Wood Sci Technol

DOI 10.1007/s00226-016-0833-1
ORIGINAL

Effect of hygrothermal treatment on wood properties:

color changes and kinetic analysis using four softwood
and seven hardwood species
Miyuki U. Matsuo1 Katsuya Mitsui2 Isao Kobayashi3
Mitsuhiro Kohara4 Masato Yoshida1 Hiroyuki Yamamoto1

Received: 27 July 2015

Springer-Verlag Berlin Heidelberg 2016

Abstract Color changes of four softwood and seven hardwood species during
hygrothermal treatment were compared among species and kinetically evaluated.
Treatment temperature ranged from 70 to 120 C, and the durations were 5150 h.

Generally, the L (lightness) decreased and the total color differences DEab



increased irrespective of the treatment temperature. a and b (redness and yellowness) values varied spuriously based on the wood species. Kinetic analysis
using the timetemperature superposition principle, which uses the whole data set,
was successfully applied to the color changes. The apparent activation energies of

the color changes calculated from DEab
were 24.340.8 kJ/mol for softwood and
32.361.3 kJ/mol for hardwood. The average apparent activation energy for
hardwood was higher than for softwood. These values were lower than those
calculated from other material properties. The obtained results will contribute to
assess the color changes during the early stage of kiln drying and hygrothermal
modification of wood.

& Miyuki U. Matsuo

miyuki@agr.nagoya-u.ac.jp
1

Graduate School of Bioagricultural Sciences, Nagoya University, Furo-cho, Chikusa-Ku,

Nagoya 464-8601, Japan

Gifu Prefectural Research Institute for Human Life Technology, 1554 Yamadamachi,
Takayama 506-0058, Japan

Forestry and Forest Products Research Institute, 1 Matsunosato, Tsukuba 305-8687, Japan

Graduate School of Education, Gifu University, 1-1 Yanagido, Gifu 501-1193, Japan

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Wood Sci Technol

Introduction
Thermal treatment of wood has been widely studied for various purposes. The
chemical and physical changes that occur in wood during thermal treatment improve
the wood properties such as the dimensional stability, decay resistance, and esthetic
properties, while simultaneously inducing degradation of wood. The beneficial
changes have been studied as thermal modification and the detrimental effects as
thermal degradation. Because thermal modification processes unavoidably induce
degradation of wood, the treatment conditions must be optimized to achieve a
delicate balance to enhance the positive effects while mitigating the negative
effects. Thus, comprehensive study of the treatment process is required to
understand, develop, and universalize the thermal treatment technique.
Heating wood under wet condition is termed hygrothermal or hydrothermal
treatments. Though thermal modification generally refers to heat treatment over
150 C (Navi and Sandberg 2012), hygrothermal treatment of wet wood below the
boiling point of water could also be considered as a kind of thermal modification
because it exerts a pre-drying effect on logs and timbers and reduces the residual
growth stress inside logs and timbers (Kubler 1987; Okuyama et al. 1988).
Previously, the effects of hygrothermal treatment on green logs of sugi
(Cryptomeria japonica) wood and the effect of heating on reducing the residual
growth stress were evaluated using a kiln (Okuyama et al. 1988, 1990); although the
inside temperature of logs did not exceed 100 C during the treatment due to water
evaporation, the simultaneous degradation of wood properties and chemical
components was also investigated. The results showed that there was a cross-point
for reducing the residual stress and increasing defects such as surface checks and
inverse crooking and the chemical degradation. The optimal treatment conditions
were successfully determined, whereby maintaining the log surface at more than
80 C for approximately 3540 h was considered ideal. For shorter treatment times,
the positive effects of the treatment were not maximized, while longer treatment
caused unacceptable degradation of the logs. However, the drawbacks of these
studies were the wide variation of the temperature in the kiln and the lack of
versatility because only one wood species was used. Hence, comprehensive and
fundamental investigation is still required for application of the thermal treatment
technique to other wood species, to determine the optimal treatment conditions, and
to understand the mechanism of modification and degradation.
The kinetic approach employing the timetemperature superposition (TTSP)
method is a powerful tool for comprehensive investigation of reaction characteristics based on the activation energy required to induce changes in the material
properties as well as for prediction of the changes at any temperature and time
within the experimental ranges. This approach has been used for years to investigate
and predict the degradation of polymers. Matsuo et al. (2010, 2011, 2012, 2014)
successfully analyzed the color changes during dry thermal treatment of wood and
cellulose filter paper as a major component of wood using a kinetic approach based
on the TTSP method. Xu et al. (2016) also analyzed the discoloration of wood
plastic composites during hygrothermal treatment using a similar approach. Goli

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et al. (2014) elucidated the effect of the rate of air exchange on weight reduction
during thermal treatment of poplar wood using the TTSP method. They evaluated
the timetemperature equivalency of the reaction before starting the kinetic
analysis; this check was important to confirm the applicability of the approach and
avoid improper interpretation of the TTSP data. These studies demonstrated the
convenience and applicability of this type of kinetic approach for investigating
complex materials such as wood and wood composites.
Herein, the hygrothermal treatment of various wood species over a wide range of
treatment temperatures and durations was evaluated to understand the reaction
characteristics by using a kinetic approach employing the TTSP method. The data
from this study can be applied to predict the changes in the properties of wood
during thermal modification as well as in the early stage of kiln drying of green
wood containing a significant amount of internal moisture. In contrast to prior
studies, (1) the present study analyzes various wood species of both softwood and
hardwood, (2) the treatment conditions such as temperature, duration, and specimen
preparation are carefully controlled, and (3) the color parameters are analyzed; these
color properties can be measured in a nondestructive manner, are of esthetic
importance, and could serve as an index of the changes in other material properties.

Materials and methods

Sample preparation
Four softwood species and seven hardwood species were used (Table 1). For
karamatsu and beimatsu, both heartwood and sapwood were tested separately, while
for all other species sapwood was evaluated. Wood samples were cut and powdered
using a Wiley mill and passed through a 42-mesh screen and retained on a 60-mesh
screen. The moisture contents of the powder of a few wood species (sugi, buna, and
keyaki wood) were measured after conditioning in a desiccator over the saturated
sodium chloride solution at 23 C (target relative humidity: 75 %) for more than
2 months. The moisture contents of sugi, buna, and keyaki wood were 14.55, 14.21,
and 11.65 %, respectively.
Hygrothermal treatment
Filter paper thimbles and stainless-steel autoclave reactors were used for the
hygrothermal treatment. Two grams of wet powder was placed into a wet filter
paper thimble and covered with wet absorbent cotton; this assembly was then put
into an autoclave reactor (Fig. 1). The autoclave reactors were heated in an oven or
water bath at each treatment temperature. After heating for 10 min, additional vapor
was ejected from a faucet of the reactor to fill the inside of the reactor with saturated
vapor. The duration of treatment was measured just after the ejection. Table 2
summarizes the treatment conditions. The treated samples were air-dried for enough
duration under the ambient conditions in a dark place to avoid photodegradation.

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Table 1 Samples
Latin name

Parts

Air-dry density (g/cm3)

Sugi

Cryptomeria japonica D. Don

Sapwood

0.34

Hiba

Thujopsis dolabrata var. hondae Makino

Sapwood

0.41

Karamatsu

Larix kaempferi Carr.

Heartwood

0.42

Sapwood

0.58

Heartwood

0.53

Sapwood

0.48

Japanese name
Softwood

Beimatsu

Pseudotsuga menziesii Franco

Hardwood
Buna

Fagus crenata Blume

Sapwood

0.59

Hannoki

Alnus rubra Bong.

Sapwood

0.49

Mizume

Betula grossa Sieb. et Zucc.

Sapwood

0.69

Kakinoki

Diospyros kaki Thunb.

0.60

Yachidamo

Fraxinus mandshurica Rupr.

Sapwood

0.53

Konara

Quercus serrata Murray

Sapwood

0.75

Keyaki

Zelkova serrata Makino

Sapwood

0.74

Part of kakinoki wood was unclear. Judging from the light-colored untreated wood, the sample was
taken from the sapwood or the heartwood where sapwood/heartwood boundary was unclear

Fig. 1 Sample setting for

hygrothermal treatment

Table 2 Treatment temperature

and duration

123

Treatment temperature (C)

Treatment duration (h)

70

10

20

50

100

150

80

10

20

50

100

150

90

10

20

50

100

150

100

10

20

50

100

150

110

10

20

50

100

150

120

10

20

50

100

150

Wood Sci Technol

Color measurement
The treated wood powders were packed in sample dishes using a glass block. The
color of the samples was measured with a spectrophotometer (SHIMADZU
CORPORATION, UV-2200) using a D65 light source and observed at an angle of
2. The CIELAB color parameters (L , a , and b , respectively, indicating lightness,
red in plus values/green in minus values, yellow in plus values/blue in minus values)

were used to express the color change. The total color differences DEab
were
calculated using the following formula (JIS Z 8730 2009; JIS Z 8781-4 2013):
q

L  L0 2 a  a0 2 b  b0 2
1
DEab
where L is the lightness and a and b are the color coordinates; L0 ; a0 ; and b0 are
the corresponding reference values from the untreated specimens. Triplicate measurements were performed for each sample, and the average values were calculated.
Kinetic analysis of color changes
Kinetic analysis was performed to evaluate the color changes occurring during
hygrothermal treatment. It is universally accepted that the rate of a chemical
reaction can be described by the Arrhenius equation:


Ea
k A exp 
2
RT
where k is the rate constant of the chemical reaction, A is the frequency factor, Ea is
the apparent activation energy, R is the gas constant, and T is the absolute temperature of the reaction. The apparent activation energy is obtained from the slope
of the Arrhenius plot, which is the logarithm of the determined time versus the
reciprocal of the treatment temperature (Zou et al. 1996). Regression analysis of the
Arrhenius plot allows for determining the reaction rate at any temperature.
The k values can be determined from reaction formulae that include k and can be
used to model the changes in the chemical components or material properties. The
k values can also be determined as the half-value period of the changes. These two
methods are commonly used to determine k. However, the realistic changes of
complex materials such as wood or wood composites often do not fit well to the
reaction formulae; only one processed data point is generally used from the data set
for each temperature curve, eliminating most of the experimental points from the
analysis. These drawbacks sometimes make it difficult to accurately calculate Ea. To
analyze the changes in color during hygrothermal treatment using all of the data, the
Arrhenius approach was adopted employing the timetemperature superposition
principle (TTSP) for the kinetic analysis (Ding and Wang 2007; Gillen and Clough
1989; Gillen and Celina 2001; Wise et al. 1995). The curves of the measured color
parameter versus logarithmic treatment time at different temperatures can be
superposed by implementing proper scale changes on the log time axis. The shift

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distance along the logarithmic time axis is called the timetemperature shift factor,
aT, and is given by:
aT tT =tref

where tref is the treatment time at a reference temperature Tref, and tT is the time
required to achieve the same response at the test temperature T. Combining (2) and
(3) gives:
 

Ea 1
1

aT exp
4
R T Tref
where T and Tref are absolute temperatures. Ea can also be determined from a plot of
ln(aT) versus 1/T.
A temperature of 120 C was selected as Tref because the changes at this
temperature were sufficiently pronounced to estimate the fitting of data to the
regression curve. The measured color properties at treatment temperatures lower
than 120 C were superposed by applying aT on the time axis, and the constants of
the regression curves were recalculated for the best fit. All parameters were
estimated using a nonlinear iterative curve-fitting method. The coefficient of
determination (R2) and the root-mean-square error (RMSE) were used as the criteria
to assess the fitting of the experimental data to the tested models, where a higher
value of R2 and a lower value of RMSE indicate a better fit of the data to the model.

A logistic function that successfully fits to the change in L and DEab
of hinoki wood


(Matsuo et al. 2010) was used for L and DEab :
f x

a
1 b expcx

where f (x) is the color parameter, x is log(tT/aT), and a, b, and c are constants.

Results and discussion

Changes in color properties

Figures 2 and 3 show the changes in L , a , b , and DEab
of softwood and hardwood
species, respectively, based on the treatment duration and temperature. The values
of L decreased for all wood species, associated with darkening of the wood. This

result corresponded to an increase in DEab
, which was largely dominated by a


decrease in L . On the other hand, the a and b chromatic parameters followed
different trends depending on the wood species. For example, the a values for hiba
and the b values for keyaki sapwood increased or decreased constantly with
increasing treatment duration and temperature. The values of a for sugi sapwood
and buna initially increased and then decreased. Furthermore, the changes in the
chromatic parameters sometimes differed depending on temperature. For example,
the a values of karamatsu sapwood, mizume, and yachidamo decreased constantly
at lower temperature, while the a values of these species initially decreased and

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(a) Sugi

12

100

30

40
Color parameter

SW
25
6

50

0
12

0
100

(b) Hiba

20
20

15
35

40
Color parameter

SW
30
6

50

20
30

0
12

0
100

(c) Karamatsu

20
25

40
Color parameter

HW
25
50

0
12

0
100

(d) Karamatsu

20
20

15
30

40
Color parameter

SW
25
50

0
18

0
100

(e) Beimatsu

20
20

15
30

40
Color parameter

HW
25
50

12

6
12

0
100

(f) Beimatsu

20
20

15
30

40
Color parameter

SW
25
6

50

20
20

0
0

log(Treatment duration) (hour)

15
0

log(Treatment duration) (hour)

log(Treatment duration) (hour)

log(Treatment duration) (hour)

Fig. 2 Color changes of softwood as a function of treatment duration. SW sapwood, HW heartwood

then increased at higher temperature. Various and complex changes of the

chromatic parameters were observed regardless of whether the samples were
softwood/hardwood or sapwood/heartwood.

Decreases in L and accompanying increases in DEab
during heat treatment have
been well documented for various wood species, although wide ranges of treatment
temperatures were tested in previous studies (Bekhta and Niemz 2003; Brischke
et al. 2007; Esteves et al. 2008; Esteves and Pereira 2009; Gonzalez-Pena and Hale
2009b, 2011; Johansson and Moren 2006; Matsuo et al. 2010; Menezzi et al. 2009;
Mottonen and Karki 2008; Navi and Sandberg 2012; Sundqvist 2002). Matsuo et al.
(2010, 2014) indicated the similar behavior of L changes irrespective of
temperature (90180 C) could be explained by the acceleration of darkening

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(a) Buna

12

100

30

40
Color parameter

SW
25
6

50

0
12

0
100

(b) Hannoki

20
20

15
30

40
Color parameter

SW
25
6

50

15
30

0
12

0
100

(c) Mizume

20
20

40
Color parameter

HW
25
50

0
12

0
100

(d) Kakinoki*

20
20

15
31

Color parameter

40
26
50

0
12

0
100

(e) Yachidamo

20
21

16
30

40
Color parameter

HW
25
50

0
12

0
100

(f) Konara

20
20

15
30

40
Color parameter

SW
25
6

50

0
12

0
100

(g) Keyaki

20
20

15
30

40
Color parameter

SW
25
6

50

20
20

0
0

log(Treatment duration) (hour)

15
0

log(Treatment duration) (hour)

log(Treatment duration) (hour)

log(Treatment duration) (hour)

Fig. 3 Color changes of hardwood as a function of treatment duration. SW sapwood, HW heartwood.

*Part of kakinoki wood was unclear. Judging from the light-colored untreated wood, the sample was
taken from the sapwood or the heartwood where sapwood/heartwood boundary was unclear

corresponding to increasing temperature, and the relationship between the

acceleration and temperature could be expressed by apparent activation energy. A
similar increase and subsequent decrease of a and b have been reported for sugi,
hinoki, beech, spruce, and pine (Brischke et al. 2007; Gonzalez-Pena and Hale

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2009a; Matsuo et al. 2010, 2014; Okuyama et al. 1990), whereas a monotonous
decline of a and b has been reported for keyaki, eucalypt, and pine (Esteves et al.
2008; Matsuo et al. 2014). In previous reports for the treatment of sugi wood
(Okuyama et al. 1990), no significant change of a and b was documented during
the first 40 h of treatment and then increased rapidly between 40 and 45 h. Some of
this inconsistency may be explained by the fact that the treatment time employed in
prior studies was insufficient. Furthermore, the crucial factors responsible for the
complex and differing changes in the chromatic parameters, a and b , of the
various wood species may include differences in the extractives and constituent
monosaccharides of hemicelluloses for the various wood species, and the reactivity
of these species also differed depending on the reaction temperature. The
inconsistency of the changes in the chromatic parameters could be explained


Fig. 4 Intensity map of changes in DEab
of softwood in relation to treatment temperature and duration.
SW sapwood, HW heartwood

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Wood Sci Technol


Fig. 5 Intensity map of changes in DEab
of hardwood in relation to treatment temperature and duration.
SW sapwood, HW heartwood. *Part of kakinoki wood was unclear. Judging from the light-colored
untreated wood, the sample was taken from the sapwood or the heartwood where sapwood/heartwood
boundary was unclear

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because the literatures cited above include the various treatment temperatures and
the various process times of the treatment. Although it is suggested that the changes
in color were affected by the reactions of the specific extractives and hemicelluloses
(Hon and Mineura 2001), color changes during hygrothermal treatment, especially
the changes in the chromatic parameters, were too complex for elucidation of the
mechanism underlying these changes for each wood species.

Visualization of intensity of color changes

Figures 4 and 5 show contour maps of the intensity of the color changes as a
function of treatment temperature and duration. The color of each area, plotted
based on the treatment temperature on the vertical axis and duration on the

horizontal axis, corresponds to the value of DEab
. Darker areas in the map indicate

were
that the wood samples became darker, given that the changes in DEab

dominated by a decrease in L . This intensity map enables easy comparison of the
color changes for the various species under the same treatment conditions. Such
maps are also useful for determining the best combination of treatment temperature
and duration to obtain a favorable color or to avoid unfavorable color degradation.
From comparison of the contour maps among various wood species, certain
hardwood species (i.e., Fig. 5b mizume, c kakinoki, and g keyaki) underwent more
rapid and intense color changes.

Kinetic analysis

Changes of L and DEab
were analyzed because these changes were sufficiently
significant and followed clear enough trends for precise analysis. Although it is
possible to analyze the complex changes of a and b based on the vertical shift of
the curves at each temperature (Matsuo et al. 2014), a and b were not analyzed

herein because their changes were relatively small compared with L and DEab
, and
there was too much variability in the data set to permit correct analysis.

(a)

(b)

(c)


Fig. 6 Procedure of kinetic analysis applying TTSP method: a Changes in DEab
of buna wood as a
function of treatment duration, b superposed data using shift factor aT, and c Arrhenius plot derived from
aT and absolute treatment temperature T

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Thujopsis dolabrata var.

hondae Makino

Larix kaempferi Carr.

Larix kaempferi

Pseudotsuga menziesii Franco

Pseudotsuga menziesii

Karamatsu
HW

Karamatsu
SW

Beimatsu
HW

Beimatsu
SW

Fagus crenata Blume

Alnus rubra Bong.

Betula grossa Sieb. et Zucc.

Diospyros kaki Thunb.

Fraxinus mandshurica Rupr.

Quercus serrata Murray

Zelkova serrata Makino

Buna SW

Hannoki SW

Mizume SW

Kakinokic

Yachidamo
SW

Konara SW

Keyaki SW

Hardwood

Cryptomeria japonica D.Don

Hiba SW

Latin name

Sugi SW

Softwood

Japanese
name

32.3

40.2

38.4

61.3

47.3

48.5

34.3

40.8

33.6

27.6

24.3

26.1

37.3

Ea
(kJ/mol)

L

1.88

1.26

0.78

1.63

1.20

0.85

0.69

1.37

1.24

1.64

0.92

0.99

0.86

RMSE for
modela

0.980

0.991

0.995

0.981

0.994

0.995

0.995

0.987

0.983

0.982

0.990

0.983

0.993

R2 for
modela

0.949

0.979

0.998

0.991

0.986

0.974

0.958

0.980

0.965

0.974

0.939

0.858

0.950

R2 for Arrhenius
plotb

32.4

42.8

33.7

60.3

48.0

47.8

35.4

40.3

34.8

26.5

23.8

28.3

36.7

Ea
(kJ/mol)


DEab

1.91

1.44

0.74

1.78

1.21

0.76

0.78

1.37

1.05

1.67

1.00

1.06

0.86

RMSE for
model

0.974

0.991

0.996

0.989

0.995

0.995

0.994

0.989

0.988

0.975

0.982

0.983

0.992

R2 for
model

Table 3 Results of kinetic analysis: [apparent activation energy (Ea), fitting of model to the measured values, and linearity of Arrhenius plots]

0.957

0.986

0.993

0.997

0.984

0.974

0.973

0.989

0.960

0.977

0.937

0.822

0.978

R2 for Arrhenius
plot

Wood Sci Technol

21.0 %

23.2 %

Cv of
softwood

Cv of
hardwood

RMSE for
modela

R2 for
modela

R2 for Arrhenius
plotb

23.4 %

20.4 %

42.9*

31.7*

Ea
(kJ/mol)


DEab

RMSE for
model

R2 of regression line for Arrhenius plot

R2 for
model

R2 for Arrhenius
plot

Part of kakinoki wood was unclear. Judging from the light-colored untreated wood, the sample was taken from the sapwood or the heartwood where sapwood/heartwood
boundary was unclear

Root-mean-square error (RMSE) and determination coefficient (R2) for measured values versus modeled values


* Average values of Ea from L and DEab
(Welchs t test, p \ 0.05) were significantly lower for softwood than for hardwood

SW sapwood, HW heartwood, Avg average value, Cv coefficient of variation

43.2*

Avg of
hardwood

Ea
(kJ/mol)

L

31.6*

Latin name

Avg of
softwood

Japanese
name

Table 3 continued

Wood Sci Technol

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Figure 6a, b, respectively, shows the changes in DEab
of buna wood as an
example of the procedure for kinetic analysis and superposition of the data on the
regression curve. The well-superposed curve implies that color changes follow the
apparently similar process when it is described as functions of logt at each

temperature. Arrhenius plots of DEab
and the corresponding linear regression lines
are presented in Fig. 6c. The apparent activation energy (Ea) for the color change
was calculated from the slope of the Arrhenius plots. Table 3 summarizes Ea,
RMSE, and R2 between measured values and estimated values from regression
curve, and R2 for the Arrhenius plot and the corresponding regression line for each
wood species. The high R2 values indicate that the regression curves fit well to the
color changes for all species. The regression lines for the Arrhenius plot showed
good linearity (R2 [ 0.822), suggesting that kinetic analysis employing TTSP can
be used for prediction of the color change of hygrothermally treated wood in the
treatment temperature range of 70120 C. Figure 7 presents a comparison of the

measured values of DEab
versus the values predicted using the model and Ea; this
figure demonstrates that the model and Ea adequately reproduce the actual changes.
This method could be applied to the prediction of the changes in wood properties.
However, to check the reliability of this method and establish the method for
accurate prediction of the changes, the comparison between the model and newly
tested specimens will be needed as a next step.
The Ea required to induce a change of L for softwood samples ranged from 24.3 to

40.8 kJ/mol, 23.840.3 kJ/mol for DEab
of softwood, 32.361.3 kJ/mol for L of

hardwood, and 32.460.3 kJ/mol DEab for hardwood. The Ea values calculated from


data were similar, given that the changes in DEab
were dominated by
the L and DEab

L . These values were apparently smaller than the Ea values calculated from the color
changes during dry thermal treatment at 90180 C (hinoki: 113 kJ/mol, keyaki:
188 kJ/mol, sugi: 123 kJ/mol, cellulose filter paper: 120 kJ/mol) (Matsuo et al. 2010,
2012, 2014), which is consistent with previous reports that chemical reactions
responsible for the changes of wood properties proceeded faster under moist
conditions than under dry conditions (Stamm 1956; Kohara 1958b). It could be
explained by the catalytic role of water during thermal treatment. In addition, since
hygrothermal treatment in this study was done in a small sealed reactor, the acidic

Fig. 7 Models of the color

changes of buna wood. Solid
lines are the theoretical values of

DEab
calculated from formula
(5) and Ea. Plots are the

measured values of DEab
, which
were the same values as Fig. 6a

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components produced by decomposition of hemicelluloses were not removed from the

reaction system and could accelerate the reaction. As shown at the bottom of Table 3,
the average Ea values obtained for softwood were significantly smaller than those

obtained for hardwood (softwood L : 31.6 kJ/mol, softwood DEab
: 31.7 kJ/mol,


hardwood L : 43.2 kJ/mol, hardwood DEab : 42.9 kJ/mol). This result suggests that the
energetic barrier for activation of the color change for hardwood is higher than that of
softwood, which differs from previous studies in which it was suggested that the
thermal degradation of hardwood proceeds faster than that of softwood because certain
chemical components of hardwood are more reactive than those of softwood (Kohara
1958a, b). The values of Ea calculated from the color parameters were notably smaller
than those obtained by other properties (Stamm 1956) such as weight reduction
(66.2 kJ/mol for coniferous wood), MOR (68.3 kJ/mol for Sitka spruce), and work to
maximum load (72.5 kJ/mol for Sitka spruce).

Conclusion
The effect of thermal treatment of four softwood species and seven hardwood
species on the color changes of wood during hygrothermal treatment at 70120 C

was evaluated. The L values decreased and the DEab
values increased at all
treatment temperatures irrespective of the wood species. The values of a and b
varied based on the wood species. The good linearity of Arrhenius plot and the
comparison between measured values and modeled values indicated the possible
application of Arrhenius equation for the prediction of the changes during
hygrothermal treatment. The apparent activation energy values calculated from

DEab
were 24.340.8 kJ/mol for softwood and 32.361.3 kJ/mol for hardwood. The
average value of the apparent activation energy of hardwood was significantly
higher than that of softwood. These values were remarkably lower than the values
calculated from the color changes during dry thermal treatment and somewhat lower
than the values calculated from other properties such as the mechanical properties
and weight decrease. These results showed that the reactivity of all wood species
investigated was higher in the presence of water than in the absence of water, higher
for softwood than for hardwood, and higher for color changes than for other
properties.
Acknowledgments The authors are grateful to the late Professor Okuyama for his guidance with this
study.

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