Production of Melamine Fortified Urea-Formaldehyde

Resins with Low Formaldehyde Emission

Nadia T. Paiva,1,2,3 Ana Henriques,1 Paulo Cruz,2 Joao M. Ferra,2 Luisa H. Carvalho,1,4
Fernao D. Magalhaes1
1

LEPAEDepartamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do Porto,

Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
2
EuroresinasIndustrias Qumicas, S.A., 7520-195 Sines, Portugal
3
ARCPAssociacao Rede de Competencias em Polmeros, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal
4
DEMadDepartamento de Engenharia de Madeiras, Instituto Politecnico de Viseu,
Campus Politecnico de Repeses, 3504-510 Viseu, Portugal
Received 7 April 2011; accepted 17 July 2011
DOI 10.1002/app.35282
Published online 26 October 2011 in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: Melamine can be incorporated in the
synthesis of urea-formaldehyde (UF) resins to improve
performance in particleboards (PB), mostly in terms of
hydrolysis resistance and formaldehyde emission. In this
work, melamine-fortified UF resins were synthesized using a
strong acid process. The best step for melamine addition
and the effect of the reaction pH on the resin characteristics
and performance were evaluated. Results showed that melamine incorporation is more effective when added on the initial acidic stage. The condensation reaction pH has a
significant effect on the synthesis process. A pH below 3.0

results on a very fast reaction that is difficult to control. On

the other hand, with pH values above 5.0, the condensation
reaction becomes excessively slow. PBs panels produced
with resins synthesized with a condensation pH between 4.5
and 4.7 showed good overall performance, both in terms of
C 2011
internal bond strength and formaldehyde emissions. V

INTRODUCTION

because of high reactivity, good performance, and

low cost. However, the hydrolytic degradation of UF
polymers causes a significant weakening of resin
bonds and is a source of formaldehyde emissions.5
Another cause of formaldehyde emission from WBP
produced with these resins is the presence of free
(unreacted) formaldehyde.1
In 2006 the International Agency for Research on
Cancer (IARC), has classified formaldehyde as carcinogenic to humans.6 The new classification has led
the industry to find strategies to limit formaldehyde
emission levels from WPB. The most common
approaches consist in: decreasing the F/U (formaldehyde/urea) molar ratio, incorporation of other comonomers in the synthesis and adding formaldehyde
scavengers to the particles/fibers before or after resin
blending.7 The F/U molar ratio has been slowly
decreased over the years from its initially high value,
but causes the manufacturing processes to be more
sensitive to perturbations in operating conditions and
leads to particleboards (PBs) with lower physical and
mechanical properties.8 Current commercial resins
have typical F/U values between 0.9 and 1.1.
The incorporation of a small percentage of melamine
to UF resins improve moisture/water resistance and
therefore decrease formaldehyde emissions. The aminomethylene bonds in UF resins are quite susceptible

Urea-formaldehyde (UF) resins are the most used

type of adhesives used in wood-based panels (WBP)
industry.1 Worldwide, these resins represent 80% of
the total production in the aminoresins class.2 The
remaining 20% correspond mainly to melamine-formaldehyde (MF) resins, with a small percentage of resins synthesized from other aldehydes and/or other
amino compounds.3 According to SRI Consulting,4 the
global production of UF resins in 2008 was ~14 mT.
Their consumption increased 2.8% in 2008, and is
expected to grow an average 3.2% per year from 2008
to 2013, and just under 2% per year from 2013 to 2018.
UF resins are thermosetting polymers that, before
cure, consist of an aqueous solution/dispersion of
unreacted monomers, linear or branched oligomeric,
and polymeric molecules.1 They are condensation
products of aldehydes with compounds containing
amino groups. Their success on the market is mostly
Correspondence to: F. D. Magalhaes ([email protected]).
Contract grant sponsor: FCTFoundation for Science
and Technology and Euroresinas (Sonae Industria);
contract grant number: SFRH/BDE/51294/2010.
Journal of Applied Polymer Science, Vol. 124, 23112317 (2012)

C 2011 Wiley Periodicals, Inc.

V

Wiley Periodicals, Inc. J Appl Polym Sci 124: 23112317, 2012

Key words: urea-formaldehyde resins; melamine; strongly

acid process; GPC/SEC; formaldehyde emissions; internal
bond strength

2312

of hydrolytic attack. However, more stable bonds

are obtained when a methylene carbon is linked to
an amide group from a melamine ring, instead of
nitrogen from urea. This is especially true at high
temperatures, probably due to the quasiaromatic ring
structure of the melamine. In addition, the slower pH
decrease in the bond line due to the buffer capacity
of melamine could also explain the higher stability of
the bonds in melamine-urea-formaldehyde (MUF)
resins.1 However, this lower decrease in pH also
causes an increase in gel time and consequently,
higher pressing times.
The wide range of formulations for MUF resins
originates different properties, performances, and
durabilities.2,3 One can distinguish two particular
cases: MUF resins, where the melamine content is
above 5%, and melamine-fortified UF resins, with melamine content below 5%. In both cases, the production
can be performed in different ways: cocondensation of
all monomers, melamine, urea and formaldehyde, in a
multistep reaction; mixing of separately synthesized
MF and UF resins; and postaddition of melamine, in
various forms (pure melamine, MF/MUF powder
resin or melamine acetates) to an UF resin during the
preparation of the glue mix.9
Melamine-fortified UF resins are now a conventional alternative to UF resins for application as
adhesives in WBP, such as PB and medium density
fiberboard (MDF). These allow reducing formaldehyde emissions and improving the physical properties of the panels. However, the costs for these fortified products are higher due to the higher price of
melamine compared to urea.1 When added to the
reaction mixture, melamine can enter in any of these
steps5: initial methylolation step (before or after the
addition of the first urea), condensation step (before
or after the addition of the second urea), or final
urea addition. The best procedure depends on the
particular process used. The studies by Shiau and
Smith 5, using an alkaline-acid process, showed that
melamine addition is more effective in the methylolation step. On the other hand, Hse studied melamine
addition in a strongly acid process, and concluded
that the best results were obtained for melamine
addition during acidic condensation (pH between 4.5
and 6.5).10 This author essentially studied the melamine reaction with a UF prepolymer formed in a
strongly acid environment, the final MUF resin produced had a F/U molar ratio of 1.2, with 4.39%
(weight basis) maximum melamine content.
Previous studies have shown that the melamine
content has a very significant effect on both the resin
and PB properties. An increase in melamine content
results in an increase in gel time, solid content, and
internal bond strength. On the other hand, there is a
decrease in thickness swelling, water absorption,
and formaldehyde emission.11
Journal of Applied Polymer Science DOI 10.1002/app

PAIVA ET AL.

MUF resins are produced according to the same

procedures as UF resins. The most common
approach is the alkaline-acid process.9 The process
consists in an initial alkaline methylolation (hydroxymethylolation) step followed by an acidic condensation. An alternative strategy is the strongly acid
process.8 In this case the initial reaction is carried
out under strongly acidic environment, in which the
methylolation and condensation reactions occur
simultaneously. The methylolation step consists in
the reaction between urea, melamine, and formaldehyde to form the so called methylolureas and methylolmelamines (Fig. 1). At this low pH, however,
these species react almost instantly to form linear
and/or branched polymers linked by methyleneether and methylene bridges (Fig. 2). The released
heat is sufficient to drive the reaction to the desired
condensation level, and can be controlled by a programmed addition of urea to the acidified formaldehyde solution. This process may reduce the reaction
time by 30% in relation to the alkaline-acid process,
with much lower energy consumption.8 The disadvantage of this process lies in the difficulty in controlling the highly acid condensation step, due to its
exothermic character.12
The present study investigates the best procedure
for incorporation of melamine in the synthesis of UF
resins, producing a MUF copolymer in the first reaction stages. The general goal is the production of a
melamine fortified UF resin with a molar ratio F/U
of 0.98, with good internal bond strength and low
thickness swelling and formaldehyde emission.

MATERIALS AND METHODS

Resin preparation
All the resins were synthesized in the laboratory reactor. The synthesis was carried out in 2.5 and 5 L
round bottom flasks, equipped with mechanical stirring and thermometer. Temperature control of the reactor is performed using a heating mantle. The resins
were synthesized using the so-called strongly acid
process, which is based on the occurrence of methylolation and condensation reactions simultaneously.13
The process begins with the methylolation/condensation reaction between a 50% formaldehyde solution and urea, at very low pHbetween 0.5 and
2.5by adding an appropriate amount of a sulfuric
acid. This reaction consists essentially in the addition
of one to three formaldehyde molecules to a urea
molecule, to form the so-called methylolureas. The
UF polymer builds up when the methylolureas react
with free urea and formaldehyde, producing linear
and partly branched molecules with medium to high
molecular weights.1 Urea is added slowly, allowing
the heat of reaction to raise the temperature from

PRODUCTION OF MELAMINE FORTIFIED UF RESINS

2313

Figure 1 Formation of methylolureas and methylolmelamines (mono-, di- and tri) by the addition of formaldehyde to
urea and melamine.

the initial 60 C to values between 80 and 90 C. The

amount of urea added to the formaldehyde solution
during this initial step is sufficient to provide an F/
U molar ratio of 3.5 to 3. If melamine is added in
this step, the reaction then proceeds until a desired
viscosity of 500 cP is reached.
The second step consists in the methylolation reaction of additional urea with free formaldehyde still
present in the reaction mixture. To make sure that
only this reaction takes place, and the condensation
is inhibited, it is necessary to adjust the pH to a neutral or slightly basic value, by adding sodium
hydroxide solution. The additional urea added in
this step must be enough to provide an F/U molar
ratio of 2.5 to 1.5. If melamine is to be added in this
step, the gain in reaction mixture viscosity is
expected to occur after this addition.

Afterwards, the reaction mixture is cooled during

30 min, until a temperature of 50 C is attained. At this
point, a final amount of urea is added to provide a
final F/U molar ratio of 0.98. The reaction is terminated by cooling the mixture to a temperature of 25 C.
Viscosity, pH reactivity, and solid content were
determined at the end of each synthesis. Viscosity
was measured with a Brookfield viscometer at a constant temperature of 25 C. The resin pH was measured using a combined glass electrode. The solid
content was determined by evaporation of volatiles
in 2 g of resin for 3 h at 120 C. The resin reactivity
was determined by measuring the gel time of a resin
sample at 100 C, after addition of a cure catalyst
(ammonium sulfate or ammonium nitrate).
As described the synthesis is divided in three different steps. Melamine can be added to the reaction

Figure 2 Condensation of the methylolureas and methylolmelamines to form methylene-ether bridges and methylene
bridges.
Journal of Applied Polymer Science DOI 10.1002/app

2314

mixture in any of these steps: in the initial methylolation/condensation step (before or after the addition of the first urea), in the methylolation step
(before or after the addition of the second urea), or
with the final urea. The first two alternatives were
studied here. In all cases, the amount of melamine
added was 3% relative of final mass of resin.
GPC/SEC analysis
A GPC/SEC equipped with a Gilson Differential RI
detector and a Rheodyne 7125 injector with a 20 lL
was used. The columns used were PSS Protema 100
and 300; 5 lm, conditioned at 60 C using an external
oven. The flow rate was 1 mL/min. Samples for
analyses were prepared by dissolving a small
amount of resin in DMSO (dimethylsulfoxide), followed by vigorous stirring. Subsequently, the sample is left to rest, and then it is filtered through a
filter of 0.45 lm.14
Particleboard production
The production of PBs is essentially divided into
four stages: preparation of raw materials, blending,
mat formation, and pressing. Wood particles were
provided by a PB manufacturer (Sonae Industria,
Oliveira do Hospital). Standard mixtures were used
for the core and face layers, which are composed of
different proportions of pine, eucalyptus, pine sawdust, and recycled wood. The moisture content of
the standard mixtures was checked before blending,
using an infrared balance. The average of the moisture content of the face and core layers particles was
2.5 and 3.5%, respectively. Wood particles were then
blended with the resin, catalyst and paraffin in a
laboratory glue blender. The gluing factor was 6.3%
resin solids in the face and 6.9% in the core, based
on the oven-dry weight of wood particles. The resin
was more catalyzed in the core layer (3% solids
based on oven-dry weight of resin) than in the face
layer (1% solids based on oven-dry weight of resin).
The paraffin level was 0.15% solids (based on ovendry weight of wood).
Three-layer PB was hand formed in an aluminum
container with 220  220  80 mm3. The total percentages of board mass were: 20% for the upper face
layer, 62% for the core layer, and for 18% bottom
face layer. The pressing of PB panels was carried out
in a hot-press, controlled by computer and equipped
with four thermocouples, a displacement sensor
(LVDT), a load cell, and a pressure transducer.
Pressing cycle (stage duration, press closing time,
platen temperature) was scheduled to simulate a
typical PB continuous pressing operation. The glued
particles were pressed at 190 C with a pressing
time of 150 s. The target thickness was 16 mm. The
Journal of Applied Polymer Science DOI 10.1002/app

PAIVA ET AL.

TABLE I
Operation Conditions for the First Four Synthesis
Attempts

Resin
UF
UF
UF
UF

1
2
3
4

Melamine
addition

pH before
melamine
addition

Final
pH

Final
viscosity
(mPa/s)

First step
Second step
First step
First step

0.52
78
0.52
57

8.83
7.81
8.90
8.82

60
142
210
64

average density of the final boards was 630 6 20

kg/m3. The thickness of the panels is measured in
five points (center and each corner) after pressing.
Physic-mechanical characterization of particleboard
After pressing, boards were stored in a conditioned
room (20 C, 65% RH) and then tested accordingly to
the European standards. The following physic-mechanical properties were evaluated: density (EN
323), moisture content (EN 322), internal bond
strength (IB) (EN 319tensile strength perpendicular to the plane of the board) and thickness swelling
(EN 317). For each experiment, four board replicates
were obtained. Formaldehyde content was determined according to EN 120 (perforator method).
Panels for the analysis of formaldehyde content
were stored in sealed plastic bags.
RESULTS AND DISCUSSION
This study essentially consisted in five distinct
approaches for the synthesis strategy. The difference
between them consists essentially in the timing and
pH for melamine addition. The first four attempts,
listed in Table I, resulted in nonviable processes or
inappropriate resin performance.
For these formulations the solid content was about
63% in all cases. It must be noted that there is a
major difference between synthesis 1 and 3, which
results in different ending viscosities. In the first
one, the pH was increased to 7 after melamine addition, by adding sodium hydroxide solution, and
then the second urea was added (second step). In
resin UF 3, on the other hand, the base was not
added after melamine addition, and there was only
a waiting time for allowing the pH to increase until
stabilizing. The final pH before the second step was
therefore between 5 and 6.
In resin UF 2, melamine addition occurs in the
second step (methylolation at neutral pH). It was
observed that the resin did not gain viscosity after
the addition, suggesting that the addition of melamine in a neutral to alkaline phase only promotes
the formation of methylolmelamines.

PRODUCTION OF MELAMINE FORTIFIED UF RESINS

2315

TABLE II
Particleboard Properties Obtained in the First Four Synthesis Attempts
Resin
UF
UF
UF
UF

1
2
3
4

Density
(kg/m3)

Internal bond
strength (N/mm2)

Thickness
swelling (%)

Moisture
content (%)

Formaldehyde content
(mg/100 g oven dry board)

666
642
633
627

0.38
0.18
0.43
0.28

28.1
38.1
28.6
33.2

6.3
6.1
4.7
6.0

3.2
2.7
3.4
3.0

Finally, in resin 4 the melamine was added in the

first step, after the addition of the first urea and at a
pH between 5 and 7 (this value is obtained with the
addition of an appropriated base).
Table II shows the results for the PB properties
obtained with the first four resins. The results
obtained for the resins 2 and 4 explain values out of
specification with regard to IB strength (lower than
0.35 N/mm2, the requirement for type P2 boards,
according to EN 319) and thickness swelling, especially in procedure 2. Comparing the results for the
UF resin 4 with the results for the UF resins 1 and 3
it is possible to observe that higher condensation pH
results in the decrease of PB properties.
The panels produced with resins UF 1 and 3 present a high performance, namely high IB strength
and low formaldehyde emission. However, the synthesis processes were very unstable (the increase of
the viscosity is too fast during the condensation
step), making these strategies unviable for industrial
use without rigorous on-line control of the degree of
condensation.
In the ensuing approach (fifth synthesis strategy)
melamine was added to the initial formaldehyde solution at its normal pH (between 3 and 3.5), instead
of decreasing it to 0.52.5 as before. After a 5 min
stabilization period, pH was raised to 4.56, and
only then the first urea was added. The second and
third steps were then performed as previously
described in synthesis described earlier. The major
difference between this approach and the previous
is the initial formation of methylolmelamines, that
posterior react with methylolureas and urea.
Table III summarizes the four syntheses that compose this fifth approach. The fundamental difference
between them is the pH set for the addition of the
first urea. For all the synthesis it was observed that
lower pH implied faster viscosity increase (higher

reaction rate). It is possible to conclude that more

acidic conditions favor the condensation of the
methylolmelamines and methylolureas produced in
the methylolation reaction, instead of a methylolation reaction between the unreacted urea and free
formaldehyde. The synthesis of UF 5.4 resin was
slightly different. During the methylolation/condensation reaction the resin did not gain the desired viscosity (500 cP) after one and a half hours of reaction
time. The temperature was therefore raised to 95 C
and the second urea was added immediately. In
these conditions the reaction progressed and the viscosity increased. The reaction mixture was then
cooled to 60 C and the final urea was added. This
synthesis was therefore different because both the
first and second urea amounts were present in the
methylolation/condensation step.
In conclusion, we can suggest that for this synthesis process for pH higher than 5.5 the condensation
reaction does not occur at low temperature and high
F/U molar ratio.
Table IV presents the physic-mechanical properties of the PB produced with the four resins. In general, the values are favorable for all features. Increasing the methylolation/condensation reaction pH
decreases the IB strength of the panels. However, all
the IB strength values are higher than the minimum
acceptable value of 0.35 N/mm2. Regarding formaldehyde emissions, all resins are below the limit
imposed by CARB II legislation corresponding to an
equivalent of perforator value of 4.0 mg/100 g
oven dry board,15 all resins having emissions below
3 mg/100 g oven dry board. The other properties
are not sensitive to the reaction pH.
To understand the impact of the development of
this resin in relation to existing commercial products, Table V shows the results for physical-mechanical properties of panels produced with three resins

TABLE III
Properties of UF Resins Produced in Fifth Synthesis Attempt
Resin
UF
UF
UF
UF

5.1
5.2
5.3
5.4

pH before 1st urea addition

Final pH

Final viscosity (mPa/s)

Solid content (%)

Gel time (s)

4.50
4.70
5.00
6.00

8.21
7.78
9.18
8.80

430
100
140
95

63.40
62.25
63.41
64.17

75
68
110
48

Journal of Applied Polymer Science DOI 10.1002/app

2316

PAIVA ET AL.

TABLE IV
Properties of Particleboards from UF Resins Produced in Fifth Synthesis Attempt
Resin
UF
UF
UF
UF

5.1
5.2
5.3
5.4

Density
(kg/m3)

Internal bond
strength (N/mm2)

Thickness
swelling (%)

Moisture
content (%)

Formaldehyde content
(mg/100 g oven dry board)

637
622
634
641

0.44
0.44
0.35
0.36

28.9
30.9
29.6
29.9

5.4
4.7
5.0
5.1

2.7
2.8
2.5
2.7

produced by different processes and with different

melamine contents. Resins 1 and 2 are produced by
the alkalineacid process, having a melamine incorporation of 0 and 0.3%, respectively. Resin 3 is produced by a basic process and has 3% melamine. The
panels and characterization procedures were performed in our lab in the same conditions as the previous ones.
The formaldehyde content for resin 5.1 is significantly lower than for the other resins. Internal resistance is lower than for resin 1, but still acceptable
and similar to the values obtained for the other two
resins. The other properties are also very similar for
these four distinct resins.
Figure 3 shows the GPC/SEC chromatograms
obtained for fifth approach resins. In this type of distribution the peaks with larger retention volume
(retention volume between 20 and 26 mL) corresponds to free urea, methylolureas, methylolmelamines, and oligomers (molecular weight <3000)
and the peaks with lower retention volume (retention volume between 6 and 14 mL) correspond to
polymer with high molecular weight (molecular
weight >12,000). Considering the high molecular
weight fraction of the chromatograms (retention volume between 7 and 12 mL), it can be seen that
increasing pH leads to higher molecular weight
polymer, for resins 5.1, 5.2, and 5.3. Resin 5.4 is an
exception, since the synthesis process was modified
as discussed above: the methylolation/condensation
step could only be carried after the addition of the
second urea and increase of temperature. Since, the
F/U molar ratio is lower; the polymer condensation
does not progress as much as for the other three resins. This occurs because the free formaldehyde
reacts with the methylolureas and methylolmelamines, and also with this new urea.

In the lower molecular weight region (retention volume between 20 and 26 mL) it is noticeable that resin
5.3 shows a lower shoulder (21 to 23 mL), which may
be related to the higher degree of condensation,
obtained at the expense of oligomeric species.
The resin 5.4 present the lower reactivity (see
Table III), which is in agreement with the lower extension of the polymerization at the end of the reaction.
The gel time values for resins 5.1 and 5.2 are very
close and are essentially equivalent. Resin 5.3 shows
the highest reactivity, which is once again relatable to
the presence of higher molecular weight material.
CONCLUSIONS
Resins UF fortified with melamine have been developed for upgrading the performance of UF bonded
PBs with low formaldehyde emissions. A strongly
acid process was used for the resin synthesis. The
addition of melamine was tested in the two main
synthesis steps: acidic methylolation/condensation
and slightly basic methylolation. Results indicated
that the first step is the most appropriate for melamine addition. The effect of pH at this step was also
studied. Very low or high pH values are not beneficial. Low pH (lower than 3) results in a very unstable reaction, as the resin gains viscosity very quickly.
A high pH value (higher than 5) results in a very
slow condensation reaction.
The PBs produced with the several resins showed
that an increase in the pH of the first reaction step
results in lower values of IB strength. Regarding
formaldehyde content, all the resins in this study
showed very low formaldehyde emissions.
This work describes a new synthesis strategy for UF
resins fortified with melamine. Moreover, this process
yields resins with good mechanical performances in

TABLE V
Properties of Particleboards Produced with Different UF Resins
Resin

Density
(kg/m3)

Internal bond
strength (N/mm2)

Thickness
swelling (%)

Moisture
content (%)

Formaldehyde content
(mg/100 g oven dry board)

Resin 1
Resin 2
Resin 3
UF 5.1

641
675
656
637

0.52
0.39
0.49
0.44

25.7
32.0
24.7
28.9

6.3
6.2
5.8
5.4

5.3
3.4
4.6
2.7

Journal of Applied Polymer Science DOI 10.1002/app

PRODUCTION OF MELAMINE FORTIFIED UF RESINS

2317

Industria) and Sonae Industria PCDM for providing the

equipment and raw materials needed for this work.

References

Figure 3 Chromatograms of UF resins produced in fifth

synthesis attempt.

terms of IB strength and formaldehyde emissions. The

novelty of this approach lies on the melamine addition
during the acidic step, promoting its reaction with formaldehyde prior to the introduction of urea. This yields a
MUF copolymer with strong bonds, instead of only
urea-formaldehyde and MF polymers.
This work is cofounded by FEDER/QREN (E0_formaldehyde project with reference FCOMP010202FEDER005347) in
the framework of Programa Operacional Factor de Competitividade. The authors wish to thank Euroresinas (Sonae

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Journal of Applied Polymer Science DOI 10.1002/app