Building and Environment 142 (2018) 188–194

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Building and Environment

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

Reducing formaldehyde emission of urea formaldehyde-bonded T

particleboard by addition of amines as formaldehyde scavenger
Aizat Ghania, Zaidon Ashaaria,b, Paiman Bawona, Seng Hua Leea,b,∗
a
Department of Forest Production, Faculty of Forestry, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
b
Institute of Tropical Forestry and Forest Products, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

A R T I C LE I N FO A B S T R A C T

Keywords: Particleboard is one of the building materials that contribute to the emittance of formaldehyde in enclosed area.
Particleboard In order to reduce the formaldehyde emission from particleboard, amines were added into the urea for-
Formaldehyde catcher maldehyde (UF) resin as formaldehyde scavenger. The amines used were methylamine, ethylamine and pro-
Methylamine pylamine. 0.5, 0.7 and 1% of each type of amine were added into UF resin and the mixtures were used to produce
Ethylamine
particleboard from rubberwood particles. The properties of the UF resin after addition of amines such as gelation
Propylamine
time, viscosity, pH, free formaldehyde content and thermal stability were evaluated. The physical, mechanical
properties and formaldehyde emission of the produced boards were also assessed. The results revealed that fully
cured amine-containing UF resin possesses higher thermal stability compared to control UF resin. Amine-con-
taining UF resin also had longer gelation time due to higher pH value. Nevertheless, both physical and me-
chanical properties of the resultant particleboard were negatively affected. Particleboard made from amine-
containing UF resin had higher thickness swelling and water absorption. In addition, lower bending strength and
internal bonding strength were also recorded. Insufficient pressing time for fully cured of resin might be the
reason for such phenomenon. Particleboard with F*** emission level (0.5 ≤ x ≤ 1.5 mg/L) as specified in
Japanese Industrial Standard (JIS) or European's E0 class equivalent were achieved when ethylamine and
propylamine were added, regardless of dosage used. This study showed the feasibility of using amines as for-
maldehyde scavenger. However, optimisation of processing parameters is needed to enhance the physico-me-
chanical properties of the particleboard.

1. Introduction
As one of the wooden materials for buildings applications, parti-
cleboard is classified as reconstructed panels that are mainly used to
manufacture furniture as well as for thermal and acoustic insulation
[1]. Particleboard is one of the important major timber products in
Malaysia. In the year 2017, the total revenue from the exportation of
Malaysian major timber products was RM 23.2 billion [2]. Particle-
board has contributed 1.88% of the total export value in 2017, which
accounted for RM 437 million. The local production line in Asian
countries, particularly Malaysia, is continuously influenced by the Ja-
panese trends as Japan is a main and vital for demand of particleboard.
Japanese Industrial Standard (JIS) has the most stringent standards in
the world where only wood panels with emission level of F****
(≤0.3 mg/L) could be used unrestrictedly within the room, while the
F*** (≤0.5 mg/L) and F** (≤1.5 mg/L) panels are only allowed pro-
vided that the room is spacious and have good ventilation [3]. Ac-
cording to Athanassiadou and Ohlmeyer [4], the respective emission
level of F****, F*** and F** are more or less equivalent to European
standard's SE0, E0 and E1.
Sick House Syndrome, a term derived from Sick Building System
that was first recognised in the year of 1983 by World Health
Organization as a medical condition, has been reported in residential
houses and educational facilities throughout the world. The occupants
experience various symptoms such as headache, nose and throat irri-
tation and fatigue [5]. Formaldehyde, acetaldehyde, acetone and 2-
ethyl-1-hexanol are the main indoor pollutants that were detected in
buildings and are closely related to the occurrence of mucosal symp-
toms among users [6]. The formaldehyde levels present in indoor air
are highly dependent on the formaldehyde sources, temperature, hu-
midity and air exchange rate in the building. The main sources of in-
door formaldehyde emission in the residential houses and educational
facilities nowadays include wood floor finishes, wood-based products
such as plywood, particleboard and medium density fiberboard, wall-
paper and paints as well as cigarette smoke [7].
Urea formaldehyde is a major aminoplastic resins used for the

∗
Corresponding author. Institute of Tropical Forestry and Forest Products, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia.
E-mail addresses: hua_cai87@hotmail.com, lee_seng@upm.edu.my (S.H. Lee).

https://doi.org/10.1016/j.buildenv.2018.06.020
Received 25 April 2018; Received in revised form 10 June 2018; Accepted 12 June 2018
Available online 12 June 2018
0360-1323/ © 2018 Elsevier Ltd. All rights reserved.
A. Ghani et al.
fabrication of interior wood-based products due to its low cost and high
reactivity [8]. A study by He et al. [9] revealed that urea formaldehyde
(UF) resin is the main source that contributes to the formaldehyde
emitted from wood-based panels. Urea and formaldehyde are highly
reactive and could react rapidly to form a strong bond. Nevertheless,
the reaction is reversible and therefore provides potential for long-term
formaldehyde release [10]. Formaldehyde emits from formaldehyde-
based adhesive bonded particleboard is mainly caused by the existence
of unreacted free formaldehyde in the board. However, this type of
release lasts only for a short period of time after manufacture. Another
release mechanism that could continue throughout the entire working
life of the board is through the hydrolysis of the aminoplastic bond
when exposed to elevated temperature and relative humidity [11].
In the past decades, great effort in reducing formaldehyde emission
from particleboard such as lowering the formaldehyde to urea (F/U)
molar ratio in UF resin has been made. However, lowering F/U ratio
inevitably lower the UF reactivity and subsequently, reduced the
properties of the resulted panels [12]. In addition, lowering of F/U ratio
has reached its limit when Maminski et al. [13] reported that the
strength of joints made with UF resin with F/U ratio of 0.85 is 20%
lower than the resin with an F/U ratio of about 1.1. To make matters
worse, no significant reduction of formaldehyde emission was recorded.
An additional amount of 15–20% of resin is needed in order to fulfill the
performance standards. Although lowering F/U ratio is the most direct
and economic method, other methods known to reduce formaldehyde
emission including incorporation of formaldehyde catcher or scavenger,
optimisation of processing parameters, and coating with nanoparticles
modified water based varnish have also been adopted by several re-
searchers [14–17]. Recently, a study by Jiang et al. [18] has proved that
particleboard thermally treated at mild temperature (50 or 60 °C) dis-
played significant reduction in formaldehyde emission. Ayrilmis et al.
[19] incorporated microfibrillated cellulose (MFC) into different grades
of urea formaldehyde (UF) resins (SE0, E0 and E1) and the for-
maldehyde emission of produced laminated veneer lumber (LVL) were
determined. The results revealed that the modification by MFC only
showed significant effect on SE0 grade UF resin in terms of for-
maldehyde emission reduction, while E0 and E1 grade UF resin did not
indicate the same observation.
Various amine-based compounds such as urea, ammonia, melamine,
dicyandiamide, and polyamides have been incorporated into for-
maldehyde-based resin to reduce its formaldehyde emission [20].
Nevertheless, studies on the addition of primary alkyl amines as for-
maldehyde scavenger are very limited. A study by Boran et al. [21]
reported on the effectiveness of adding different amine compounds in
the reduction of formaldehyde emission of medium density fiberboard
bonded with urea formaldehyde (UF) resin. Another study by Ghani
et al. [22] revealed that the addition of 1% propylamine into UF resin
could reduce the formaldehyde emission of the particleboard from
0.7 mg/L to around 0.3 mg/L. Nevertheless, physical and mechanical
properties of the produced particleboard were adversely affected. This
study aims to produce UF-bonded particleboard with lower for-
maldehyde emission using three primary alkyl amines, namely methy-
lamine, ethylamine and propylamine. The effects of incorporating dif-
ferent amines and dosages on the properties of urea formaldehyde resin
were investigated. In addition, the mechanical, physical properties and
formaldehyde emission of the resultant particleboard were also eval-
uated.
2. Materials and methods
2.1. Preparation of materials
Rubberwood particles were obtained from a local particleboard
plant, HeveaBoard Berhad, which is located in Gemas. The binding
agents used in this study, urea formaldehyde (UF) resin type E1, was
supplied by Aica Chemicals (M) Sdn. Bhd from Senawang. Three
189
Building and Environment 142 (2018) 188–194
different types of amines, namely, methylamine, ethylamine and pro-
pylamine which were used as formaldehyde scavenger om this study
were purchased from Evergreen Engineering & Resources. The hardener
used in this study was ammonium sulphate and wax was applied as
water repellent.
2.2. Resin properties after addition of amines
Several properties such as acidity (pH), viscosity of the resin, gelatin
time and free formaldehyde content were tested in the UF resin after
addition of different dosage of amines. The Mi105 pH/temperature
professional portable meter was calibrated with buffer solutions at pH 4
and 10 before testing begins. The resin/amine mixtures were cooled to
30 °C. Following that, the pH meter electrode was immersed into the
mixtures and pH reading was recorded. For viscosity measurements,
75 ml UF resin was poured into a 100 ml beaker. The viscosity of the
mixture was measured with an AMETEK Brookfield rotational visc-
ometer & rheometer at 20 °C with a spinning rate of 1 rpm. As for pH
determination, mixtures of UF resin and amines were poured into a
beaker and stirred well. Then, 6.5 g of the mixture was poured into a
test tube which was immersed (below water line) in a 100 °C water
bath. Immediately, the content was stirred continuously and the time
(in seconds) required for resin mixtures to cure was recorded.
For free formaldehyde content determination, 10 g UF resin was
weighed and poured into a 250 ml Eerlenmyer flask and 50 ml of di-
methyl sulphoxide solution was added. Rapidly, within 5 s whilst stir-
ring, 30 ml of 0.1 M HCl and Na2SO3 were added. Next, to ensure
complete reaction of the formaldehyde with sulphite, the mixture so-
lution was cooled in ice cubes for 3 min. Then, 1 ml 0.1% thy-
molphthalein solution was added. The excess acid was immediately
titrated with 0.1 M NaOH solution until it changed to blue color.
Volume of the 0.1 M NaOH used was recorded as V1. The blank test
under the same condition but without the UF resin was also carried out
and the volume of 0.1 M NaOH used was recorded as V2. The free
formaldehyde content was calculated using Equation (1).
Free formaldehyde (%) = ((V1eV2) x M x 3.002) / W [1]
where; V1 = volume of 0.1 M NaOH solution for resin, mlV2 = volume
of 0.1 M NaOH solution for blank, mlM = molarity of NaOH
solutionW = weight in grams for resin, g.
The experiment was repeated for the UF resin admixed with dif-
ferent dosage of amines. Two replicate measurements for each sample
were made.
2.3. Fourier transform infrared (FT-IR) spectroscopy analysis
A FT-IR spectrometer was used to determine any differences oc-
curring to the functional group on pure formaldehyde sample and after
the formaldehyde was mixed with different amounts of amine com-
pounds. FT-IR spectra tests were run at ambient temperature using pure
samples within the wave number range of 4000 to 400 cm−1 and at a
resolution of 4 cm−1. The infrared spectra of the samples were mea-
sured on a Perkin-Elmer FT-IR (model spectrum 100 series, USA).
2.4. Thermal stability of UF resin and amine-containing UF resins
Samples of cured control UF resin and amine-containing (methyla-
mine, ethylamine and propylamine) UF resins were tested for thermo-
gravimetric analysis (TGA) using Thermal Gravimetric Analyzer, TA
Instrument Q500 model. About 8 mg samples were placed in alumina
crucible. An empty alumina crucible was used as reference. All the
samples were heated from ambient temperature to 600 °C in a
50 mL min −1 flow of nitrogen at 10 °C min −1 heating rate.
A. Ghani et al. Building and Environment 142 (2018) 188–194

2.5. Particleboard fabrication Table 1

Physical properties of UF resin admixed with different dosage of amines.
Single-layer particleboard (340 mm width x 340 mm length x UF type Gelation time (s)a Viscosity (cp) pH FFCb (%)
12 mm thickness) with targeted density of 650 kg/m3 was fabricated.
8% UF resin based on the dry weight of rubberwood particles were M0.5 240 222 9.2 0.21
M0.7 256 265 8.9 0.20
prepared. 0.5, 0.7 and 1.0% of methylamine, ethylamine and propyla-
M1.0 264 286 9.1 0.19
mine based on the solid weight of UF resin were added into the UF E0.5 268 270 9.3 0.18
resin, respectively. 1% of ammonium sulphate (NH2SO4) based on the E0.7 271 282 9.5 0.16
solid weight of UF resin was used as hardener. 0.5% of wax emulsion E1.0 283 314 9.6 0.14
based on the dry weight of rubberwood particles was mixed together P0.5 267 278 9.4 0.15
P0.7 304 279 9.6 0.13
into the UF resin. The admixture was then sprayed evenly on the wood
P1.0 306 308 9.8 0.11
particles and blended for 3 min. After blending, the resinated particles Control 65 217 5.5 0.22
were formed manually into a mat using a wooden forming box. Next,
the mat was placed into a hot press and pressed at 180 °C for 270 s with ***M = methylamine, E = ethylamine, P = propylamine.
a
pressure of 4 Mpa. After hot pressing, the particleboard was condi- Gelation time at 100 °C.
b
tioned in a conditioning room to acquire constant weight before Free formaldehyde content.
properties evaluation. A set of particleboards was produced using UF
resin without addition of amines for comparison purpose. value, the initial pH value of control UF resin is 5.5 and turned into
basic (pH around 9) after the incorporation of amines. The higher pH
2.6. Properties evaluation of particleboard values were reportedly to have slowed down the gelation time of the
amines containing UF resin as UF resin is an acid-catalyzed resin which
2.6.1. Physical and mechanical properties requires an acidic condition to cure [25]. The critical pH point for UF
Physical properties such as thickness swelling (TS) and water ab- resin is 7, where above this point, the resin curing rate begins to in-
sorption (WA) was conducted according to the procedure specified in crease dramatically [26]. It can be observed that the application of
Japanese Industrial Standard (JIS) A 5908: 2003 [23]. A amines has reduced the free formaldehyde content in the UF resin.
50 mm × 50 mm section was cut from each board. The samples were When 0.5%, 0.7% and 1.0% of methylamine were incorporated into the
weighed and the thickness was measured before immersion in water at UF resin, a reduction of 4%, 9% and 14%, respectively, in free for-
25 ± 2 °C for 24 h. After soaking, the weight and thickness of the maldehyde content were observed. Meanwhile, addition of 0.5%, 0.7%
samples were remeasured to determine and express the TS and WA and 1.0% of ethylamine into UF resin were found to be able to reduce
values in percentage. Mechanical properties of particleboard such as 18%–36% of the free formaldehyde content from the UF resin. On the
modulus of rupture (MOR), modulus of elasticity (MOE) and internal other hand, propylamine portrays a relatively higher effectiveness in
bonding (IB) were tested according to procedure specified in JIS A the reduction of free formaldehyde in UF resin, where the addition of
5908: 2003 [23]. 0.5%, 0.7% and 1.0% propylamine has successfully reduced the free
formaldehyde content by 31%, 42% and 50%, respectively. Effective-
2.6.2. Formaldehyde emission by desiccator method ness of propylamine in the reduction of free formaldehyde content
Formaldehyde emission from the produced particleboards was compared to ethylamine and methylamine might be due to its higher
tested using desiccator method based on JIS A 1460: 2001 [24]. 300 ml reactivity. Differences in reactivity could be attributed to differences in
of distilled water was filled into a glass crystalizing dish, which is CeH bond dissociation energies where methylamine, ethylamine and
centrally located at the bottom of the desiccator. Nine pieces of samples propylamine were reported to have dissociation energies of 103 kcal/
(50 mm width x 150 mm length x 12 mm thickness) having surface area mol, 98 kcal/mol and 95 kcal/mol, respectively [27]. Propylamine with
approximately 1800 cm2 were placed into a desiccator, right above the the least bond dissociation energies have the weakest bond and broke
water-filled glass crystalizing dish. After 24 h, the water in the crys- more easily compared to methylamine and ethylamine. From methyl to
talizing dish was collected and the concentration of formaldehyde in propyl, the electron pushing effects increases on the C1 carbon atom
the solution was measured by acetylacetone molecular absorption and hence, electron density increases on C1 carbon to which NH2 group
spectrometry. is attached and hence, faster cleavage. Therefore, propylamine is the
most reactive and able to bind with higher amount of free for-
2.7. Statistical analysis maldehyde in the resin.

The data were analysed statistically to verify the significance of the
variables studied using Statistical Package for the Social Science (SPSS).
The collected data were analysed using one-way analysis of variance
(ANOVA) and the means were separated using Tukey's HSD test.
3. Results and discussion
3.1. UF properties after addition of amines
Gelation time, viscosity, pH and free formaldehyde content of the
UF resin after addition of different dosage of amines are listed in
Table 1. The UF resin with the addition of 0.5, 0.7 and 1.0% of me-
thylamine (M), ethylamine (E) and propylamine (P) were denoted as
M0.5, M0.7, M1.0, E0.5, E0.7, E1.0, P0.5, P0.7 and P1.0, respectively.
The gelation time of the control UF resin was 65 s. After the addition
of amines, the gelation time increased to a range of 240–306 s.
Similarly, the viscosity of the UF resin also increased by a range of
2%–41% compared to control after the addition of amines. As for pH
3.2. Characterisation of formaldehyde with different amine compound using
FT-IR spectroscopy
Fig. 1 illustrates the FT-IR spectrum of pure formaldehyde solution
before and after the addition of amine compounds. The pure for-
maldehyde solution showed band at 3307 cm−1 for the OeH stretch,
2986 and 2915 cm−1 for the CH2 symmetric stretch, 1644 cm−1 for the
C]O aldehyde saturated aliphatic and 1429 cm−1 for the CH2 methy-
lene bonds [28]. After the addition of amines, the formation of imine
bond linkages was confirmed by the FT-IR spectra where all the amine
compounds exhibit stretching bending imine (C]N) absorption at
about 1640 cm−1 to 1690 cm−1 in the spectrum as shown in Fig. 1b
[29,30]. These bands verified the formation of C]N in all amine
compound where the formaldehyde reacted with methylamine, ethy-
lamine and propylamine to produce methylmethanimine, ethylmetha-
nimine and propylmethanimine, respectively. Another absorbance band
at 1446 cm−1, 1453 cm−1 and 1425 cm−1 were observed from the
spectrum which correspond to the CeH bending alkane of CeH in CH3

190
A. Ghani et al.
Formaldehyde
Formaldehyde + Methylamine
100
Formaldehyde + Ethylamine
Formaldehyde + Propylamine
90
80
Transmittance (%)
C=N, stretching imines
70
C=O, aldehyde saturated aliphatic
60
50
40
1800 1600 1400 1200
Fig. 1. A comparison between the FT-IR spectrum (1800–600 cm−1) of pure
formaldehyde solution and formaldehyde admixed with different amines.
and CH2 resulting from CeC and CeCH interaction from the structure
[31,32]. The two bands near 1387 cm−1 and 1351 cm−1 might be at-
tributed to CO2− symmetric stretch of carboxylic acid salts [33],
probably due to the occurrence of Cannizzaro reaction that yields
formic acid salts and methanol [34].
Addition-elimination reaction occurs when amine reacts with alde-
hyde. This mechanism happens in two parts. In the first part, the amine
nitrogen attacks the carbonyl carbon to form a hemiaminal (RNH-
C(OH)R2) after the transfer of a proton from nitrogen to oxygen. In the
second part, the hemiaminal is protonated and H2O is eliminated, fol-
lowed by deprotonation, forms the imine (RN = CR2) [35,36]. Based on
the FT-IR analysis, the possible reaction between formaldehyde and
methylamine, ethylamine and propylamine amine compound are
shown in Fig. 2. For methylamine, the amine compound reacts with free
formaldehyde in the UF adhesive to produce N-methylmethanimine and
water. As for ethylamine, the amine compound will react with free
formaldehyde, which will then liberate N- ethylmethanimine and
water. By using propylamine as a formaldehyde catcher, the reaction
will produce N-popylmethanimine and water as by product.
3.3. Thermogravimetric analysis (TGA)
Thermogravimetric analysis curves for the UF resin and resin added
with different dosage of methylamine, ethylamine and propylamine are
presented in Fig. 3.
The thermal stability of the cured amine-containing UF resins are
higher compared to that of the control UF resin as higher residues were
recorded in the cured amine-containing UF resins as shown in Table 2.
As the amines react with free formaldehyde during the curing process in
the UF resin system, lower weight lost was observed compared to the
control UF resin [37]. Table 2 shows the weight loss of the control UF
resin and amine-containing UF resins in the temperature range from
100 to 600 °C. The control UF resin has lost up to 30.39% of its weight
at the temperature of 200 °C, almost two-folds compared to that of the
Fig. 2. Possible reaction between free formaldehyde and amine.
Building and Environment 142 (2018) 188–194
amine-containing UF resins which ranged from 11.42 to 20.87% at the
same temperature. UF resin admixed with propylamine had a higher
thermal stability as it has higher residual weight at 600 °C
(16.05–16.56%) compared to ethylamine (15.14–16.05%) and methy-
lamine (14.29–14.87). This phenomenon might be attributed to the
higher reactivity of propylamine with the free formaldehyde that was
present in the UF resin.
3.4. Physical and mechanical properties of particleboard
The density of the particleboard produced ranged from 640 to
685 kg/m3. Table 3 exhibits the thickness swelling (TS) and water ab-
sorption (WA) values of the particleboard made from UF resin and
amines-containing UF resin. The thickness swelling and water absorp-
1000 800 600
tion of the particleboard bonded with control UF resin were 28.01%
and 46.07%, respectively. However, after the addition of amines, the TS
values increased within a range of 59.96%–72.43%. Similarly, WA
values were increased within a range of 92.94%–117.43%. Regardless
of the types of amines used, both TS and WA values of the particle-
boards increased with increasing dosage of amines. This behaviour
might be correlated to the reduction in IB strength of the particleboard
produced with amine-containing UF resin. Higher IB strength should be
positively correlated to the TS and WA of the particleboard as better
bonding between particles could hold them tightly and resulted in
lower TS and WA [38].
Table 4 displays the mechanical properties of the particleboard
made from UF resin and amines containing UF resin. The modulus of
rupture (MOR) and modulus of elasticity (MOE) for control UF-bonded
particleboard were 15.13 N/mm2 and 1772 N/m2, respectively. After
the addition of amines, both MOR and MOE decreased. A reduction of
33.6% in MOR was observed when 1% methylamine was added while
MOR of the 1% propylamine-added samples reduced 42.4%. Similar
trends were also observed for MOE. Internal bonding (IB) strength of
the particleboard made with amines containing UF were 0.29–1.38 N/
mm2, whereas the control UF-bonded particleboard was 1.40 N/mm2.
When 1% of methylamine, ethylamine and propylamine were added,
the IB strength decreased to 1.30, 1.05 and 0.29 N/mm2, respectively.
The findings agree with Roffael et al. [39] who reported addition of
tannin as formaldehyde scavenger markedly reduced the IB strength of
the resulted particleboard. IB strength of particleboard is the most
sensitive physical characteristics that is highly dependent on the
crosslinking density of cured resin network [40]. The results suggest
that the crosslinking of the cured resin network was interfered by the
addition of amines. The reduction in mechanical properties might be
due to the pre-consumption of formaldehyde by amines that dispersed
in the UF resin [41]. As the free formaldehyde content decreased, the
degree of the crosslinking in the cured network also decreased corre-
spondingly and resulted in poorer mechanical properties. In addition,
high pH values after the addition of amines also contributed to the
reduction in mechanical properties. The rate and degree of the curing
reaction of the amine-containing UF resin decreased as well as the
numbers of the cross-linked structures in the cured resin. As a result, the
mechanical properties of the particleboard were adversely affected.
191
A. Ghani et al. Building and Environment 142 (2018) 188–194

Fig. 3. Temperature dependent mass loss (TG) of control UF resin and UF admixed with (a) methylamine (M), (b) ethylamine (E) and (c) propylamine (P).

Table 2 Table 4
Percentage of weight loss of cured UF resin and amine-containing UF resin by Mechanical properties of particleboard produced from UF and amine-con-
Thermogravimetric analysis (TGA). taining UF resin (n = 5).
Type of amine Percentage weight loss (%) Residuea (%) Board type Modulus of rupture Modulus of Elasticity Internal bonding
(N/mm2) (N/mm2) (N/mm2)
100 °C 200 °C 300 °C 400 °C 500 °C
M0.5 12.74ab (0.98) 1697a (165) 1.38a (0.15)
UF 25.54 30.39 71.08 80.65 84.14 13.65 M0.7 12.22ab (1.04) 1592a (197) 1.34a (0.16)
M0.5 11.32 18.62 64.60 77.00 81.09 14.87 M1.0 10.05bcd (1.05) 1542a (134) 1.30a (0.16)
M0.7 12.95 20.87 65.70 77.33 81.33 14.29 E0.5 12.06bcd (1.51) 1591a (193) 1.22ab (0.46)
M1.0 12.25 17.95 65.96 76.83 80.85 14.56 E0.7 11.45abc (1.71) 1545a (334) 1.13ab (0.22)
E0.5 13.33 19.48 65.49 77.01 81.12 15.14 E1.0 10.26bcd (1.16) 1487a (427) 1.05ab (0.36)
E0.7 13.38 20.18 67.65 78.97 82.37 15.68 P0.5 10.47bcd (0.67) 1317a (575) 0.74bc (0.23)
E1.0 11.54 17.92 67.24 78.82 82.54 16.05 P0.7 9.74cd (0.43) 1267a (166) 0.72bc (0.16)
P0.5 12.27 18.50 66.48 77.97 81.75 16.37 P1.0 8.71d (0.89) 1144a (431) 0.29c (0.05)
P0.7 11.67 17.32 68.23 78.99 82.75 16.05 Control 15.13a (1.9) 1772b (231) 1.40a (0.31)
P1.0 11.42 11.42 56.16 68.55 77.84 16.56
*number in the parentheses are standard deviation; Means followed by the
**M = methylamine, E = ethylamine, P = propylamine. same letter is not significant at p ≤ 0.05.
a
Residue at 600 °C. **M = methylamine, E = ethylamine, P = propylamine.

Table 3 0.8
Physical properties of particleboard produced from UF and amine-containing a
0.7
UF resin (n = 5).
Formaldehyde emisison (mg/L)

0.6 b
Board type Thickness swelling (%) Water absorption (%) c c F***
0.5 d de
M0.5 59.96b (4.99) 92.94a (6.91) e
M0.7 60.27b (6.17) 98.69a (17.58) 0.4 f g
M1.0 60.53b (9.00) 101.02a (10.90) g
0.3 F****
E0.5 60.84ab (4.89) 101.20a (26.30)
E0.7 60.99ab (5.24) 106.65a (2.75)
0.2
E1.0 61.19ab (2.37) 111.37a (7.26)
P0.5 63.18ab (2.74) 111.85a (9.15) 0.1
P0.7 64.54ab (4.03) 114.40a (9.98)
P1.0 72.43a (7.86) 117.43a (18.43) 0
Control 28.01c (2.9) 46.07b (1.5) Control M0.5 M0.7 M1.0 E0.5 E0.7 E1.0 P0.5 P0.7 P1.0
UF resin type
*number in the parentheses are standard deviation; Means followed by the
same letter is not significant at p ≤ 0.05. Fig. 4. Formaldehyde emission of particleboard from UF and amine-containing
**M = methylamine, E = ethylamine, P = propylamine. UF resins.
*Means followed by the same letter is not significant at p ≤ 0.05.
3.5. Formaldehyde emission of particleboard **M = methylamine, E = ethylamine, P = propylamine.

The formaldehyde emission values of the particleboard panels pro-

duced from UF added with different dosage of amines are tabulated in
Fig. 4. Statistically significant reduction in formaldehyde emission was

192
A. Ghani et al.
observed. The formaldehyde emission of the control board produced
using E1 UF resin was 0.7 mg/L, which is F** class according to JIS
standard (0.5 ≤ x ≤ 1.5 mg/L). The value was approximately
equivalent to European E1 class [4]. After the addition of amines, the
formaldehyde emission values of all the particleboard panels were
ranging from 0.31 mg/L to 0.56 mg/L. All the particleboard achieved at
least F*** or European E0 class equivalent (0.3 ≤ x ≤ 0.5 mg/L)
emission level with the exception of particleboard bonded with 0.5%
methylamine added-UF resin. As the formaldehyde emission of parti-
cleboard continuously decreased with the increasing dosage of the three
amines, addition of propylamine has resulted in the most reduction in
formaldehyde emission among the three amines used. The highest de-
crement in formaldehyde emission values were 50%, 54% and 56%
after the addition of 0.5%. 0.7% and 1.0% propylamine, respectively.
The emission limit for F**** class is ≤ 0.3 mg/L and the emission levels
of the board produced with 0.7% and 1% propylamine is on the
threshold of this limit value (0.32 and 0.31 mg/L).
The results are in agreement with Boran et al. [21] who reported
that propylamine is more effective in reducing the formaldehyde
emission of the MDF panels compared to other amines used. Ghani et al.
[22] also reported that the addition of 1.0% propylamine has success-
fully reduced 33% of the formaldehyde emission from UF-bonded
particleboard. The effectiveness of amines could be attributed to the
fact that incorporation of amines led to diminishing density of amino-
methylene bonds along the chain of the resin and successively reduced
the amount of formaldehyde emittance. The reduction in formaldehyde
emission could also be caused by the Cannizzaro reaction, a chemical
reaction that involves the base-induced disproportionation of an alde-
hyde when reacts with amine molecules [34]. As a result, the for-
maldehyde simultaneously oxidized and reduced in the Cannizzaro
reaction to form methanol and formic acid [42]. Superficially, effec-
tiveness of propylamine in formaldehyde reduction compared to ethy-
lamine and methylamine might be due to its higher reactivity as dis-
cussed earlier.
Apart from amines, other scavengers such as tannin, urea, sodium
metabisulfite and nanomaterials also proved effective in reducing the
formaldehyde emission from wood composite. Boran et al. [43] used
tannin solution extracted from white oak bark as formaldehyde sca-
venger in the production of UF-bonded medium density fibreboard
(MDF). The results revealed that, at the rate of 15% UF resin dosage and
1% tannin solution, the formaldehyde content of the MDF determined
by perforator method decreased 28% compared to that of the control
MDF. Correspondingly, IB, MOR and MOE experienced reduction of
12%, 28% and 18%, respectively. However, the obtained perforator
value (20–40 mg/100 g) is far from the E1 limit of ≤6.5 mg/100 g [44].
Sodium metabisulfite and urea were reported to be effective in reducing
the formaldehyde emission of particleboard [45,46]. In comparison to
urea, sodium metabisulfite was found to be a much superior for-
maldehyde scavenger while the reduction in mechanical properties is
still within acceptable value [41]. Nevertheless, the dosage needed to
achieve F**** class or SE0 class is 5% based on the solid resin, which is
much higher compared to dosage of amines used in this study
(0.5%–1%). In addition, the initial formaldehyde emission of the con-
trol board (0.45 mg/L) in the study by Costa et al. [47] is much lower
than the control board in this study (0.7 mg/L).
The practice of using nanomaterials in the production of low for-
maldehyde emission wood composites have been widely adopted by
several researchers. Nanoclay, organo-modified montmorillonite
(MMT), has been used as formaldehyde scavenger for the production of
oriented strand board (OSB). Four levels of MMT, namely 0, 1, 3 and
5% were added into 10% UF resin in the production of paulownia OSB.
Incorporation of MMT was found to have significantly decreased the
formaldehyde emission of the OSB. The maximum decrement of 39%
was recorded when 5% MMT was added (0.69 mg/L) compared to that
of the control OSB (1.13 mg/L). Unlike the other scavengers, im-
provement in mechanical properties was observed [48]. Another study
193
Building and Environment 142 (2018) 188–194
by Cadan and Akbulut [49] revealed that the addition of 1% and 3%
nanosilica, nanoalumina and nanozinc oxide particles had significantly
reduced the emission of formaldehyde from the UF-bonded particle-
boards. On the other hand, decrement of 53% and 21% in the for-
maldehyde emission was observed in the UF-bonded plywood added
with 3-aminopropyltriethoxysilane- and 3-methacryloxypropyl-
trimethoxysilane-modified nanocrystalline cellulose [50]. Despite their
superiority in scavenging the formaldehyde emission from wood com-
posites, production of nanomaterials is very costly and therefore is not
favourable in terms of economic sense. By comparison, primary amines
are preferable due to its higher effectiveness in reducing formaldehyde
emission and cheaper price.
4. Conclusion
This study examined the effects of incorporating of different amines
into UF resin and its relation to the properties of the resultant parti-
cleboard. From the current study, amine-containing UF resin had higher
pH values, gelation time and viscosity compared to the control UF resin.
When the added amines react with the existing free formaldehyde in the
UF resin, free formaldehyde content of the resin is reduced. Although
TGA results showed that a fully cured amine-containing UF resins
possess better thermal stability than control UF resin, it did not reflect
on the physical and mechanical properties of the resultant particle-
board. Addition of amines negatively affected both physical and me-
chanical properties of the particleboard, with higher TS and WA values
but lower MOR and MOE as well as IB values were recorded. The
pressing parameters (180 °C and 270 s) used in this study were adopted
from the particleboard plant. However, it seems not enough to fully
cure the amine-containing UF resins and resulted in poor physical and
mechanical properties of the particleboard. UF is an acid-catalyzed
resin and therefore longer pressing time is needed for the amine-con-
taining UF resin having higher pH values. However, low emission
particleboard (F*** class) were successfully produced when ethylamine
and propylamine were added, regardless of dosage used. This study
shows great potential in producing particleboard with F**** level had
the processing parameters been optimised. Optimisation of processing
parameters such as longer pressing time or higher pressing temperature
is needed for future study.
Acknowledgement
This work was supported by the Research University Grant Scheme
(RUGS) [grant numbers 9444600 & 9575500] and the Higher
Institution Centre of Excellence (HICoE) [grant number 6369107].
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