Journal of Polymers and the Environment, Vol. 14, No.

1, January 2006 (
2006)

DOI: 10.1007/s10924-005-8713-z

Effect of the Pretreatment with UV and Gamma Radiations

on the Modification of Plywood Surface by Photocuring
with Epoxy Acrylate

Mubarak A. Khan,1,3 Ruhul A. Khan,1 B. S. Aliya,1 and Z. Nasreen2

In order to further improve the physical properties of plywood surface that was pretreated
with UV and Gamma radiation at different radiation intensities before photocuring. After
pretreatment with radiation the plywood surface was coated with different prepared formu-
lations containing epoxyacrylate (EA-1020) as an oligomer, difunctional monomers such as
tripropylene glycol diacrylate (TPGDA), 2-hexadioldiacrylate (HDDA), Ethylene Glycol di-
methacrylate (EGDMA) and trifunctional monomer trimethyl propen triacrylate (TMPTA)
with photoinitiator Darocur 1664. Thin polymer films were prepared on glass plate with these
formulated solutions and cured under UV radiation. Pendulum hardness (PH) and gel content
of the film were studied for selecting the formulations as top coat and as base coat. The
polished plywood surface was coated with selected formulation and cured under UV radiation.
Various rheological properties of UV cured plywood surface such as pendulum hardness,
scratch hardness, microgloss, adhesion strength, percentage chipped off area and abrasion
resistance were studied.

KEY WORDS: Gamma radiation; photo-curing; plywood; surface coating; UV-radiation.

INTRODUCTION by photocuring process. Curing of surface coating

can be carried out by conventional thermal and
Plywood is composed of relatively thin layers
radiation process. Radiation process involves infra-
or plies. All plies affect the shape and permanent
red (IR), microwave, ultraviolet (UV) and electron
form of thin plywood panels. Plywood has been
beam (EB). Among these UV and EB are finding
treated for protection against fire or decay is avail-
applications in the field of coatings [1–3]. Radia-
able. Although it is technically feasible to treat
tion curing process become more important and
veneers with chemical solutions and then glue
useful because this process reduces or eliminates
them into plywood, a more general practice is to
the need of volatile solvent and the energy re-
treat the plywood after gluing, either with fire-
quired to cure, are substantially less than that
retardant or wood preservative solutions and then
required in conventional method [4]. Other major
to dry the panels. To make the adequate perfor-
advantages of radiation curing technique are – (i)
mance of plywood surface, it is necessary to treat
it generates little or no heat (ii) it is space saving
and one pack system. A UV curing coating con-
1
Radiation and Polymer Chemistry Laboratory, Institute of tains a mixture of liquid prepolymers, monomers,
Nuclear Science and Technology, Bangladesh Atomic Energy pigments and extenders, together with a photo
Commission, P.O. Box 3787, Dhaka, Bangladesh.
2
Department of Chemistry, DUET, Gazipur, 1700, Bangladesh.
active compound (photoinitiator). When UV light
3
To whom all correspondence shoulbe addressed. E-mail: penetrates the coating, the photoinitiator breaks
makhan@bangla.net down into free radicals. The free radicals are then
111
1566-2543/06/0100-0111/0
2006 Springer Science+Business Media, Inc.
112
able to initiate a rapid addition polymerization reac-
tion, with unsaturated groups which are present in
the oligomer and monomers [5]. High-energy ioniz-
ing radiation (c rays) produces ionization, resulting
in the formation of ions, electrons and free radicals.
Since ionization is a nonspecific reaction, the cellu-
lose molecules of wood have a certain probability of
involvement which depends on the radiation inten-
sity. In contrast, the absorption of UV light is rather
specific; molecules can be excited to a higher elec-
tron energy level and dissociated to form free radi-
cals. The radiation is absorbed selectively by
chromophoric system, which have excitation ener-
gies to the quantum energy of the wavelength of
light used; hence, the absorption is very dependent
on chemical structure, Consequently the particles of
high energy radiation can penetrate into wood easily
to a uniform bulk reaction, whereas UV irradiation
can only initiate a surface reaction. When wood is
subjected to Gamma radiation at doses of 50 Mrad,
no remarkable changes to the surfaces of the cell
walls is observed. However, for white oak at doses
of 650 Mrad, the tangential vessel diameter, ray cell
length, length and width of intervessel pits increase
on exposure, whereas tangential vessel wall thick-
ness, ray cell double wall thickness and late-wood fi-
ber double wall thickness decrease. As a result of
exposure to high energy radiation wood degradation
and chemical changes have been occurred. However,
owing to the complexity of chemical components in
wood, no clear picture of the process has yet ap-
peared. It is generally accepted that chemical bonds
in wood polymers (cellulose, hemicellulose and lig-
nin) are broken to produce an irreversible degrada-
tion. Free radicals are generated in the interim.
However, dosages of about 10 Mrad are required to
produce appreciable chemical breakdown of wood.
After irradiation the cellulose component becomes
vulnerable to attack by bovine rumen bacteria. The
lignin component is less affected by radiation and
may serve to protect the cellulose to some extent.
From the effect of Gamma radiation dosages on
wood components, the increase in extractives con-
tent with reduced holocellulose content indicates
that the decreases in cell wall thickness is related to
cellulose degradation. The lignin content remains
relatively unchanged. Chemical changes are also ob-
served for wood irradiation with UV light. Unlike
high-energy radiation, however, UV light seems to
interact strongly with lignin and make it water solu-
ble whereas cellulose is less affected [6]. It is known
that wood is the best construction materials for civil
Khan, Khan, Aliya, and Nasreen
works, industries, household articles and inner
panels etc. Wood is, therefore, being demolished as
an increase of population... People are therefore,
using low grade wood as substitute. The present
work is, therefore, undertaken to develop the physi-
cal properties such as hardness, gloss etc. of ply-
wood surface by curing with UV radiation. The
effect of pretreatment by UV and gamma radiation
on the physical properties of plywood sample was
also monitored.
EXPERIMENTAL
Materials
The oligomer EA-1020, a diacrylated epoxy oli-
gomer, was procured from Radcure (Drogenbos,
Belgium). A trifunction monomer, trimethylol
propane triacrylate (TMPTA) and difunctional
monomers tripropylene glycol diacrylate (TPGDA),
2-hexyl diol diacylate (HDDA), ethylene glycol
dimethacrylate (EGDMA) were obtained from
Merck (Germany). Darocur-1664 was procured
from Ciba-Geigy used as photoinitiator to initiate
photochemical reaction during UV radiation pro-
cess. Filler (sand) SiO2 and plywood samples were
collected from local market.
Methods
Different formulation were developed with
epoxy acrylate EA-1020 in combination with reac-
tive monomers TPGDA, HDDA, EGDMA and
TMPTA in the presence of filler and photoinitiator
Darocur-1664 in the proportions as mentioned in
Table I. To prepare thin polymer films these formu-
lated solutions were used on glass plates with the
help of a bar coater (No. 0.018 and 0.028 of abbey
chemical Co., Australia). The thickness of the poly-
mer films were 36 ± 3 lm on the glass plate. The
thickness of the films was measured by digital
micrometer (Mitutoyo, Japan). To cure the polymer
films on the plate as well as on the plywood sur-
face, a UV minicure machine (IST Technik, Ger-
many, Model Me-200-UV) was used by using UV
lamp (254–313 nm, 2 kW). The coated substrate
was run under the UV lamp at a speed of 4 m/min
with the help of a conveyor belt interlocked with
the machine. Film hardness of the UV cured film
was measured while the film was still on the sub-
strate after 24 h pendulum hardness (PH) tester
(model 5458, BYKE labotron, Germany). PH of the
Effect of the Pretreatment with UV and Gamma Radiations 113

Table I. Composition of Different Formulations (% w/w)

Chemicals S1 S2 S3 S4 S5 S6 S7 S8

EA-1020 50 50 50 50 50 50 50 50
EGDMA 48 – – – 47 – – –
TPGDA – 48 – – – 47 – –
TMPTA – – – 48 – – 47 –
HDDA – – – 48 – – – 47
Darocur-1664 2 2 2 2 2 2 2 2
SiO2 – – – – 1 1 1 1

cured plywood surface was also determined by
extracting a known weight of the cured film with
hot benzene for 48 h in a soxhlet. The film was
wrapped in a stainless steel net that was put into
the soxhlet and extracted with the solvent. The loss
of weight of the cured film due to extraction yields
the gel content. It was calculated using the formula,
[% gel=100)100(Wo)We)/Wo] Where Wo is the
weight of the cured film before extraction and We is
weight of extracted film after drying at 105 C until
a constant weight was achieved.
Application on the Plywood Surface
The plywood sample was cut into small pieces
(size 4¢¢ 4¢¢ 1/6¢¢) and dried in an oven at 105C
to remove the free moisture from plywood until con-
stant weight. The surface of the plywood samples
were polished smoothly with the help of suitable
sand paper (No. 0 and 1). Then it was treated under
UV (5, 10 and 15 pass) and Gamma (50, 100 and
500 krad) radiation at different intensities. After
treatment the plywood samples were coated with
base coat formulation using a drawn down bar (No.
0.028) and cured by a single pass under the UV
lamp. It was polished again and coated with a top
coat using the bar (No. 0.018) and finally the coating
was cured under UV radiation at different intensities
as mentioned earlier. Marco scratch hardness
(MSH) was measured by a Universal Hardness Tes-
ter (Model 413/E, Erichen, Germany); Adhesin
strength of the curded film on plywood surface was
determined by an adhesion tester (Model 525,
ASTM, D4541, Erikson Co., Germany). Surface
gloss of the UV cured film on the plywood surface
was measured at 60 and 20 angles using a micro-
gloss meter (Model Sheen 155, Germany).
Abrasion wear of the coated plywood surface
was measured by a tabor abrader (Model 5130,
Richness Co., and Germany). The lower tabor
index indicates better resistance to abrasion by the
cured film on plywood surface. The adhesion ability
of the UV cured film was determined by measuring
the force that was applied to peel a certain portion
of the cured film with the help of an adhesion tester
(Model 525, Erikson Co., Germany).
RESULTS AND DISCUSSION
It is necessary to characterize UV cured poly-
mer films before applying to the surface of plywood.
Most of the data presented in this report are average
of at least six different values.
Characterization of Polymer Films
Film Hardness
Hardness of UV cured polymer film was deter-
mined by the pendulum method, using a digital pen-
dulum hardness tester, whenever the films were still
on glass plate after 24 h of radiation. Results of pen-
dulum hardness (PH) of the UV cured films repre-
sented by the number of passes are graphically shown
in Fig. 1. It is found that the hardness of the UV
cured polymer films prepared with different formula-
tions increase with radiation dose intensity. The cur-
ing process continued with UV radiation up to a
certain UV dose at which it gains the maximum hard-
ness which were found at the 8th pass, while others at
the 10th pass. After attaining the maximum surface
hardness the pendulum hardness values are found to
be decreased. This means that degradation of poly-
mer films attain at higher radiation doses [7]. The
highest PH value (96%) was showed at the 10th pass
from the formulation S3 containing TMPTA without
filler. The second highest PH value (86%) was given
by the formulation S5 containing EGDMA with 1%
sand. TMPTA (S3) is a trifunctional monomer
containing three acrylated reactive sides to help the
quick polymerization and three trifunctional
114
Fig. 1. Pendulum hardness of UV-cured polymer of different
formulations against number of passes.
networks are accomplished [8]. Formulation S2
(TPGDA) showed the moderate PH value compared
to formulation S3 due to glycol moiety in TPGDA.
Once more S2 showed the higher PH values than that
of HDDA (S4) and EGDMA (S1). When the filler
sand was mixed with the formulation S1, S2, S3 and
S4, the PH of the new formulated solutions S5–S8
were observed to decrease than that of original one.
Filler sand may act as a free radical scavenger due to
its inherent chemical nature.
Gel Content
The gel content represents the crossliking den-
sity through the entire polymer films. Figure 2
showed the gel content of polymer films against the
number of passes. The maximum gel content value
(98%) was given by formulation S3 containing
TMPTA and it is known that TMPTA has trifunc-
tional acrylated groups that have a branching effect
[9] and can yield more crosslinking in the cured film.
The second highest gel content was obtained by the
formulation S2 (95%) followed by from the formula-
tions S4–S8. The maximum gel content varies
between 98% and 91% indicates very good crosslink-
ing phenomena among the various constituents pres-
ent in different formulations. The gel content values
of the films were found to be gradually decreased
whenever the filler was used in the formulations.
Khan, Khan, Aliya, and Nasreen
Fig. 2. Gel content (%) of UV-cured polymer of different
formulations against number of passes.
However, the gel content values which are all still
quite high, indicate high crosslinking ability under
UV radiation (see Table II).
Application on the Plywood Surface
Among all the formulations only formulation
S7 as a base coat and formulation S3 as a top coat,
were selected to apply on the radiation treated ply-
wood surface due to their best performance of pen-
dulum hardness and get content values on glass
plate. The base coat formulation S7 was applied on
polished and radiation treated plywood surface,
then the substrates were polished with the help of
a suitable sand paper (No. 0 and 1) and cured un-
der UV radiation at a single pass. After polishing
the substrates were again coated with the top coat
formulation S3 and finally cured under UV radia-
tion at different intensities. Various physical
parameters such as macro scratch hardness, pendu-
lum hardness, microgloss, adhesion strength, per-
cent chipped off area, abrasion resistance were
determined. In the Fig. 4, 10 J denotes without any
pretreatment of the plywood sample, on the other
hand K, L and M denote pretreatment with 5, 10,
and 15 passes of UV radiation intensities, and N,
O and P represent the pretreatment of gamma
radiation intensities of 50, 100, and 500 krad,
respectively.
Effect of the Pretreatment with UV and Gamma Radiations 115

Table II. Physical Properties of UV-Cured Films

Formulations

Properties No. of pass S1 S2 S3 S4 S5 S6 S7 S8

Pendulum hardness (%) 4 78.02 81.44 85.44 68.97 25.55 78.77 81.67 52.94
6 81.24 82.58 89.80 75.91 29.81 81.64 83.53 56.57
8 83.65 87.48 92.43 77.95 26.94 84.56 84.24 72.88
10 81.58 86.83 96.45 81.22 23.96 85.21 84.88 75.91
12 80.35 84.08 88.43 84.08 20.61 86.05 87.42 80.02
14 76.02 81.22 77.41 78.11 16.50 80.70 80.66 71.81
Gel content (%) 4 73.39 67.92 89.32 68.88 73.43 84.10 86.31 75.86
6 75.86 75.86 91.52 70.96 78.38 89.32 90.51 83.89
8 79.48 92.04 94.93 79.98 80.52 94.93 92.09 86.44
10 81.62 95.28 97.69 93.39 85.61 88.42 95.83 88.09
12 85.36 81.25 93.39 94.93 83.21 78.94 90.66 90.66
14 80.96 74.46 91.52 83.89 81.43 75.59 82.90 85.36

Pendulum Hardness treated with gamma radiation the PH values

Pendulum hardness (PH) of the UV cured ply-
wood surface was measured by pendulum technique.
The results of PH against the number of passes of
different pretreated plywood substrates were shown
in Fig. 3. The sample pretreated with 15 passes of
UV radiation showed the highest PH value (82%).
As the intensities of UV radiation increase, the PH
values also increase due to better impregnation of
the plywood surfaces. This reflects that there is an
increase of crosslinking with the increase of UV
dose. Alternatively when plywood samples are pre-
Fig. 3. Pendulum hardness of UV-cured pretreated plywood
surfaces against number of passes.
decrease significantly. The lowest PH values were
found for the plywood samples pretreated with
500 krad gamma radiation intensities before curing
under UV radiation. This indicates that high energy
radiation causes depolymerization and decomposi-
tion of cellulose structures in plywood [10]. Gamma
radiation also causes the plywood into crumble [11].
Similar result was also found for cotton cellulose
when treated with gamma radiation [12].
Adhesion Strength
Adhesion is the test where a certain force is
applied to pull out the coating from the surface of a
substrate such as plywood, partex etc. It is a pulling
out mechanism; if a coating is loosely bound with
the substrate surface then it can be easily peeled off
by applying a small peeling force and vice-versa.
Adhesion strength of the UV cured pretreated ply-
wood surface was measured through the cross cut
method and by the pulling out mechanism. The re-
sults of adhesion strength are shown in Fig. 4
against the number of passes of different pretreated
plywood surfaces. The highest adhesion value
(1.5 N/mm2) was observed from the sample pre-
treated with UV radiation at 15 passes before cur-
ing and there are a few chipped off area during
crosscut technique among all the pretreated sam-
ples. The lowest adhesion value was obtained from
the sample pretreated with gamma radiation at
500 krad. More strength is required if the adhesion
is stronger. Thus, it is found that plywood sample
pretreated with UV radiation at 15 passes showed
the best adhesion among the pretreated plywood
116 Khan, Khan, Aliya, and Nasreen

Fig. 4. Adhesion strength of UV-cured pretreated plywood sur-

face against different intensities treated plywood samples before Fig. 5. Highest values of macro scratch hardness of UV-cured
curing. polymer films on the plywood surface against pretreated plywood
surfaces at different intensities.

surfaces before curing. Increase the doses of UV

radiation on plywood surface, the adhesion increase increases, the value of MSH increases. But the ply-
which indicates the increase of crosslinking of cellu- wood pretreated with 500 krad, demonstrate the
lose with monomer due to better impregnation and lowest MSH value.
lower humidity and moisture [13]. In contrast when
plywood samples are pretreated with gamma radia-
tion the adhesion values decrease. This indicates
that high energy radiation causes profound changes
in cellulose of plywood [13, 14]. The loss of intrinsic
viscosity at higher doses of gamma radiation [15]
may cause low adhesion values.

Surface Hardness
Macro scratch hardness (MSH) of the coating
was measured in terms of load (weight) in grams
required to manifest a scratch or the surface of coat-
ings. More weight is needed if the resistance is high-
er due to its better physical properties. Thus, the
more the index of macro scratch hardness the better
the coating. The results of MSH are plotted in Fig. 5
against the pretreated condition. The highest value
was given by the sample pretreated with UV radia-
tion at 15th pass and the lowest value coated with
same the formulation which was pretreated with
500 krad gamma radiations. As the gamma radia- Fig. 6. Effect of pretreatment (with both UV and c radiation) on
tion intensities of the pretreated plywood surface gloss at 20 of UV-cured plywood surfaces.
Effect of the Pretreatment with UV and Gamma Radiations 117

Fig. 8. Minimum taber wear index of UV-cured pretreatment

Fig. 7. Effect of pretreatment (with both UV c radiation) non plywood surface against different intensities treated plywood
gloss at 60 of UV-cured plywood surfaces. samples before curing.

gradually increases. The substrate pretreated with

Surface Gloss UV radiation at 15 passes before curing under UV
Gloss is an important property of UV cured radiation showed the minimum taber index and the
polymer films on plywood surface. Generally it is maximum taber index were observed from the
measured at two angles (60 and 20) of the plane substrate pretreated with gamma radiation at
modified surface. Results of surface gloss are 500 krad. This means that the coating using 15th
shown in Figs. 6 and 7, respectively for 60 and pass pretreatment of the plywood sample has the
20 angles. The highest gloss at 60 angle (125%) highest resistance pertained by 100 cycles in the
was observed for the sample pretreated with gam-
ma radiation at 50 krad before curing under UV
radiation. Gloss is related to the extent of curing.
The lowest gloss value at 60 and at 20 angles
was observed for the sample pretreated with 5th
pass of UV radiation before curing under UV
radiation.

Abrasion Resistance
The coated plywood surface was abraded
between two abradents revolving wheels applying a
load of 100 g/cycle. The weight loss obtained by the
sample due to such abrasion between the wheels in
100 cycles is related to the taber wear index. This
means that the abrasion resistance is high when the
taber wear index is low. The best results of taber
wear index (lowest values) are shown in Fig. 8
against the formulations. It is observed that abra-
sion resistance increases as the intensities of UV at
15 passes on the pretreated plywood surface
increases. But for higher intensities of both UV and Fig. 9. Comparative study of different properties of UV-cured
gamma radiation cured polymer films on the pretreated plywood surface against different intensities treated
plywood surfaces, the values of the taber index plywood samples before curing.
118
involving wheels compared to other pretreated
plywood surface.
CONCLUSION
After pretreatment with UV and gamma radia-
tion at different intensities, the physical properties
of the plywood samples changed significantly. When
the pretreatment was done by the UV radiation,
pendulum hardness, adhesion strength, surface
hardness and percent gloss values were increased as
the radiation intensities increased. But the values of
the physical properties decreased with the increase
of the high energy gamma radiation intensity
increased. The abrasion resistance showed lower
values as the increase of UV radiation intensity, on
the other hand higher values were found with the
increase of gamma radiation intensity. Different
types of physical properties of UV cured polymer
coatings on the pretreatment plywood surfaces
obtained by using the same formulation (base coat,
S7+top coat, S3) are shown in Fig. 9 where a com-
parison is clearly demonstrated. Considering all the
properties of the pretreated plywood samples, it was
found that the quality of plywood was better when
pretreated with UV radiation than the other
untreated or gamma treated plywood samples. With
the increase of intensity of UV radiation the physi-
cal properties of the plywood samples were also
enhanced. Plywood samples pretreated with 15th
pass of UV radiation showed the best performance
than the other pretreated substrates. This is a
unique achievement in the sense that all of the
Khan, Khan, Aliya, and Nasreen
physical properties were improved by the polymer
coating on the plywood surface with specially
formulated solutions and the curing under UV radi-
ation. The same improved materials can sustain
improved properties in normal conditions and the
loss of these properties was also minimal when these
were exposed in accelerated weathering testing.
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