Construction and Building Materials 392 (2023) 131923

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Construction and Building Materials

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Kinetic studies on photo-degradation of thermally-treated spruce wood

during natural weathering: Surface performance, lignin and
cellulose crystallinity
Akbar Mastouri a,*, Mohammad Azadfallah a,*, Gourav kamboj b, c, d, Fatemeh Rezaei e,
Asghar Tarmian a, Davood Efhamisisi a, Morad Mahmoudkia a, Carola Esposito Corcione f
a
Department of Wood and Paper Science and Technology, Faculty of Natural Resources, University of Tehran, Karaj, Iran
b
Department of Furniture, Design and Habitat (FFWT), Mendel University in Brno, Zemˇedˇelska´ 1665, 613 00 Brno-sever-Cˇ erna´ Pole, Czech Republic
c
FRISSBE, Slovenian National Building and Civil Engineering Institute (ZAG), 1000 Ljubljana, Slovenia
d
Department of Wood Processing and Biomaterials, Czech University of Life Sciences in Prague, Kamýcka´ 1176, Prague 6 - Suchdol, 16521, Czech Republic
e
Department of Sustainable Biomaterials, Mississippi State University, 201 Locksley Way, Starkville, MS State, USA
f
Department of Innovation Engineering, University of Salento, Lecce, Italy

A R T I C L E I N F O
A B S T R A C T
Keywords:
Natural weathering The hygroscopic behavior of wood-based materials is undoubtedly influential on the material surfaces exposed to
Thermally-treated wood climatic conditions. The paper aims to kinetically investigate the photo-degradation and surface characteristics
Photo-yellowing of thermally-treated spruce wood at 185 ◦C and un-treated (reference) sample through 2 years of natural
Color change weathering. Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy and X-ray
Photo-stability
diffraction (XRD) were employed to investigate the chemical changes occurred in lignin and crystalline structure
Cellulose crystallinity
of cellulose as a function of outdoor exposure. Detailed measurements of morphological and surface changes
Lignin reactions
were evaluated during exposing periods. Surface wettability and roughness as well as cracks were increased for
all samples due to weathering as the exposure time extended. Prominently, the color changes ( ΔE) and photo-
chemical reactions were found to be negligible in short-time weathering thanks to thermal modification. In
the long–term exposing, more OH-bonds caused by lignin leaching out resulted in presence of cracks and the
affinity for water on reference sample. Degree of crystallinity significantly decreased by 12.7% in thermally
treated wood and 18.3% in reference sample after long-term weathering while, the crystallinity index of thermally-
treated wood increased to 4.7% in 6-month weathering. Hence, the amorphous structures and chro- mophores
groups appeared on the reference wood at a faster and more intense rate during exposing time. Thermal
treatment delayed photo-yellowing as well as color change of wood due to up-graded lignin and cel- lulose
crystallinity through a photo-stable structure. Accordingly, kinetic studies ascertained the service-time of wood
products in exterior uses.

1. Introduction
Nowadays, the environmental issue considers as one of the influen-
tial factors in life cycle of wood materials including manufacturing
process, protection methods and its application. Thermal modification
of wood due to its attractive color, better anti-biological and improved
water-related properties as well as absence of hazardous chemicals
utilize for building industry especially in decorative purposes. During
thermal modification, wood bio-polymers are modified by subjecting
wood to high temperature in steam (160–230 ◦C) or nitrogen
(160–260 ◦C) atmosphere for certain time [1,2]. This process is not
recommended to high temperatures, >240 ◦C, since the degradation of
the wood structure becomes too severe to make the process commer-
cially useful [3]. Bois Perdure and Rectification (France), Thermo
wood (Finland), Oil Heat Treatment (Germany) and the Plato Wood
(Netherlands) are commercial processes developed in this regard [3,4].
However, depending on the wood species and thermal process some
mechanical properties such as modulus of rupture (MOR) and impact
toughness can be impaired, the other outstanding advantages of the
product have made it commercial. Outdoor applications are the most

* Corresponding authors.
E-mail addresses: akbarmastouri@gmail.com (A. Mastouri), adfallah@ut.ac.ir (M. Azadfallah).

https://doi.org/10.1016/j.conbuildmat.2023.131923
Received 27 February 2023; Received in revised form 21 May 2023; Accepted 22 May 2023
Available online 31 May 2023
0950-0618/© 2023 Elsevier Ltd. All rights reserved.
 A. Mastouri et Construction and Building Materials 392 (2023)

important commercialization purpose of thermally treated wood by

concerning its aesthetic appeal and physical properties. Some weath- Table 1
ering studies indicated that thermally-treated wood is more resistant The meteorological data for Karaj city from 1-Mar-2019 until 31-Feb-2021. The
to photo-degradation than un-treated reference wood [5–8]. However, numbers reported for each parameters are the average of about 180 days.
opposite results have been reported about weathering resistance of Climatological 1-Mar-2019, 31- 1-Sep- 1-Mar- 1-Sep-
thermally-treated wood [9–11]. In this regard, a detailed study through parameters Aug-2019 2019, 2020, 2020,
(average) 31-Feb- 31-Aug- 31-Feb-
kinetic reviews can answer these contradictions. The discoloration of
2020 20 2021
wood owning to the emendation of the chromophore structure into 2
Rad. T.S.R. Kg/m 24223 13986.3 24685 13745
modification process, hinder the UV absorption through >300 nm
Sun Shine (hrs.) 9.4 6.73 9.8 7.2
[12]. Crosslinking and more lignin content led to reduction in the Humidity (%) 39.8 57.3 42.4 60.5
accessible Rain Precipitation 0.71 1.2 0.9 1.66
hydroXyl groups, increase in the crystalline structure of cellulose were (mm)*
o
suggested to be the main reasons for improving the water related Max, Air Temp ( C)
o
27.8 16.3 27.8 15.5
Min, Temp ( C) 14.8 6 13.6 4.9
properties of wood caused by thermal modification process [13–14]. It
Wind Speed (m/s) 3.1 2.3 2.9 2.4
has been observed that variation of the crystallinity degree in the aging Max, Wind Speed 7.9 7.6 9.9 7.87
and accelerated weathering can affect the performance of the structure (m/s)
in service time [4,15–16]. However, comprehensive information on
*- 1 cm of snow is equal to 1 mm of rainfall.
these items during natural weathering are not available accurately.
Environmental agents such as UV, moisture, o Xygen, pollutants, tem-
perature fluctuation, wetting and drying process, biological agents and (tangential) ×
100 mm (longitudinal). Generally, 14 specimens (treated
abrasion due to windblown particulates reduce aesthetic appearance and untreated) were used for the experiments. The specimens were
and surface performance [10,17–18]. The wavelengths in the UV-A re- ± 2 ◦C and 65
conditioned to 12% (MC) for 3 weeks at 22 ± 3% relative
gion (340–420 nm) as well as UV-B (280–315 nm) depends on ozone- humidity (RH) before any further analyses and measurements of
layer depletion, were reported to cause changes in the average molec- properties.
ular weight and yellowness of both natural biopolymer materials and
synthetic polymers on exposure [19–20]. It was reported that about 2.2. Natural weathering
80–95% of the light absorption of wood can be ascribed to lignin [20–
21]. UV irradiation has adequate energy to chemically break down After moisture conditioning, the specimens with tangential surfaces
wood structures, mainly photo-chemical reactions related to depoly- as target, were exposed to 24 months natural weathering on a grid
merization of lignin component [22–23]. Following the leaching of screen at a 45◦ angle to a height of 120 cm above the ground level to-
lignin as an adhesive agent, polysaccharides are the main structures ward south. The weathering location was in Karaj, Iran (with
exposed to radiation and demolition. Color change is the first sign of geographic coordinates, 35◦50′ 08′′ N 51◦00′ 37′′ E). The weathering test
weathering, then cracks appear because of eroded and loosen fibers was per- formed from March 1, 2019 to February 31, 2021.
under exposure to weathering [17]. Water has a supplementary role in Meteorological in- formation of the test site was prepared and
photo-degradation of wood. The presence of moisture intensifies the evaluated by the meteorological organization of Alborz province,
photo-degradation of wood because its swelling property, thereby which was reported in
opening up inaccessible regions of the cell wall and facilitating their Table 1. Quantitative measurements and chemical changes during
degradation by light [24–25]. Finally, the lack of surface quality, re- weathering periods were measured. Qualitative and appearance evalu-
duces the service life of wooden structure and causes economical loss. ation of sample as well as surface morphology were also considered as an
Knowledge on the crystallinity index of cellulose and photo-chemical evaluation criterion related to natural weathering. For this purpose,
reactions into lignin as function of exposing periods as well as its characteristics of samples during the weathering process were periodi-
related to photo-yellowing, reveals the longevity of wood based struc- cally examined at intervals of 0 (Un-weathered), 6, 12, 18 and 24
tures. On the other hand, most of the studies have been done in accel- months.
erated and artificial conditions. Therefore, a kinetic study on natural
weathering of thermally-treated and normal wood, will certainly present 2.3. Color measurements
more realistic information for real-world application.
The main goal of this research is to kinetically evaluation of photo- The color measurements were carried out with a portable digital
degradation and surface performance of thermally treated wood spectrophotometer NRF 145 (China) on the surface before and after
compared to the untreated (reference or control) sample under natural weathering periods. It was performed with 6 replicas. The CIE L*a*b*
weathering periods. During this study, changes in color, system, L* (lightness), a* (redness (, b* (yellowness)) were measured
hydrophobicity and surface morphology were investigated during 2 for each specimen at the same location before and after weathering
years outdoor period. The total color changes (ΔЕ*) was calculated according to Eq.
(1).
exposure in details. Moreover, chemical changes in the structure of
√̅ ̅ ̅ ̅ ̅ ̅ ̅ ̅ ̅ ̅ ̅ ̅ ̅ ̅ ̅ ̅ ̅ (1)
lignin and polysaccharides as function of short- and long-term *2
ΔE* = (Δa*2+Δb +ΔL 2)
*
exposing periods were evaluated by ATR-FTIR spectroscopy and XRD
analysis in
line with photo-yellowing and hydrophobicity. according to
Finland Thermowood instructions (VTT) for 3 h [26]. For weathering
2. Materials and methods studies, the thermally modified and unmodified specimens were then
cut into pieces with the dimensions of 18 mm (radial) × 80 mm
2.1. Materials

Specimens were obtained from spruce (Picea abies L.) sapwood

board with an approXimate dimension of 200 cm × (length) 20 × cm
(width) 5 cm (thickness). Thermal modification process was carried
out at a temperature of 185 ◦C in the presence of water vapors

2
 A. Mastouri et Construction and Building Materials 392 (2023)
Where ΔL*, Δa* and Δb* are the changes of L*, a* and b* color pa-
rameters before and after weathering process, respectively.

2.4. Surface roughness

Measurements of surface roughness parameters were carried out

by using a Mitutoyo SJ-301 Portable tool (Model, Japan) in the
scanning length of 10 mm. The mean arithmetic deviation of profile
(Ra), mean peak-to-valley height (Rz) were the main parameters of
the surface roughness used to evaluate the roughness of the surface
before and after exposure periods. The tests conducted on the
tangential surface of wood specimens, perpendicular to the fiber
direction. Then, the results were presented as the mean of four
measurements.

3
 A. Mastouri et Construction and Building Materials 392 (2023)

Fig. 1. ATR-FTIR spectra of thermally-treated and un-treated spruce wood samples before weathering.

2.5. Contact angle and normalization of the spectra were also performed prior to inter-
pretation of the results.
The surface wettability of the samples was measured as described
in previous work [13], during 60 s. 10 µl volume water drop applied on
2.7. X-ray diffraction (XRD)
the surface and the status of drops was captured with a high-resolution
digital camera. The obtained images were analyzed by Fiji software
The crystalline structures of the untreated and thermally-treated
(advanced version of Image J, Dec. 2007) to achieve contact angle.
spruce wood samples were analyzed by X-ray diffraction analysis
Average of four measurements were used to assess the surface perfor-
mance before and after weathering intervals. (Panalytical X’Pert pro MPD, Netherlands). The X-ray measurement was
performed with X-ray recorded on an X-ray diffractometer using Cu Ka
radiation (λ = 1.78 Å, 40 kV, 30 mA) to quantify the degree of wood
2.6. ATR-FTIR spectroscopy crystallinity. The crystallinity index (CrI) was calculated based on the
Eq.2 (Segal et al. 1959).
The attenuated total reflection Fourier transform infrared (ATR- I200 — Iam
FTIR) spectra of samples were collected to investigate functional CrI(%) = × 100 (2)
I200
groups of wood surface due to natural weathering. Before analysis, the
wood samples (weathered and un-weathered) prepared from the where I 200 is the intensity of the crystalline peak at = 22◦–23◦
2θ
tangential surface were properly dried at 60 ◦C for 24 h. In this reflecting both crystal and amorphous material, and I am is the mini-
regard, a spec- mum intensity between the 200 and 101 peaks at = 18◦–19◦,
2θ
trophotometer (Nicolet, Kˇrelovick ́a, Czech Republic) with 64 scans in reflecting only amorphous material.
—1
the range of 4000–500 cm region was employed. Baseline correction

Fig. 2. FTIR spectra of thermally-treated (T) which was set in the top section and untreated (C) spruce wood after natural weathering at different intervals of 0, 6 and
24 months.

4
 A. Mastouri et Construction and Building Materials 392 (2023)

3. Results and discussion

Table 2
3.1. ATR-FTIR analyses Lignin variation of thermally-treated and un-treated spruce wood samples after
short- and long-term natural weathering.
The FTIR spectra of the reference and thermally-treated spruce wood Reference wood Thermally-treated wood
—1
are shown in Fig. 1. Variation in the band, 3800 to 2750 cm region Weathering time (month) 0 6 24 0 6 24
was assigned to hydroXyl (OH) and methyl/methylene (CH 2) stretching I1506 / I1367 0.7 0.06 0.05 0.73 0.09 0.09
vibrations in the polysaccharides and lignin [27]. The increase of these
peaks intensity caused by thermal process were probably because of the
—1
high lignin content. More interesting issue, the 3500/2900 cm
Table 3
bonds ratio is inversely connected to the contact angle in terms of Color measurements data of un-treated (Reference) and thermally treated wood
hydropho- bicity [13]. In the present research, this ratio was 1.07 and during weathering periods.
0.75 for un- treated and thermally-treated wood, respectively.
Concerning to this, it Weathering periods L* a* b* ΔL* Δa* Δb*
seems that the wettability of wood should be reduced during thermal (months)
—1
modification process. The peak at 1728 cm is attributed to stretching Reference 0 86.9 6.0 18.3 – – –
of acetyl and carboXylic acid (C–O) in hemicelluloses and lignin wood (0.9) (0.5) (0.4)
6 63.3 11.1 15.7 —23.6 5.1 —2.6
structure [11,28–29]. Which increased by heat treatment due to lignin (0.3) (0.7) (2.3) (0.4) (0.5)
—1 —1 (2.4)
reactions. The changes at 1316 cm and 1367 cm peaks are attrib- 12 60.0 7.9 12.8 —27.0 1.9 —5.5
uted to mainly celluloses and hemicelluloses [11,30]. These peaks in- (2.5) (0.6) (0.7) (2.6) (1.0) (1.1)
tensity increased, which confirmed carbohydrate deformation during 18 56.9 4.4 11.3 —30.0 —1.6 —7.0
—1 (1.4) (0.5) (0.6) (1.17) (0.8) (0.6)
thermally modification process. The variations at peaks 1167 cm and
—1 24 58.6 3.1 10.2 —28.3 —2.9 —8.1
1105 cm were assigned to carbohydrate particularly hemicelluloses (1.1) (0.5) (0.6) (2.0) (0.1) (0.9)
[1,11]. Which increased for thermally-treated wood. Thermally- 0 67.2 13.9 27.1 – – –
Assessment of photo-chemical reactions in the structure of lignin treated (0.9) (0.5) (1.0)
wood 6 54.7 11.0 24.6 —12.4 —2.9 —2.5
are important for understanding the surface performance of wood
(0.5) (0.3) (0.8) (0.5) (0.7) (0.6)
during weathering. FTIR spectroscopy were used to characterize the 12 48.2 12.6 22.7 —19.0 —1.3 —4.4
chemical changes of thermally and reference samples before and after (1.0) (0.5) (0.9) (0.9) (1.0) (0.2)
weathering periods by focusing on lignin structure (Fig. 2). It seems 18 42.5 11.5 20.3 —24.7 —2.4 —6.7
(2.4) (1.5) (0.7) (3.0) (1.9) (1.6)
that significant changes have occurred within a few months of natural
24 41.2 9.6 18.1 —25.9 —4.2 —9.0
exposing irradi- (1.2) (1.4) (0.6) (1.1) (1.9) (1.5)
ation. The intensity of absorption bands at around 1506, 1450, 1260
—1
and 1420 cm decreased rapidly during photo-degradation for all
wood
samples. The changes in the peaks were attributed to the removal of which can indicate hemicellulose and cellulose are more available due
some methoXy groups of the guaiacyl rings of lignin and delignification to lignin leaching. Interestingly, this peak has shifted over time and has
—1
[31]. This indicates that natural weathering affected the surface prop- been transferred to peak 1321 cm after 2 years of exposure. This can
erties of all thermally-treated and un-treated reference samples. Rapid display many changes in the glycoside chain and probably alteration of
reduction in the intensity of C–C band at 1506 cm also confirmed
—1
cellulose crystallinity with increasing exposure time.
degradation of the lignin due to exposing condition. This result was in
—1
line with previous researches [12,24]. The intensity of peak 1728 cm
assigned to carbonyl bond in lignin and hemicellulose decreased for
reference and treated wood. A resistance to reduction was observed for
thermally-treated wood at 6 months exposing, which is probably due to
—1
the stability of lignin. Also, peak 1615 cm assigned to carbonyl bond
in lignin/carbohydrate increased during the exposure time. Variation
in these peaks has been used several times by authors to understand
the photo-cleavage of lignin, as a function of outdoor weathering.
Forma- tion of carbonyl-based chromophore groups as a result of
cleavage in the
β-O-4 bond of lignin led to the color changes, is associated with
intensity of C–O band at 1728 and 1615 cm [19,21,24]. PhenoXy
—1

free radical
formation following chromophores (quinone) groups led to photo-
yellowing are as well as related to variation at 1505–1510 and
—1 —1
1700–1650 cm bonds [21,32]. The peak at 1635–1650 cm was
attributed to the H-O-H deformation vibration of absorbed water to
aromatic carbonyl groups and aromatic rings [21,33]. Intensity of this
peak increased with the weathering periods especially for un-treated
wood. This issue was aligned with the results of literature in regards
to outdoor weathering of wood [7]. The increase in water peak is most
probably due to changes of surface chemistry by the environmental ef-
fects, which coincided with formation of cracks on the wood surface
—1
after weathering. The absorption peak at 1317 cm assigned to O-H
bending vibration in carbohydrates [19,30]. There is an incremental
change in this peak at un-treated sample as a result of irradiation time,

5
 A. Mastouri et Construction and Building Materials 392 (2023)
*The numbers in parentheses are the standard deviation.

Delignification intensity can be calculated by height ratio of lignin

—1 —
peaks (1506–1510 cm ) and peaks of carbohydrates (1367–1375 cm
1
) as proposed in the literatures [19,34]. Lignin degradation as a
function of outdoor exposing periods is presented in Table. 2. As it
can be seen, lignin of un-treated spruce wood is degraded at a faster
rate than thermally-treated samples during the exposure time, which
is slightly different in results for accelerated weathering of birch
wood [35]. Meanwhile, lignin of thermally modified wood exhibits
high stability against leaching as well as literatures [5]. Increase in
lignin content and variation within amorphous structures due to heat
treatment, induce its photo-stability [6]. It should be noted that
hemicellulose, as a sensitive agent to degradation, probably slightly
affects this ratio. On other hand, it is possible that thermal
modification depending on the type of wood species, can be affected
in terms of photo-stability under weathering conditions.

3.2. Color changes

Based on Table 3, the amount of color change of wood due to the

thermally treatment process before weathering time was 23%. This
result confirmed the appropriate chemical changes into spruce wood
through thermal modification. More importantly, the kinetics evalua-
tion of color changes for thermally-treated and reference wood
samples due to 2 year- natural weathering are shown in Table 3 and
Fig. 3.
All samples experienced significant variations with increasing
exposure time. Practically, the changes in the color of the wood
surface in weathering conditions will reach a stable state after a given
time [35]. Dominant color change occurred for reference sample in
the short time photo-exposing while, for thermally modified wood,
this process has been postponed for a longer time, which was
consistent with the pre- vious study [30]. The reduction of photo-
degradation in terms of reduced color changes on the modified wood
surface might be due to boosted lignin and cellulose crystallinty
alternation. Presence of

6
 A. Mastouri et Construction and Building Materials 392 (2023)

40

35 Un-treated wood (Reference) Thermally-treated wood

30

25
ΔE
20

15

10

0
6 12
18 24
Time(month)

Fig. 3. Total color changes (ΔE) of thermally treated and un-treated spruce wood after natural weathering for different periods of 6, 12, 18 and 24 months.

Fig. 4. Roughness
of thermally treated and un-treated spruce wood after natural weathering for different periods of 6, 12, 18 and 24 months.

Fig. 5. Visual assessment of surface morphology and appearance of thermally-treated (top row) and un-treated (bottom row) spruce wood as a function of natural
weathering time (0, 6, 12, 18 and 24 month).

7
 A. Mastouri et
Fig. 6. XRD diagrams of thermally-treated (T) which was set in the top section and un-treated spruce wood samples(C) naturally weathered for different periods of 6
and 24 months.
antioXidant in lignin compounds after thermally treatment can limit
surface degradation caused by oXygen and free radicals [36]. The color
changes of wood are mainly due to some photo-chemical reactions into
lignin resulted in chromophoric procedure for yellowing, occurred in
lignin [12,32,34,36]. Darkness and more color changes of the reference
samples in the short-term are in line with FTIR results that can be caused
by high delignification and quinones reactions. Additionally, air pollu-
tion, biological agents, hemicellulose content of the sample and species
are other factors that determine color changes and loss of surface
beauty under natural weathering.
3.3. Surface roughness
Variation of surface roughness of thermally treated and reference
spruce wood has been reported in Fig. 4. The results showed that both
roughness factors, Ra and Rz increased with extending the periods for
natural weathering for treated and untreated samples. The trend of
surface morphology variation was almost similar for both samples, but it
seems that the Ra factor was slightly higher for thermally-treated
wood. This can be elucidated by the effect of temperature on the
sensitive structure such as parenchyma and cell walls led to rupture
into wood components during thermal modification [26,37]. The
observed rough wood surface may be attributed to the surface erosion
occurring mostly in the early wood due to its thin cell walls and low
density [38]. In addition, increasing surface roughness during natural
weathering can be related to photo-degradation/leaching of lignin,
removed degrading materials and formation of micro-cracks, followed
by surface erosion occurrence by rain and wind [18].
Table 4
Crystallinity index of thermally-treated and untreated wood as a function of
natural weathering time determined by XRD technique.
Crystallinity index (%)
Weathering time (month) 0 6 24
Reference wood 71.4 (0.9) 71.79 (1.2) 58 (1.3)
Thermally-treated wood 74.5 (1.0) 78 (0.7) 65 (1.2)
*The numbers in parentheses are the standard deviation.
8
Construction and Building Materials 392 (2023)
3.4. Surface morphology and visual observation
The comparative images of the morphology and appearance
changes of the thermally-treated and un-treated samples are presented
in Fig. 5 as a function of weathering time. It can be observed that the
color of all samples tends to be changed with increasing weathering
time at different rates. In general, it is obvious from visual assessments
that the changes for the thermally treated sample are less than the
reference sample, especially up to 1 year. It seems that the lightness of
the refer- ence sample decreased rapidly in a short exposing time and
there was more tendency to get darker in reference sample. As can be
seen from Table 3, this is in consistent with quantitative measurements of
lightness changes. The darkening of untreated wood might be caused
by inducing the migration of extractives to the wood surface [37]. In
addition, by evaluating the surface morphology as a function of
exposing time, micro-cracks and surface roughening occurred in all the
samples affected through promoting the weathering process. The
presence of moisture intensifies the photo-degradation of wood [25].
Based on the meteorological information reported in Table 2, there is a
significant increase for rain precipitation and humidity in the last
period of weathering, which caused to rough surface morphology and
the for- mation of large/deeper cracks (see Fig. 5, 24 months). In
fact, the presence of wetting agent in the form of liquid or vapor water
from the surrounding atmosphere, due to its swelling property on the
cell wall and leaching of sedimentary materials, aggravated the
delignification and cracks formation. On the other hand, this issue can
probably play a significant role in terms of surface wettability, loss of
cellulose crystal- linity and photo-yellowing. It has also been reported
that climatic changes, especially humidity, increase color changes
caused by biolog- ical agents such as mold [18]. Accordingly, treated
wood shows better performance or a delay for degradation in natural
weathering due to improving the physical properties as a result of
thermal modification process. Nevertheless, it seems that thermal
treatment at medium tem-
perature (185 ◦C) shows no significant negative impact in terms of
mechanical loss on the performance of thermally-treated wood in ser-
vice time. This is in line with the findings of previous studies about the
◦ ◦
treatment of
influence process on mechanical
temperatures and 190
between the anatomical
C and 240structure of soft-
C of thermal
woods [39].
 A. Mastouri et
Fig. 7. Contact angle of thermally treated (T) and un-treated (C) spruce wood after natural weathering for different periods of 0 (Un-weathered), 6, 12, 18 and
24 months.
3.5. Crystallinity variation
The X-ray diffraction diagrams of thermally-treated and untreated
reference samples as a function of weathering periods are shown in
Fig. 6. Intensity and position of diffraction peak at 2θ = ~22 corre-
sponded to cellulose I crystalline structure, was subject to changes which
may be affected by crystallinity variation during weathering periods.
After heat-treatment, there was a tendency to increase in the crystal-
linity index, owing to degradation of amorphous regions in cellulose
and hemicelluloses as a result of thermal process. This finding is in line
with the previous researches [15,40].
As summarized in Table 4, long-term natural weathering (2 years)
gave rise to significantly decrease the crystallinity index around 12.7%
in thermally treated wood and 18.3% in reference spruce sample. The
leach out of lignin and extractives due to photo-degradation led to in-
crease surface cracks and more exposure of polysaccharides to envi-
ronmental factors can be an acceptable reason for the loss of crystallinity
in long-term outdoor exposure. The crystalline property of cellulose
microfibers as well as lignin, barricade the access of water molecules to
the OH groups on wood structures. On the other hand, in the short-
term natural weathering (6 months), the crystallinity of the reference
wood did not change, but the crystallinity index of thermally-treated
wood increased to 4.7%. It has been stated that the reduction of the
amor- phous polysaccharides of wood enriches the relative crystalline
content [41]. In previous research, we found that the loss of
crystallinity as a result of accelerated aging, is related to equilibrium
moisture content (EMC) and hygroscopicity of thermally treated wood
[15]. Therefore, crystallinity variation can be a sign of changes in water
related prop- erties of wood in weathering periods.
3.6. Wettability
The effect of thermal treatment on contact angle in comparison
with reference samples exposed for 6-, 12-, 18- and 24-month natural
weathering is shown in Fig. 7. Outside of weathering issue, thermal
treatment improved the hydrophobicity of spruce wood attributed to
crystalline degree and chemical change into lignin. In terms of weath-
ering, the contact angle of all samples decreased over exposure time. It is
clear that the heat treatment process has improved the hydrophobic
performance of the surface in service conditions, especially up to one
year. Water, as an effective solvent, causes the erosion about 50 µm of
wood surface per year during weathering condition [42]. Therefore,
leaching hydrophobic lignin component, development of new cracks
and increased amorphous region of cellulose led to loss in crystallinity
degree and the free hydroXyl groups, caused to increase surface wetta-
bility after weathering. According to the results of FTIR and XRD spec-
troscopy, it can be stated that high crystallinity and less lignin-
degradation may be the reason why the performance of modified sam-
ples in natural weathering is better to some extent.
9
Construction and Building Materials 392 (2023)
4. Conclusion
It was found that the hydrophobicity and crystalline structure of
cellulose improved during the thermal treatment. Natural weathering
due to climatic factors caused photo-chemical and morphological
changes on the both thermally treated and reference spruce wood sur-
faces. So, during 2 years of natural weathering, the roughness, wetta-
bility and color changes of all samples increased over time. The color
changes in the thermally modified wood was found to be negligible in
the early stages of weathering, owning to increased crystallinity to 4.7%
and low delignification. As a function of long-term weathering, crys-
tallinity index of cellulose decreased for all samples with 12.7% in
thermally treated wood and 18.3% in reference sample. Thermal treat-
ment delayed photo-yellowing and photo-degradation of wood due to
chemical reactions into lignin and crystallinity index of wood through a
photo-stable structure. Kinetic studies on the surface photo-degradation,
determined the service time of wood products for exterior uses.
Funding
This research received no external funding.
CRediT authorship contribution statement
Akbar Mastouri: Validation, Resources, Methodology, Data cura-
tion, Conceptualization, Software, Writing – original draft. Mohammad
Azadfallah: Writing – review & editing, Validation, Supervision,
Investigation. Gourav kamboj: Writing – review & editing, Resources.
Fatemeh Rezaei: Writing – review & editing, Formal analysis. Asghar
Tarmian: Writing – review & editing, Validation. Davood Efhamisisi:
Visualization, Investigation. Morad Mahmoudkia: Resources, Formal
analysis.
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.
Data availability
The authors are unable or have chosen not to specify which data
has been used.
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