~

Pergamon

Radiat. Phys. Chem. Vol. 45, No. 4, pp. 623-627, 1995

Copyright 1995ElsevierScienceLtd
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W O O D PLASTIC COMPOSITE AT D I F F E R E N T U R E A
CONCENTRATIONS
M. M. H U S A I N , l M U B A R A K A. K H A N , 2 K. M. IDRISS ALI2t
and A. J. M. M O Y N U L H A S A N I
~Bangladesh Council and Scientificand Industrial Research, Dhaka and 2Radiation Chemistry Laboratory,
Institute of Nuclear Science and Technology, Bangladesh Atomic Energy Commission, P.O. Box 3787,
Dhaka, Bangladesh

(Received 25 April 1994)

Abstract--Wood plastic composite (WPC) has been prepared with a low grade wood simul (Salmalia
malabarica) of Bangladesh under Co-60 gamma irradiation using MMA as the bulk monomer combined
with methanol as the swelling solvent at different urea concentrations. Effect of a second solute such as
NVP, TPGDA and TMPTA in the impregnating solution is evaluated. NVP appears to be the best
co-additive/second solute among all the additives used to yield the composite with the highest polymer
loading (PL) and tensile strength (TS) at 0.5% urea concentration.

INTRODUCTION
Wood Plastic Composite (WPC) can be suitably
prepared with low grade wood using a bulk monomer
under the radiation of a Co-60 gamma source. Low
density wood yields a better composite (Khan and
Ali, 1992a). Among various bulk monomers so far
used to prepare the composites, styrene (ST), methylmethacrylate (MMA), butylmethacrylate (BMA),
and acrylamide (AM) are important (Khan and Ali,
1993; Khan et al., 1992b). Incorporation of small
amounts (1%) of additives selected from functional
monomers, acid, inorganic salts and urea into the
monomer enhances the polymer loading significantly
for the composites with increased tensile strength in
most cases (Khan and Ali, 1992c). Acid decreases
the tensile property as it breaks the backbone chain
of the cellulose during composite formation. Li ions
retain the tensile property with enhanced polymer
loading while Cu 2 ions form some sort of organometallic complexes with the bulk monomer occupying
the void spaces in the wood cellulose providing a
slight increase of the tensile strength to the composite.
Most important is that Cu 2+ ions render protective
and preservative properties to the composite against
attack by insects and microbes. Carboamide
( ~ N - - - C O - - ) present in any bulk monomer or additive provides very significant enhancement of tensile
strength with substantial increase of the polymer
loading to the composite. A number of compounds
containing a carboamide ( ~ N - - C O - - ) group has
been used for the preparation of WPC (Ali et al.,
1994). Urea is the cheapest among these; similarly
tAuthor to whom all correspondence should be addressed.

among all the bulk monomers, styrene (ST) and

methylmethacrylate (MMA) are also cheap. In the
present investigation the bulk monomer M M A and
the co-additive urea are used as a model case. The
effect of functional monomers such as N-vinylpyrrolidone, NVP (monofunctional), tripropylene glycol
diacrylate, T P G D A (difunctional) and trimethylol
propane triacrylate is also studied in this system.

EXPERIMENTAL
Simul (Salmalia malabarica) wood sample (6 1
x 0.5 cm) was selected from long, flat-grained planks
and was uniformly polished with suitable sandpapers.
Free water was removed from the samples by heating
them at 60C and 50 mm Hg for 24 h. Bulk monomers methylmethacrylate (MMA), butylmethacrylate
(BMA), styrene (ST) and acrylamide (AM) were
used as received from the supplier E. Merck without
removing the inhibitor. Urea, N-vinyl pyrrolidone
(NVP), tripropylene glycol diacrylate (TPGDA)
and trimethylol propane triacrylate (TMPTA) were
procured from Aldrich Chemical Co. and were also
used as additives without any further purification.
Impregnating solution was formulated with a bulk
monomer at different compositions with the swelling
solvent methanol. A minute amount (1%) of additive
was incorporated into the impregnating solution.
Dried wood samples were soaked into the impregnating solutions for 16 h under normal conditions. They
were then taken out of the solutions, wiped with tissue
paper to remove the excess solution, encapsulated
into polyethylene bags and were finally irradiated
with Co-60 gamma source at 3 Mrad (dose rate is
800 krad/h). The irradiated samples were heated at
623

624

M. M. Husain et al.
Table 1. Effect of urea on polymer loading of simul with different monomers
MMA
in
MeOH
(v/v)
10
30
50
70
90
Tr=

%PL
AM
B
10
51
68
102
74
1.51

BMA
U
12
67
82
143
81
1.56

ST

7
34
50
63
96
1.10

11
48
73
92
138
1.36

MMA

5
20
27
35
41
1.07

6
25
35
47
51
1.12

13
30
38
41
44
1.12

20
40
46
48
52
1.27

Tr = TSwpJTSwood; B = blank, U = urea.

60C and 50 mm Hg to remove the unreacted (unused) impregnating solution. Polymer loading (PL),
index of composite formation was determined from
the weight increase of the wood sample after the
whole treatment. Tensile strengths (TS) of the treated
and untreated samples were directly measured using
INSTRON (model 1011, UK). The change in tensile
strength due to this treatment was determined by
tensile strength factor Tr following the equation,
Z f = TSwp~/TSwood.
RESULTS AND D I S C U S S I O N

Among the various additives (Khan and Ali, 1992c;

1992d) used for the improvement of wood plastic
composite (WPC) of simul, a Bangladesh low grade
wood, the additive containing a carboamide group
(~N---CO---) has been found (Ali et aL, 1994) to
yield WPC with superior property of tensile strength,
polymer loading, water absorption resistivity, resistance to attacks by insects, microbes and chemical
corrosion. Urea (U) contains such a group and is a
very cheap material. A number of bulk monomers
such as MMA, BMA, AM and ST has been used to
prepare WPC of simul with urea as additive by 1%
(w/w). Table I represents the polymer loading (PL) of
these bulk monomers in the presence or absence of
urea. The highest PL (102%) is obtained with AM
which also contains a - - N - - C O - - group. The order
of PL values achieved by these bulk monomers is
AM > BMA > MMA > ST. The introduction of
urea (1%) into these monomers has further enhanced
the PL values, the order of PL values remaining the
same. It is already explained that the lone pair of
electrons of nitrogen (N) attached to carbonyl group
(--CO---) helps create congenial and favourable conditions for diffusion of the molecule into the backbone chain of the cellulose during the equilibrium
phenomena needed for overall polymerization process of the wood plastic composite formation. The
Table 2. Effect of additives on polymer loading of simul + M M A
M M A in
MeOH
(v/v)

Blank

NVP

%PL
TPGDA

TMPTA

Urea

10
30
50
70
90

13
30
38
41
58

14
40
42
47
58

22
40
50
60
48

45
55
70
65
43

20
40
46
48
52

lowest PL values of the styrene series is attributed to

the steric hindrance rendered by the benzene ring
which remains outside the plane of the molecule. The
augmentation of AM with cellulose is also high and
this is reflected by the highest tensile strength factor
of the WPC prepared in the presence of AM as well
as of AM + U. Among these bulk monomers both
MMA and styrene are very cheap, but MMA has
advantage over ST because MMA has plain molecule
and needs less radiation dose than ST. So MMA is
taken as a model bulk monomer in order to optimize
the concentration of urea for the preparation of WPC
in the presence of other additives which are normally
selected from functional monomers for the improvement of the composite.
Table 2 shows the comparative PL values of
MMA with simul in the presence of additives NVP,
TPGDA, TMPTA and urea. TMPTA imparts the
highest PL values among these additives. This is
because TMPTA has trifunctional acrylated groups
with branching effect to reach cellulose backbone in
three different directions. The highest PL value is at
50% MMA. This enables the reduction of the cost for
the bulk monomer. Similarly TPGDA is a difunctional
monomer and has two effective sites at two acrylated
groups for combination with cellulose backbone
and as such yields the second highest PL value. Both
urea and NVP have - - N - - C O - - group and thus
have comparable PL values. The highest PL values
obtained by urea and NVP are at 90% MMA and
that with TPGDA is at 70% MMA. The presence of
polyfunctional monomers in the system creates hardness and brittleness in the polymeric film (Hossain
et al., 1994) and the same may occur with WPC also.
However, when urea is used at different concentrations (0.05-10% w/w) in the MMA + MeOH systems,
it is observed (Fig. 1) that the PL values increase quite
sharply at the initial urea concentrations (up to 1%).
The highest PL is obtained at 70% MMA with
2% urea. Urea is not soluble in MMA but it is in
methanol. As the MMA concentration increases,
MeOH proportions decrease and thus it becomes
difficult to prepare the impregnating solution with
higher urea concentrations. Therefore, the maximum
amount of urea which can be dissolved in 90% MMA
solution (10% MeOH) is 1%, and 6% urea can be
dissolved in 50% MMA solution. The maximum PL
values attained by l0 and 30% MMA solutions are
achieved between urea concentrations of 4 and 5%,

W o o d plastic composite at different urea concentrations

625

90

60

80

50
70

~tj

10%

+ 30%
50%
70%
x 90%

60

40

50

"+

r~
30

,.~ 40
o

"6
u

./~
/"

20

10

~ 50%
a70%
><90%

20

l0

10

10

Urea concentration (%)

Urea concentration (%)

Fig. 1. Polymer loading against urea concentration with

respect to M M A concentration in MeOH.

Fig. 2. Polymer loading against urea concentration with

respect to M M A concentration in MeOH in presence of
NVP 0 % ) .

80

70

60

~0
o~,,~

50

40
O

30

20

70%

90%
10

10

U r e a c o n c e n t r a t i o n (%)
Fig. 3. Polymer loading against urea concentration with respect to M M A concentration in M e O H in
presence o f T P G D A (1%).

626

M . M . Husain

et al.

100
90
~.

80

70

~.O

60

!~~"

i A.

50
x
40

I
0

Urea

90%
I

10

concentration (%)

Fig. 4. Polymer loading against urea concentration with respect to MMA concentration in MeOH in
presence of TMPTA (1%).
after which PL values remain steady, indicating a
sort of equilibrium conditions reached among urea,
M e O H , M M A at the time of the polymerization
process within the void space of the cellulose and the
cellulose backbone chain.
When N V P is used as a second solute (1%) in
the impregnating solution, the overall PL values are
enhanced at all concentrations of M M A . The highest
PL value ( ~ 8 0 % ) is attained with 90% M M A at
1% urea. The decrease of PL values after attaining

the maximum at 1% urea with 90 and 70% M M A

and at 4 % urea with 50% M M A solutions can be
attributed to the involvement of N V P with urea at
higher urea concentrations. When the second solute
(NVP) is replaced with T P G D A (Fig. 3) or T M P T A
(Fig. 4), it is observed that the highest PL is obtained
with 70% M M A at 1% urea in the presence of
T P G D A (1%) while the 50% M M A yields the
highest PL with T M P T A (1%). A s explained earlier,
the branching effect of trifunctional acrylated group

Table 3. Effect of urea on tensile strength of WPC of the highest PL

Blank

NVP

TPGDA

TMPTA

Urea
(%)

PL

Tr

PL

Tr

PL

Tr

PL

Tr

0
0.05
0.10
0.25
0.50
1.00
2.00
4.00
6.00
10.00

42
44
44
46
48
52
56
52
55
35

1.12
1.18
1.23
1.25
1.28
1.27
1.40
1.29
1.40
1.20

58
59
60
65
74
72
65
65
60
50

1.50
1.55
1.59
1.61
1.68
1.65
1.60
1.63
1.56
1.53

60
51
62
63
67
68
70
65
67
56

1.27
1.29
1.30
1.32
1.38
1.39
1.47
1.42
1.40
1.34

70
70
74
76
83
87
88
90
86
70

1.34
1.35
1.35
1.36
1.37
1.38
1.42
1.47
1.40
1.38

Tf = Tswp~/TSwood

Wood plastic composite at different urea concentrations

of T M P T A and difunctionality of T P G D A causes
favourable conditions for polymerization process
with the cellulose backbone chain. The decrease of PL
in the presence of high urea concentration and high
methanol proportions (low MMA) can be attributed
to the different rates of reactions among urea,
MeOH, M M A and the second solutes. The PL values
attained by T M P T A is the highest, followed by NVP
system. Though T P G D A is a difunctional monomer
additive, NVP is a unique monomer containing
~---N--CO--- group which helps polymerization
process providing high tensile strength for the WPC.
Table 3 shows the Tf values against the highest PL
values obtained at different urea concentrations in the
presence of NVP, T P G D A or TMPTA. It is observed
that the highest PL values obtained at different urea
concentrations increase as the urea concentration
increases up to 2% urea and all these PL values are
achieved at 90% M M A up to 1% urea and the 70%
M M A yields the maximum PL values (56%) along
with the highest Tf values at 2% urea and beyond this
concentration (2% urea), ,the PL values decrease. It
is also observed that the tensile strengths of the
composites obtained with 70% M M A at 2% urea and
with 50% M M A at 6% urea are similar (Tf = 1.4).
This can be explained by the fact that the urea
concentrations are saturated at both these M M A
concentrations (70 and 50%) in the impregnating
solutions and the PL values are also very similar. The
40% increase in TS values is mainly attributed to the
contribution of urea in the impregnating solution.
Addition of minute amount (1% w/w) of NVP to
the M M A + MeOH + urea solution increases the PL
values further with the highest PL values attained
with 70% M M A at 0.5% urea. The highest TS value
(Tr = 1.68) is also obtained at this PL value (74%).
As the urea concentration increases beyond 0.5%,
the change in PL and Tf values are slightly decreasing.
The 28% further increase in TS values of the composite is solely attributed to the contribution of NVP
added to the urea + MeOH + M M A system. NVP is
a monofunctional monomer. It is known that polyfunctional monomers enhance the tensile properties
of the polymeric films with reduction of elongation
(Ali and Sasaki, 1994). Thus, T P G D A (a difunctional
monomer) and T M P T A (a trifunctional monomer)

627

were added to the urea + MeOH + M M A system at

different urea concentrations. It is observed that the
highest PL and T S values are obtained with 70%
M M A at 2% urea for T P G D A and with 50% M M A
at 4% urea for TMPTA. Both the multifunctional
monomers (TPGDA and TMPTA) have enhanced
the PL values significantly compared to urea + M M A
+ MeOH system. However, the increase of TS values
is slightly enhanced by the presence of T P G D A
an d TMPTA. It shows here that the presence of NVP
is much more effective in bringing both PL and TS
values higher than the corresponding Values achieved
with the multifunctional monomers (TPGDA and
T M P T A ) . It can be concluded here that the best
composite (WPC) can be prepared with simul +
M M A system at 0.5% urea and 70% M M A in the
presence of 30% swelling solvent methanol and 1%
NVP. The TS of the composite can be enhanced
further by using AM in place of M M A as the bulk
monomer (Khan and Ali, 1993). In: this case bulk
monomer AM, additive urea and NVP all contain the
--N---C------O group which increases the augmentation
process; but the cost of AM is very high compared to
MMA. Thus, M M A can be recommended for the
composite preparation.
Acknowledgement--The authors acknowledge the members
of the GammaTech LTD Chittagong for irradiating the
samples by 6Co facilities.

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(1994) Polym.-Plast. TechnoL Eng. 33, 1.167.
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Khan M. A. and Ali K. M. I. (1993) J. Appl. Polym. Sci.
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Khan M. A. and Ali K. M. I. (1992c) Radiat. Phys. Chem.
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