ARTICLE IN PRESS

International Journal of Adhesion & Adhesives 25 (2005) 371–378

www.elsevier.com/locate/ijadhadh

Synthesis and characterization of a new adhesion-activator for

polymer surface
Dong Ri Zhanga, Sun Wha Ohb, Yong Pyo Hongc, Young Soo Kanga,
a
Department of Chemistry, Pukyong National University, 599-1 Daeyon 3-dong, Nam-gu, Busan 608-737, Korea
b
Basic Science Research Institute, Pukyong National University, Busan 608-737, Korea
c
Department of Applied Chemistry, Andong National University, Andong, Kyongbuk 760-749, Korea
Accepted 10 July 2004
Available online 17 February 2005

Abstract

We developed a new type of adhesion-activator, Lichlor-6, consisting of lithium chlorohexylisocyanurate (LCI) and lithium
dichloroisocyanurate (LDI), which can be soluble in water very well (more than 30 g/water 100 g), to replace trichloroisocyanuric
acid (TCIA) which is only soluble in organic solvent. LDI acts as an adhesion-activator and LCI is used as additive to improve
wetting ability of LDI on the polymer surface. The surfaces of styrene-butadiene rubber (SBR) and ethylene vinyl acetate (EVA)
were treated with Lichlor-6 solution and bonded together using water-soluble polyurethane adhesive. Contact angle measurements,
attenuated total reflectance-FTIR spectroscopy and scanning electron microscopy were carried out to characterize the treated
surfaces. Tear resistance was also tested to compare adhesion strengths. After treatment with 16 wt% solution of Lichlor-6, the
water contact angles decreased from 891 and 881 to 341 and 361 for SBR and EVA, respectively. The treatment with the higher
concentration of Lichlor-6 produced the more marked chemical and morphology modifications on the SBR and EVA surfaces. The
increased surface roughness of SBR and EVA caused by the treatment with Lichlor-6 have larger effects on the decrease of the
contact angle than chemical modification. Tear resistance values obtained are 4.9, 6.5, 8.4 and 10.2 kgf/2 cm for the treatment with 0,
2, 5 and 8 wt% solutions of Lichlor-6, respectively, and the tested tear resistance is almost inversely proportional to the larger one
between the two contact angles of SBR and EVA surfaces.
r 2004 Elsevier Ltd. All rights reserved.

Keywords: Adhesion-activator; Trichloroisocyanuric acid; Styrene-butadiene rubber; Ethylene vinyl acetate

1. Introduction Chlorination with TCIA is a common surface

So far trichloroisocyanuric acid (TCIA) has been used
as an adhesion-activator to treat polymer surface for
enhancing the adhesion between polymers. TCIA has to
be used by dissolving in organic solvent and it produces
chlorine due to unstableness in ambient condition.
Unfortunately, TCIA is only soluble in organic solvents
such as acetone and chloroform which are harmful. So
these problems require a new type of adhesion-activator
to get an improved environmental condition.
Corresponding author. Tel.: +82 51 620 6379;
fax: +82 51 628 8147.
E-mail address: yskang@pknu.ac.kr (Y.S. Kang).
treatment to improve the adhesion of synthetic vulca-
nized styrene-butadiene rubber (SBR) to polyurethane
(PU) and epoxy adhesives [1,2]. TCIA has been used as
an adhesion-activator to chlorinate the polymer surfaces
to improve the adhesion between them and the surface
treatment of SBR with TCIA has been widely studied in
different conditions. Romero-Sanchez et al. [1] used
ethyl, propyl and butyl acetates as solvents for TCIA to
chlorinate SBR and found that the solvent is a key
factor in the effectiveness of the chlorination of SBR
containing zinc stearate and paraffin wax. They clarified
that the solvents with slower evaporation rate led to
more pronounced modifications on the SBR and the
increase in TCIA percentage in the chlorinating solution

0143-7496/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijadhadh.2004.07.008
 ARTICLE IN PRESS
372 D. Ri Zhang et al. / International Journal of Adhesion & Adhesives 25 (2005) 371–378

produced more marked modifications on the SBR
surface. It has been considered that the surface
treatment of SBR with TCIA produces chemical
structure change and surface morphology modifications
that enhance the adhesion between SBR and EVA
or PU [3–9].
One of the most applications of adhesive has been
done in the footwear industry. The bottom of a footwear
usually consists of two layers that are bonded together
using adhesive. One layer is made of SBR and the other
layer is made of EVA or PU. In order to improve the
adhesion between the two layers a kind of adhesion-
activator is usually applied to treat the surfaces of the
layers. However, it must be noticed that TCIA is only
soluble in organic solvents and the organic solvents may
cause considerable hazards to health by absorbing
harmful vapors. In order to avoid using harmful organic
solvent, we synthesized a new type of adhesive-activator,
Lichlor-6 (chlorine releasing agent), consisting of
lithium chlorohexylisocyanurate (LCI) and lithium
dichloroisocyanurate (LDI), which can be soluble in
water very well. LDI acts as an adhesion-activator and
LCI is used as an additive to improve wetting property
of LDI on the polymer surface.
2. Experimental
60 1C. After cooling to room temperature the reaction
solution was evaporated in vacuo to give the white solid
4 in a quantitative yield.
2.1.3. Preparation of mixture solution of Lichlor-6
(chlorine releasing agent) Consisting of Lithium Chloro-
hexylisocyanurate 6 and Lithium Dichloroisocyanurate 7
Dilithium hexylisocyanurate (LHXIC) 4 dissolved in
water was loaded to a beaker with a pH meter (320,
METTLER TOLEDO, UK). TCIA 5 was slowly added
to the solution under vigorous stirring. The final pH of
the product solution was 7.6570.12. White powder of
Lichlor-6 was finally obtained by freezing and drying the
solution [11].
Synthetic procedures and chemical structures of each
product are shown in Fig. 1. The structures of all
products were identified with fourier transform nuclear
magnetic resonance (FT-NMR) spectrometer (JNM
ECP-400, Jeol, Japan) and Fourier transform infrared
(FT-IR) spectrometer (SPECTRUM 2000, Perkin El-
mer, England).
According to the chemical structure of synthesized
adhesion-activator, it is referred to as Lichlor-6, in
which Li, chlor and 6 stand for lithium, chlorine, hexyl
group, respectively. SBR and EVA for this study were
used as substrates.

2.1. Materials

All chemicals used in this experiments were purchased

from Aldrich Chemical Company, Inc., USA, and used
as received.

2.1.1. Synthesis of hexylisocyanuric acid 3 [10]

To a suspension of cyanuric acid (98%) 1 in water,
LiOH
H2O (98%) was added followed by stirring for
3 h at 100 1C. After cooling to room temperature, the
precipitated product was filtered and washed with water.
The product was dried at 110 1C for 24 h to give white
crystals 2. The lithium salt 2 was dissolved in MeOH
(99%) at 50 1C, and then 1-bromohexane (98%) was
slowly added to the solution. After refluxing for 24 h the
reaction solution was concentrated in vacuo. The
residue was diluted with ethyl acetate (99.8%) and
extracted with water to remove the unreacted lithium
salt. The organic layer was concentrated in vacuo and
then, the residue gave the white solid 3 after several
washing with benzene (99.5%) to remove the remaining
1-bromohexane.

2.1.2. Synthesis of dilithium hexylisocyanurate

Fig. 1. Synthetic procedures and chemical structures of hexylisocya-
(LHXIC) 4 nuric acid 3, dilithium hexylisocyanurate (LHXIC) 4 and preparation
To a solution of hexylisocyanuric acid 3 in EtOH of Lichlor-6 consisting of lithium chlorohexylisocyanurate 6 and
(99.5%), LiOH
H2O in water was slowly added at lithium dichloroisocyanurate 7.
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D. Ri Zhang et al. / International Journal of Adhesion & Adhesives 25 (2005) 371–378
2.2. Experimental techniques
2.2.1. Water contact angle measurements
The surfaces of SBR and EVA treated with solution
of Lichlor-6 were characterized by measuring water
contact angle. Before measuring contact angle, the SBR
samples were washed with toluene (98%) and dried at
60 1C for 30 min and EVA samples were washed with
methyl ethyl ketone (MEK, 98%) and dried at 60 1C for
30 min, then the SBR and EVA samples were treated
with 2, 5, 8, 12 and 16 wt% aqueous solutions of
Lichlor-6, using a brush, and dried at 60 1C for 5 min.
The surface treated SBR or EVA pieces were placed
on the plate of Contact Angle Measuring System (G 10,
Kruss, Germany). Deionized water of 10 ml was carefully
dropped on the surfaces of the samples. Distilled water
was passed through a six-cartridge Barnstead Nanopure
II purification train consisting of Macropure pretreat-
ment (NANO Pure ultrapure water system, Barnstead,
USA). After 10 min, the contact angles of both sides of
the drops were measured. Three drops were measured
and averaged. The contact angles on the surface of non-
treated sample were also measured. The measurements
were carried out in ambient condition.
2.2.2. Fourier transform infrared spectroscopy (FTIR)
A FTIR spectrometer (SPECTRUM 2000, Perkin
Elmer, England) was used to obtain the attenuated total
reflectance-FTIR (ATR-FTIR) spectra of SBR and
EVA treated with 0, 2, 5 and 8 wt% aqueous solution
of Lichlor-6. 50 scans were done and average values with
a resolution of 1 cm1 were obtained.
2.2.3. Scanning electron microscopy (SEM)
Scanning electron microscopy was carried out to
observe the morphological modifications of SBR and
EVA surfaces treated with 0 wt% (non-treated), 2 and
8 wt% aqueous solution of Lichlor-6 using SEM system
(S-2400, Hitachi, Japan) at an acceleration voltage of
20 kV. SBR and EVA samples were gold-coated to
obtain enough contrast in the SEM micrographs.
2.2.4. Tear resistance measurements
SBR/PU adhesive/EVA joints were made using SBR
and EVA strip test pieces (200 mm  20 mm  3 mm).
Prior to applying adhesive, 0, 2, 5 and 8 wt% aqueous
solution of Lichlor-6 were applied on the surfaces of the
samples with a brush and dried at 60 1C for 1 h, then, the
water-based PU adhesive was applied on the surfaces of
SBR and EVA pieces with a brush and dried at 60 1C for
5 min. Then, the two surfaces of SBR and EVA pieces
were brought into contact under a roll pressure of 28 kg/
m2, and the joints were kept at 23 1C and 48% relative
humidity for 48 h before testing tear resistance. The
strengths of the SBR/PU adhesive/EVA joints were
determined using a tensile testing machine (HST-50 DL,
373
HANSEUNGENI CO.LTD, KOREA) with a tearing
rate of 100 mm/min. The strengths were tested three
times and averaged.
3. Results and discussion
3.1. Surface wettability
One of the most effective methods for studying
surface wettability is the measurement of contact angle.
Fig. 2 shows the mean values of the water contact angles
on the SBR and EVA surfaces treated with Lichlor-6
solution as a function of the concentrations of Lichlor-6.
The non-treated SBR and EVA show high contact
angles of 891 and 881, respectively, resulting from the
poor wettability of the SBR and EVA, indicating that
both SBR and EVA surfaces have hydrophobic prop-
erty. After surface treatment with Lichlor-6, water
contact angles show decreasing trends with the increas-
ing concentration of Lichlor-6, from 891 to 341 for SBR
and from 881 to 361 for EVA, respectively, and both
shows the similar decreasing trend in the water contact
angle values with the increasing concentrations of
Lichlor-6. This is a great improvement of wettability
compared with TCIA solution [1,2]. The decrease in the
water contact angle is probably in part due to the
increased hydrophilicity of surfaces caused by LCI
included in Lichlor-6. Martin-Martinez et al. [1] used
ethyl, propyl and butyl acetates as solvents for TCIA to
chlorinate the surface of SBR. They found that water
contact angle values of the surfaces treated with TCIA
solutions were as high as about 801, but always smaller
than those of as-received and solvent wiped SBR. They
considered that the chlorination of SBR with TCIA
solutions leads to the decrease in the contact angle due
to the modifications produced on the surface by the
Lichlor-6
90
SBR
EVA
80
Contact angle (degrees)
70
60
50
40
30
-2 0 2 4 6 8 10 12 14 16 18
Concentration (wt%)
Fig. 2. Water contact angles of SBR and EVA treated with different
concentrations of Lichlor-6 at 23 1C.

374 D. Ri Zhang et al. / International Journal of Adhesion & Adhesives 25 (2005) 371–378
treatment of TCIA solution. Lee et al. [12] studied the
effect of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)
(PHBV) surfaces with different wettability on fibroblast
behavior and found that the water contact angles of the
chloric acid treated PHBV film surfaces gradually
decreased from 75.31 to 29.51. The chlorination and
oxidation reaction of SBR and EVA caused by Lichlor-6
solution resulted in the increase of the portion of
hydrophilic functional groups on the SBR and EVA
surfaces. The changes in chemical structure of the
treated surfaces will be discussed in the following
ATR-FTIR results. Contact angle is also affected by
the surface roughness and it usually decreases with
increasing surface roughness. As shown in Fig. 5, the
increased surface roughness contributed to the decrease
in the contact angle of sample. The effect of surface
roughness will be discussed further in the SEM results.
3.2. ATR-FTIR spectra
In order to investigate chemical variation on the
surfaces of samples, ATR-FTIR spectra were recorded.
As shown in Fig. 3, ATR-FTIR spectrum of non-treated
SBR shows the presence of styrene and butadiene bands:
C-H(2913, 2846 and 718 cm1), CH2 (1461, 1386 cm1 ),
C¼C (960 cm1). Strong carboxylic band of zinc
stearate (1536 cm1) is also detected, which is a
component in the SBR formulation and act as a
antiadhesion, and there is a broad silica bands (about
1080 cm1). The ATR-FTIR spectra of SBR treated
with 2, 5 and 8 wt% solutions of Lichlor-6 show
characteristic bands of C¼O (1685 cm1) and N–C¼O
(1582 cm1). It must be noticed that the intensity of zinc
stearate band decreased dramatically after treatment
with Lichlor-6 and gradually decreased with increasing
Lichlor-6 / SBR
N-C=O
C=O
8 wt%
Absorbance
5 wt%
2 wt%
C-H
Zn stearate
Non-treated
4000 3500 3000 2500 2000
-1
Wavenumber (cm )
Fig. 3. ATR-FTIR spectra of SBR treated with different concentra-
tions of Lichlor-6.
ARTICLE IN PRESS
concentration of Lichlor-6. The intensities of Si–O and
C–H bands also gradually decreased with the increasing
concentration of Lichlor-6 while the intensities of
N–C¼O and C¼O bands increased with the increasing
concentration of Lichlor-6. ATR-FTIR spectrum of
non-treated EVA is shown in Fig. 4, there are bands of
C–H (2914, 2856 cm1), CH2 (1445, 1361 cm1), C¼O
(1737 cm1) and C–O (1019 cm1), there is also band of
C–N (1235 cm1) from the azo compound (filler).
Typical band of N–C¼O (1582 cm1) was detected for
EVA treated with 2, 5 and 8 wt% solutions of Lichlor-6.
It is shown that the relative intensity of the band of
N–C¼O increased with the increasing concentration of
Lichlor-6 while that of the bands of C–H, CH2, C¼O,
C–O and C–N decreased with the increasing concentra-
tion of Lichlor-6. Pramanik et al. [13] reported IR
spectra of EVA/clay nanocomposite and the character-
istic bands from EVA/clay were found to be C¼O, CH2,
C–O and Si–O at 1747, 1460, 1243 and 1044 cm1,
respectively.
Pastor-Blas et al. [7] reported X-ray photoelectron
spectroscopy (XPS) analyses to determine the chemical
compositions of the surfaces treated by TCIA. XPS is a
useful technique for surface chemistry, and it can
characterize the outmost surface (about 5 nm) of the
sample. Their XPS results showed 92.7 at% carbon and
0.8 at% chlorine for SBR treated with 2 wt% TCIA, and
95.7 at% carbon and 0 at% chlorine for untreated SBR,
respectively. They contributed the reduction of the
atomic concentrations of carbon to the chlorination by
TCIA. In addition, C–Cl band was not found in their
ATR-FTIR spectra, probably due to very low atomic
concentration of chlorine. According to their XPS
results, it is believed that C–Cl bands were not detected
in our ATR-FTIR spectra because of too low concen-
tration of chlorine.
Lichlor-6 / EVA N-C=O CH2
C-N
C-O
C-H C=O
Absorbance
8 wt%
5 wt%
CH 2 Si-O 2 wt%
C=C
Non-treated
1500 1000 4000 3500 3000 2500 2000 1500 1000
-1
Wavenumber (cm )
Fig. 4. ATR-FTIR spectra of EVA treated with different concentra-
tions of Lichlor-6.
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D. Ri Zhang et al. / International Journal of Adhesion & Adhesives 25 (2005) 371–378
However, it must be kept in mind that the variations
of contact angle on a surface depend not only on the
chemical modifications of the surface-treated substrate,
but also on the morphological modifications of the
surface-treated substrate. So it can be believed that the
chemical change on a surface-treated substrate is only
one of reasons leading to the variation of contact angle.
On the basis of above results, we can explain to some
extent why the contact angles of SBR and EVA
decreased with the increasing concentration of Lichlor-
6. As we know, non-polar compositions lead to the
hydrophobicity while polar compositions result in the
hydrophilicity. As a sequence, total effect of chemical
composition on the contact angle will be determined by
the competition between the non-polar and polar
compositions on the surface.
In the case of untreated SBR, the effect of zinc
stearate (non-polar) is larger than that of silica (polar),
leading to the high contact angle. After treatment with
Lichlor-6, the intensity of zinc stearate band dramati-
cally reduced, and the intensity of silica (polar) band
also gradually decreased with the increasing concentra-
tion of Lichlor-6, however, new polar group (N–C¼O)
was produced due to the treatment with Lichlor-6 and
its intensity increased with the increasing concentration
of Lichlor-6. As a result, the effect of polar composi-
tions seemed to become large, leading in part to the
decrease in the contact angle with the increasing
concentration of Lichlor-6.
In the cases of EVA, new polar group (N–C¼O) was
also produced due to the treatment with Lichlor-6 and
its relative intensity compared with that of CH2 (non-
polar group) increased with the increasing concentration
of Lichlor-6, but the intensities of other polar groups
such as C¼O, C–N, C–O decreased with the increasing
concentration of Lichlor-6. As a sequence, total effect of
polar groups cannot be determined qualitatively.
3.3. SEM micrographs
Scanning electron microscopy (SEM) is a strong tool
in exploring surface morphology in the range of
microdimension. In order to find one of the reasons
for lowering the contact angles due to the treatment with
Lichlor-6, the changes of surface roughness were
investigated by SEM.
The morphological modifications produced on the
SBR and EVA surfaces by the treatment with 0, 2 and
8 wt% solutions of Lichlor-6 are shown in Fig. 5. Fig.
5A–C of SBR and Fig. 5D–F of EVA correspond to the
treatment of 8, 2 and 0 wt% solutions of Lichlor-6,
respectively. In the case of SBR, as shown in Fig. 5C, the
non-treated surface appears rough in the large dimen-
sion. After treatment with 2 and 8 wt% solutions of
Lichlor-6, the surface roughness increased and some
small particles are observed in Fig. 5B and A,
375
respectively. The fractured surface is also observed in
Fig. 5A. In the case of EVA, the non-treated surface
shown in Fig. 5F displays a relatively more flat surface
than that of SBR. Fig. 5E shows more roughness than
Fig. 5F and relatively homogeneous distribution of
small like-crystal particles is observed while Fig. 5D
shows significantly increased surface roughness and
apparently fractured surface is observed. It is reasonable
from Fig. 5 to conclude that the treatment with Lichlor-
6 leaded to the significant morphological changes on
the SBR and EVA surfaces. The roughness of the SBR
and EVA surface treated with TCIA were reported in
the literatures [1,2] and the chlorination and further-
more oxidation reaction is considered to result in the
roughness of the surfaces. In the present study, the
morphological modifications of SBR are larger than
those of reports [1,2], in which TCIA dissolved in
organic solvents were used. Larger morphological
changes of the surfaces are probably due to the better
wettability of Lichlor-6 solutions on the SBR and EVA
surfaces.
The influence of roughness on the value of the contact
angle has been quantified by Wenzel [14] and it has the
form:
r ¼ cos yw =cos y,
where yw is Wenzel’s angle (contact angle on a rough
surface), y is the contact angle on an ideally smooth
surface, and r is the surface roughness. It means that the
value of the contact angle decreases in the range of 0–901
with increasing the surface roughness.
Although the surface roughness of non-treated SBR
and EVA are quite different from each other, their
contact angles are almost same, and as high as 891 and
881, respectively, indicating that the effects of non-polar
groups are dominant on the both SBR and EVA
surfaces. For the treatment with 2 wt% Lichlor-6, the
change of surface roughness of SBR seems to be larger
than that of EVA, and also on the basis of above
discussions in the ATR-FTIR spectra, the contact angle
of SBR is expected to be smaller than that of EVA, this
is in agreement with the results obtained in the contact
angle measurements. For the treatment with 8 wt%
Lichlor-6, the change of surface roughness of SBR is
smaller than that of EVA having more cracks on it,
resulting in the smaller contact angle of EVA than that
of SBR, therefore, the effect of surface roughness on the
contact angle believed to be larger than that of chemical
modifications in this case.
3.4. Tear resistance test
The function of adhesion-activator is to obtain well
dispersion of adhesive on the surfaces of substrates to be
bonded so as to enhance the strength of adhesion.
In order to test the effect of new synthesized
 ARTICLE IN PRESS
376 D. Ri Zhang et al. / International Journal of Adhesion & Adhesives 25 (2005) 371–378
Fig. 5. SEM micrographs of surfaces treated with different concentrations of Lichlor-6. SBR: A (8 wt%), B (2 wt%), C (Non-treated) and EVA: D
(8 wt%), E (2 wt%), F (non-treated).
adhesion-activator on the adhesion with the increasing
concentration of Lichlor-6, tear resistance was tested for
the treatment with 0, 2, 5 and 8 wt% solutions of
Lichlor-6. The tested values are given in Table 1.
Tear resistance values obtained are 4.970.2, 6.570.1,
8.470.3 and 10.270.2 kgf/2 cm for the treatment with
0, 2, 5 and 8 wt% solutions of Lichlor-6, respectively. It
is easily seen that the tear resistance increased with the
increasing concentration of Lichlor-6, resulting from the
chemical modifications shown in ATR-FTIR spectra
and the increased surface roughness shown in SEM
micrographs. In practice, it is recognized that the
behavior of the adhesion depends on the surface
characteristics such as wettability (hydrophilicity/hydro-
phobicity or surface free energy), chemistry, charge,
roughness, and rigidity, and so on. The enhancement of
adhesion strength with the increasing concentration of
Lichlor-6 can be mainly explained by two adhesion
mechanisms.
The first is the surface roughness. One reason of the
enhancement of the adhesion strength caused by surface
roughness is that adhesion is purely a matter of contact
of physical area, the increased surface roughness means
the increased surface area, leading to the larger
interactions between the adhesive and substrate surface
to be bonded. Another reason of surface roughness aids
in adhesion strength is the interlocking effect, the so-
called ‘‘lock and key’’ effect. A key, when turned in the
tumbler of a lock, cannot be removed from the lock
because of the physical impediment provided by the
tumblers. It is obvious in this study that the surface
roughness of SBR and EVA noticeably increased with
the increasing concentration of Lichlor-6, so we believed
that the increased surface roughness greatly contributed
to the adhesion strength of the samples. For the
treatment with 8 wt% Lichlor-6, the fractured surfaces
were observed on the SBR and EVA surfaces, so ‘‘lock
and key’’ effect played additional role in this cases. The
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D. Ri Zhang et al. / International Journal of Adhesion & Adhesives 25 (2005) 371–378 377

Table 1 100 11
Tear resistance values of SBR/PU adhesive/EVA joints treated with 95
different concentrations of Lichlor-6 90
10

Tear resistance (Kgf/20 mm)

85
Concentration (wt%) 0 2 5 8

Contact angle (degrees)

9
80
Tear resistance (kgf/2 cm) 4.970.2 6.570.1 8.470.3 10.270.2 75 8
70

65 7

60
6
EVA 55
Adhesion-activator
50
5
PU adhesive 45

40 4
SBR -1 0 1 2 3 4 5 6 7 8 9
Lichlor-6 concentration (wt%)

Fig. 6. Schematic structure of SBR/PU adhesive/EVA joint. Fig. 7. Relation of tear resistance–water contact angle.

second is the surface polarity of the substrate. The relates with larger one between the contact angles of two
greater polarity of the surfaces results in the greater substrates. Eventually, we can obtain the relation
interactions between the adhesive and substrate surface. between tear resistance and larger contact angle by
The polarities of SBR and EVA surfaces increased to plotting against the Lichlor-6 concentration. It can be
some extent with the increasing concentration of found from Fig. 7 that the tested tear resistance is
Lichlor-6, contributing to the adhesion strength. As a almost inversely proportional to the larger one between
result on the whole, the tear resistance increased with the the two contact angles of SBR and EVA surfaces.
increasing concentration of Lichlor-6.
Now, let us discuss the relation between the contact
angle and tear resistance in detail on the basis of tear
4. Conclusions
resistance mechanism.
Schematic structure of SBR/PU adhesive/EVA joint is
The water contact angles decreased from 891 and 881
shown in Fig. 6. It can be seen from Fig. 6 that the
of the non-treated samples to 341 and 361 of samples
structure of joint consists of five parts: SBR, adhesion-
treated with 16 wt% aqueous solution of Lichlor-6 for
activator layer, PU adhesive layer, adhesion-activator
the SBR and EVA, respectively. The contact angle
layer, EVA, in turn. There are five kinds of interactions
decreases with the increasing concentration of Lichlor-6
in the joint: SBR molecules—SBR molecules, EVA
due to the enhanced wettability of the surface by the
molecules—EVA molecules, PU adhesive molecules—
treatment of Lichlor-6. The treatment with the higher
PU adhesive molecules, SBR molecules—PU adhesive
concentration of Lichlor-6 produced the more marked
molecules, EVA molecules—PU adhesive molecules.
chemical and morphological modifications on the SBR
The interactions between adhesion-activator molecules
and EVA surfaces and resulted in the greater tear
and other layer molecules can be ignored because of
resistance values. The increased surface roughness of
very thin layer of adhesion-activator. So we can image
SBR and EVA caused by the treatment with Lichlor-6
that the break of joint will be occurred in the layer of the
have larger effects on the decrease of the contact angle
weakest interaction among the five interactions. In
than chemical modifications. Tear resistance values
general, the former three interactions are stronger than
obtained are 4.970.2, 6.570.1, 8.470.3 and
the latter two interactions; therefore, the break of joint
10.270.2 kgf/2 cm for the treatment with 0, 2, 5 and 8
usually take place in the latter two interactions.
wt% solutions of Lichlor-6, respectively, and the tested
For the cases of 2 and 5 wt% Lichlor-6, since the
tear resistance is almost inversely proportional to the
contact angles of SBR surface are smaller than that of
larger one between the two contact angles of SBR and
EVA surfaces, the breaks of joints are expected to occur
EVA surfaces.
in the layers between EVA and PU adhesive, while for
the case of 8 wt% Lichlor-6, since the contact angle of
SBR surface is larger than that of EVA surface, the
break of joint is expected to occur in the layer between Acknowledgements
SBR and PU adhesive. So we can easily find that the
break of a joint always occurs in the layer containing a This work was supported by Korea Research
substrate of which the contact angle is larger than that Foundation Grant (KRF–2002–050–C00007) and also
of the other substrate, indicating that tear resistance by Korean Ministry of Industry and Resources of the
 ARTICLE IN PRESS
378 D. Ri Zhang et al. / International Journal of Adhesion & Adhesives 25 (2005) 371–378
program of Development of Industrial Technology,
2001.
References
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