources 14 (4)
(2019) 9557–9574.