Sei sulla pagina 1di 9

International Journal of Adhesion & Adhesives 31 (2011) 389397

Contents lists available at ScienceDirect

International Journal of Adhesion & Adhesives


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

Migration of low molecular weight moiety at rubberpolyurethane interface:


An ATR-IR spectroscopy study
Rafael Torregrosa-Coque, Sonia Alvarez-Garca, Jose Miguel Martn-Martnez n
Adhesion and Adhesives Laboratory, University of Alicante, 03080 Alicante, Spain

a r t i c l e i n f o

abstract

Article history:
Accepted 7 March 2010
Available online 16 March 2011

In this study, a novel approach based on ATR-IR spectroscopy consisting in the combined use of two
prisms of different nature and refraction index (germaniumabout 1 mm depth and zinc selenideabout
3 mm depth) was proposed to study the polyurethanerubber interface. More precisely, the migration of
parafn wax additive in as-received and MEK cleaned vulcanized styrenebutadiene rubber (SBR)
polyurethane coating interface was monitored. Polyurethane coating with thickness of about 2 mm was
applied on the SBR rubber surface and the ATR-IR spectra were recorded in the polyurethane coating.
Thus, the ATR-IR spectrum obtained with Ge prism analyzed only the polyurethane coating whereas the
ATR-IR spectrum obtained with ZnSe analyzed both the polyurethane coating and the near surface SBR.
The results obtained showed that the parafn wax migrated from the SBR rubber bulk to the rubber
polyurethane interface, then diffused into the polyurethane and nally migrated to the polyurethane
surface.
& 2011 Elsevier Ltd. All rights reserved.

Keywords:
Polyurethane
Rubbers
Infrared spectra
Interfaces

1. Introduction
One of the applications of the IR spectroscopy is the analysis of
region near the surface of polymers using the attenuated total
reectance technique (ATR-IR spectroscopy) [1]. This analysis
technique has similar signal patterns and provides the same
information than the conventional IR absorption spectroscopy,
although the spectra obtained are not identical.
The ATR-IR spectroscopy requires that the sample should be
placed in contact with an internal reection element (prism). The IR
beam is directed with a given incidence angle onto the prism with
high refractive index in intimate contact with the top surface of the
material to allow the infrared light beam undergoes internal
reection. Consequently, the IR beam is forced to be totally reected
at the interface between the prism and the sample, and as a result
an evanescent electric eld penetrates into the sample where it
undergoes an exponential decay in its intensity (Fig. 1) [2,3]. Thus,
the frequencies of the evanescent and incoming waves are the same,
but the eld amplitude is exponentially decaying with distance from
the surface, as it indicated by Eq. (1).
E E0 Uez=dp

where E is the electric eld amplitude at penetration distance (z)


into the sample, E0 is the electric eld amplitude at the interface,
n

Corresponding author. Tel.: 34 965 90 39 77; fax: 34 965 903454.


E-mail address: jm.martin@ua.es (J.M. Martn-Martnez).

0143-7496/$ - see front matter & 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijadhadh.2011.03.003

and dp is the penetration depth, a characteristic parameter dened


as the distance in the material at which the electric eld E is reduced
depending on the wavelength. Both the electric eld E and the
penetration depth dp are functions of the frequency of the IR light.
The evanescent wave of the infrared radiation has different
penetration depths depending on the angle of incidence of the IR
beam and the refractive index of the prism, among other experimental set-up parameters. On the other hand, the absorbance in
the ATR-IR spectroscopy corresponds to the number of reections
of the IR beam in the interface between the sample surface and
the prism. Thus, the penetration depth dp of the IR beam into the
sample, usually dened as the distance, is given by Eq. (2).
dp

l
2pnc sin2 yns =nc 2 1=2

where l is the wavelength of the IR incident radiation, y is the


angle of incidence of the IR radiation, and ns and nc are the
refractive index of the sample and prism, respectively. Although
the ATR-IR spectroscopy is not a purely surface analysis technique, depending on the values of the parameters in Eq. (2), the
ATR-IR spectroscopy allows different penetration of the IR radiation in the material surface, providing information on a depth of
110 mm [3].
In this study, the analysis of rubberpolyurethane coating
interfaces was carried out by ATR-IR spectroscopy with Ge and
ZnSe prisms, since the penetration of the evanescence wave into
the material is different in function of the used prism. To the best
of our knowledge, this is the rst time in the literature that this

390

R. Torregrosa-Coque et al. / International Journal of Adhesion & Adhesives 31 (2011) 389397

Fig. 1. Scheme of the ATR-IR spectroscopy.

method is used for monitoring the chemical changes produced


by migration of low molecular weight moieties in rubber
polyurethane interface. Rubber material was selected in this
study because, when it is in contact with other polymer, the
migration of additives of low molecular weight from the rubber
surface produces modications at the rubberpolymer interface.
In physically bonded interfaces, this migration may cause the
formation of weak boundary layers that are deleterious to
adhesion [4].
Rubbers are polymeric materials able to suffer considerable
deformations under relatively low stresses. Rubber properties are
improved by vulcanization with sulfur and by proper compounding; particularly, rubber needs to be protected against degradation by oxygen and ozone attack during life service, and therefore
appropriate antioxidant and antiozonant moieties (mainly parafn wax) are added [5]. However, because of the concentration of
antioxidants and antiozonants is usually higher than their saturation limits in the rubber phase, they tend to migrate (blooming
process) to the rubber surface after vulcanization. Hence, according to thermodynamics of multi-component phases, de-mixing
goes on via migration until the concentration corresponds to the
appropriate Gibbs free energy of the phase, which depends on the
chemical potential of the antioxidant and antiozonant. This
migration is supposed to occur continuously until equilibrium is
reached between the concentration of parafn wax on the surface
and in the rubber bulk, creating an external layer of about 2 mm
thickness [6]. Therefore, although wax blooming allows to protect
the rubber against ozone attack by formation of an impervious
physical barrier [7,8], this parafn wax lm on the rubber surface
creates a weak boundary layer that inhibits its interfacial and
adhesion properties. In fact, the existence of weak boundary
layers of antiozonant parafn wax on the surface of vulcanized
rubber is recognized as one of the main causes of poor adhesion of
rubber to adhesives and coatings [9]. The extent of migration of
the wax to the rubber surface is a function of the solubility and
mobility of the wax, which depends upon the temperature and
time among other factors [10,11].
The most common parafn waxes for rubber materials have
melting points of 5070 1C and, for this reason, during mixing and
vulcanization (in which the rubber temperature reaches well
above 200 1C), the wax dissolves readily in the rubber. However,
after vulcanization when the rubber is cooled down to ambient
temperature, the solubility of the wax is greatly reduced and the

wax becomes supersaturated in the rubber [12]. As a result, some


crystallization of the wax can be produced on the rubber surface
to reduce the concentration of the dissolved wax to its equilibrium value, and the migration of wax to the rubber surface is
determined by the diffusion produced by the relative insolubility
of the wax below its melting point [13]. Moreover, the parafn
wax is able to migrate to rubbercoating interface, forming a lm
that interferes in the formation of physical bond (such as Van der
Waals or hydrogen bonds) at the rubber/polyurethane interface.
In this way, supposing a physical adhesion mechanism, the wax
lm forms a weak boundary layer able to cause catastrophic
adhesion failure [4,14,15]. Even though some studies have been
carried out [1623], the wax migration in a vulcanized rubber had
not been properly studied in the existing literature and factors
favouring or inhibiting the migration of antiozonants to the
rubber surfaces have not been fully understood. Similarly, the
processes produced at the rubberpolymer interface facilitating
the decrease in adhesion have not been fully determined.
In this work, a vulcanized styrenebutadiene rubber (SBR) was
coated with a thin lm of polyurethane and the migration of
parafn wax with time after joint formation to the interface was
studied. The usefulness of using two prisms with different
refractive index in ATR-IR spectroscopy analysis of the
SBR-polyurethane interface was demonstrated by placing a polyurethane lm of about 2 mm on the rubber. Using Ge and ZnSe
prism, different degrees of IR evanescent wave penetration into
the polyurethane lm was obtained and, therefore, the migration
of the parafn wax to the interface was monitored.

2. Materials and methods


2.1. Materials
Vulcanized styrenebutadiene rubber supplied by Iresa
Consultores S.L. (Alicante, Spain) was used. This rubber is used
in the manufacture of soles in the footwear industry and it was
compounded according manufacturer suggestion. The generic
rubber formulation is given in Table 1 as the specic compounding and vulcanization procedure was not disclosed. The composition of the rubber was expressed as part per hundred parts of
rubber, the usual way to express the composition of rubber
materials. This rubber is a mixture of synthetic and natural rubber
and contains precipitated silica as ller and zinc stearate as
processing aid. During vulcanization, the zinc oxide reacts with
the stearic acid producing zinc stearate. The rubber formulation
also includes microcrystalline parafn wax as antiozonant
(Tiozone 2000, supplied by Iberceras, Madrid, Spain). Wax melting point is 6469 1C (measured according ASTM D.938) and its
viscosity at 100 1C is 5 mPa s (ASTM D.3236). It has been
Table 1
Typical formulation of the vulcanized styrenebutadiene rubber. Composition is
given in phr (parts per hundred parts of rubber).
Ingredient

Content (phr)

Styrenebutadiene rubber (SBR1502)


Natural rubber (pale crepe grade)
Precipitated silica
Zinc oxide
Stearic acid
Polyethylene glycol
Parafn wax
Plasticizer
Sulfur
2-mercaptobenzothiazol disulde
Tetramethyl thiuram disulde

60
40
33
1.7
1.0
1.7
0.7
3.3
2.3
1.5
0.3

R. Torregrosa-Coque et al. / International Journal of Adhesion & Adhesives 31 (2011) 389397

established that both, the microcrystalline parafn wax and the


zinc stearate, are responsible for the poor adhesion of the rubber.
For some experiments, the properties of the rubber bulk were
analyzed. Fresh bulk rubber pieces were obtained by cutting the
rubber pieces in half longitudinally with a scalpel blade. To
avoid low molecular weight moieties migration, the fresh cut
rubber bulk pieces were immediately analyzed by contact angle
measurement and ATR-IR spectroscopy.
For comparison, a thin lm of the antiozonant parafn wax
Tiozone 2000 used in the rubber formulation was prepared by
melting into a Teon plate. The wax lm was cooled down for
48 h at room temperature before analysis.
With the aim of investigating the changes produced in the
concentration gradient of parafn wax in the rubber surface, the
parafn wax lm on the as-received rubber surface was removed.
The removal of the wax layer was carried out by immersion in
MEK (methyl ethyl ketone) in ultrasonic bath (FISA, Barcelona,
Spain) at 45 1C for 10 min. Then, the rubber samples were dried to
remove residual MEK at room temperature for 40 min, before
characterization.

391

Fig. 2. Depth of penetration of the IR beam as a function of the wavenumber in a


material obtained by ATR-IR spectroscopy measured with Ge and ZnSe prisms.

2.2. Application of the polyurethane coating on cleaned rubber


surfaces
MEK solution containing 2 wt% of polyurethane commercial
pellets (D540, provided by Bayer, Leverkusen, Germany) was
prepared by placing into a glass bottle for 48 h under stirring at
750 rpm. The polyurethane solution was applied on MEK-ultrasonic cleaned rubber surface by spin coating to render a thin
coating of about 2 mm thickness (measured in SEM micrographs
of cross-sections of the rubber/polyurethane samples; ten SEM
micrographs were taken and averaged). After spin-coating, the
samples were dried at room temperature for 2 h to remove all
remaining solvent.
Some measurements were carried out in polyurethane lms
obtained by placing the polyurethane solution in Teon mold
allowing the removal of solvent at room temperature for seven
days. The thickness of the polyurethane lm was about 0.7 mm.
On the other hand, the migration of the parafn wax to the
rubberpolyurethane interface was monitored in polyurethane
coated rubber maintained at room temperature for 2 weeks.

Fig. 3. Scheme of the principle of analysis of interfaces in coated polymeric


materials by ATR-IR spectroscopy combining Ge and ZnSe prisms.

2.3. ATR-IR spectroscopy


The chemical changes in the as-received and MEK cleaned
rubber were monitored by ATR-IR spectroscopy. All samples were
studied using two different prisms in Tensor 27 spectrometer
(Bruker Optik, Ettlingen, Germany). The experimental conditions
used were an angle of incidence of the IR radiation of 451 in the
wavenumber range 4000650 cm  1, and 200 scans were
obtained and averaged with a resolution of 4 cm  1.
Both Ge and ZnSe prisms were used. The depth of penetration
of the IR beam as a function of the wavenumber for the two
prisms is given in Fig. 2. The lower the wavenumber, the higher
the penetration of the evanescence wave into the material;
always, the depth of penetration of the IR beam is lower when
Ge prism is used. Thus, when ZnSe prism (nc 2.4) is used, the
penetration depth for a material with ns 1.5 (refractive index in
most of the polymeric materials) at 1000 cm  1 is estimated to be
2.03.0 mm for an angle of incidence of the IR radiation of 451. On
the other hand, if Ge prism is used under the same experimental
conditions, because of its higher refractive index (nc 4.0), the
penetration depth is much lower (0.651.0 mm). It should be
noted that the value of ns for polyurethane and rubber used in this
study is an approximation due to the difculty of the measurement of the refractive index in polymeric materials. Therefore, the

Fig. 4. Contact angle measurement on polyurethane coated rubber material.

analysis of a polymeric material with the two prisms will allow to


distinguish the chemical composition in a depth from the external
surface between 0.651.0 and 2.03.0 mm. Furthermore, if the
rubber material is coated with a polyurethane lm of 2.03.0 mm
thickness, the analysis by ATR-IR spectroscopy with Ge and ZnSe
prisms will allow the chemical analysis of the interface (Fig. 3).
2.4. Contact angle measurements
The wettability of the rubber and polyurethane coating on
rubber (Fig. 4) was evaluated by contact angle measurements in

392

R. Torregrosa-Coque et al. / International Journal of Adhesion & Adhesives 31 (2011) 389397

Rame-Hart 100 goniometer (Rame-Hart, Mountain Lakes, NJ,


USA). The sessile drop procedure was used. The test liquid was
deionized bi-distilled water obtained with a Milli-Q system
(Millipore, Paris, France), with a surface tension of 72.8 mN m  1.
The test pieces were placed into the hermetic and isothermal
(25 1C) chamber of the goniometer previously saturated with
water vapor for at least 30 min before placing the drop. Water
drops (4 ml) were placed on the rubber or on the polyurethane
coating surface using a micro-syringe (Hamilton Instruments)
provided with a at end needle. Contact angle values were
obtained 10 min after water drop deposition on the sample
surface. At least 8 drops were placed on the samples and averaged
with an experimental error of 721.
2.5. Scanning electron microscopy (SEM)
The topography of the rubber surface was analyzed in Jeol
JSM-840 (Peabody, MA, USA) scanning electron microscope
(SEM). The rubber and the polyurethane coated rubber samples
were gold-coated before analysis and an electron beam of 20 kV
was used.

3. Result and discussion


3.1. Use of ATR-IR spectroscopy with Ge and ZnSe prisms for analysis
of parafn wax migration to the rubber surface
Fig. 5 shows the ATR-IR spectrum obtained with ZnSe prism of
rubber bulk (immediately obtained after cut the rubber piece by
the middle) and parafn wax lm. The ATR-IR spectra obtained
with Ge prism are similar because of lack of wax migration to the
surface. The ATR-IR spectrum of the rubber bulk in Fig. 5 shows
the absorption bands of trans-1,4-C C stretching (963 cm  1),
CH2 wagging motion (1380 cm  1) and CH2 scissoring
(1462 cm  1) in butadiene. Styrene absorptions occur at 698
(CH out-of-plane deformation) and 912 cm  1 (aromatic CH
stretching). The ATR-IR spectrum of the rubber bulk also shows a
broad and intense band at 1062 cm  1 due to the silica ller
(SiO stretching) and the absorption band at 1537 cm  1 corresponds

to zinc stearate. In addition, other lower intensity bands in the ATR-IR


spectrum of the rubber bulk (2950, 2915, 2845, 1473, and 719 cm  1)
correspond to the characteristic CH2 rocking bands in the parafn
wax (Fig. 5). As the parafn wax has CH3 end-groups, the CH3
absorption at 2950 cm  1 may also indicate the presence of parafn
wax in the rubber bulk.
Fig. 6 shows the ATR-IR spectra of the as-received rubber
obtained with ZnSe and Ge prisms. The most intense absorption
bands in both ATR-IR spectra appear at 2950, 2915, 2845, 1473,
and 719 cm  1 and they correspond to the characteristic CH2
rocking bands of the parafn wax (Fig. 5), indicating that on the
rubber surface and/or near the rubber surface a lm of parafn
wax exists [21]. Moreover, the ATR-IR spectrum of the as-received
rubber obtained with Ge prism is very similar to that of the
parafn wax, except for the presence of the low intensity bands at
1537 and 1462 cm  1 due to zinc stearate and CH2 scissoring in
butadiene, respectively. When the ATR-IR spectrum is obtained
with ZnSe prism, the intensity of the bands at 1537 and
1462 cm  1 is clearly reduced and the broad and moderately
intense band at 1075 cm  1 due to the silica ller (SiO stretching)
is also observed; furthermore, several bands of butadiene (1380
and 963 cm  1) and styrene (912 and 698 cm  1) of the rubber can
be distinguished.
Because of the lower depth analyzed in the ATR-IR spectrum
obtained with Ge prism of the as-received rubber (0.651.0 mm),
the main chemicals existing near the surface are parafn wax and
zinc stearate. However, the ATR-IR spectrum obtained with ZnSe
prism of the as-received rubber analyzed a thicker depth
(2.03.0 mm) and thus the characteristics bands of rubber can
also be analyzed. It can be concluded that the layer of parafn
wax and zinc stearate in the rubber surface has a thickness lower
than 2.0 mm. This value is consistent with previous ndings [7,8].
The existence of parafn wax on the as-received rubber
surface is evidenced by SEM. Fig. 7 shows that the as-received
rubber surface is quite at and it is fully covered with patches of
parafn wax crystals. Furthermore, the existence of the parafn
wax layer on the as-received rubber surface was evidenced by
contact angle measurements. According to Table 2, the water
contact angle on the as-received rubber is 107172, which it is
similar to that of the parafn wax lm (1101 72) indicating the

Fig. 5. ATR-IR spectra obtained with ZnSe prism of the rubber bulk and parafn wax lm.

R. Torregrosa-Coque et al. / International Journal of Adhesion & Adhesives 31 (2011) 389397

393

Fig. 6. ATR-IR spectra obtained with (a) ZnSe prism and (b) Ge prism of the as-received and MEK surface cleaned rubber.

Fig. 7. SEM micrographs of the as-received and MEK surface cleaned rubber.
Table 2
Contact angle values (water, 25 1C) on different samples.
Sample

Contact angle (deg.)

As-received rubber
Bulk rubber
Cleaned rubber
Polyurethane lm
Parafn wax lm

107
83
85
66
110

existence of an external parafn wax lm on the surface; for


comparison, the water contact angle value on the rubber bulk is
831 72. Therefore, SEM and water contact angle measurements
conrm the results obtained from ATR-IR spectroscopy using Ge
and ZnSe prism.

For further conrmation of the existence of parafn wax layer


on the as-received rubber surface, a cleaning with MEK in
ultrasonic bath was carried out. The ATR-IR spectra of the MEK
cleaned rubber obtained with Ge and ZnSe prism are shown in
Fig. 6. The ATR-IR spectra of the MEK cleaned rubber mainly show
the bands due to the rubber and the bands due to parafn wax
have quite low intensity. The typical bands of the rubber
formulation appear at 1065 cm  1 due to silica ller, and at 963
and 698 cm  1 corresponding to butadiene and styrene, respectively. The main difference between the ATR-IR spectra obtained
with Ge and ZnSe prism corresponds to the band at 1537 cm  1
due to zinc stearate; as the intensity is higher in the ATR-IR spectrum obtained with ZnSe prism, the zinc stearate is not present on
the rubber surface but below 2 mm from the external surface.

394

R. Torregrosa-Coque et al. / International Journal of Adhesion & Adhesives 31 (2011) 389397

Furthermore, the water contact angle of the MEK cleaned rubber


851 72 (Table 2), similar to that of the rubber bulk (83172),
conrms the removal of parafn wax. On the other hand, the SEM
micrograph of the MEK cleaned rubber (Fig. 7) does not show the
patches of parafn wax due to their removal by MEK cleaning.
3.2. Analysis of the rubberpolyurethane interface by ATR-IR
spectroscopy with Ge and ZnSe prism
Polyurethane solutions were spin coated on MEK cleaned
rubber and the migration of parafn wax from the rubber bulk
to the rubberpolyurethane interface was studied. Under the
experimental conditions used in this study, the polyurethane
coating on the cleaned rubber surface has a thickness of about
1.52 mm, measured in SEM micrographs of cross-sections of the
polyurethane coated rubber specimens (Fig. 8). Therefore, the
ATR-IR spectra obtained with Ge prism, allows only the chemistry
of the polyurethane to be analyzed (Fig. 3), whereas the ATR-IR
spectra obtained with ZnSe prism will analyze both the polyurethane and the rubber surfaces. In this way, the changes in the
rubberpolyurethane interface can be monitored.

Fig. 8. SEM micrograph showing the polyurethane coating on the MEK surface
cleaned rubber.

The ATR-IR spectrum of polyurethane lm was obtained using


ZnSe and Ge prism. Both spectra are very similar and thus only
the ATR-IR spectrum obtained with ZnSe prism is shown in Fig. 9.
The bands at 2934 and 2862 cm  1 correspond to the CH
stretching in the polyurethane and the bands due to NH are
found at 3334 and 1530 cm  1. Other absorption bands are NH
plane (1168 cm  1) and NH out-of-plane deformations
(734 cm  1). The band at 1724 cm  1 corresponds to the CO
stretching of urethane and the bands at 1261 and 970 cm  1 are
due to CN stretching and COC in urethane, respectively.
Furthermore, the bands at 1219 and 1073 cm  1 correspond to
antisymmetrical
and
symmetrical
NCO
stretching,
respectively.
The ATR-IR spectra of the polyurethane coating on MEK
cleaned rubber obtained with ZnSe and Ge prisms are shown in
Figs. 10a and 11a, respectively; the 31002700 cm  1 region has
been enlarged in Figs. 10b and 11b. The ATR-IR spectra obtained
immediately after applying the polyurethane coating on the
cleaned rubber differ when Ge and ZnSe prism are used. Thus,
as expected, the ATR-IR spectrum obtained with ZnSe prism
shows both the bands due to polyurethane and rubber (styrene
(698 cm  1), butadiene (963 cm  1), and silica ller (1062 cm  1)).
The ATR-IR spectrum obtained with Ge prism shows only the
bands due to the polyurethane and the spectrum is the same than
that of the polyurethane lm (Fig. 9). Therefore, immediately after
application of the polyurethane coating on the cleaned rubber, the
migration of parafn wax is not produced.
By increasing the time after polyurethane coating application
on the cleaned rubber surface up to 14 days, some bands due to
the parafn wax appear in the ATR-IR spectra (Figs. 10 and 11).
Whereas the ATR-IR spectra obtained with ZnSe prism are similar
in the polyurethane coating immediately and 14 days after
deposition, they are different when they are obtained with Ge
prism. The ATR-IR spectrum obtained with Ge prism of the
polyurethane coating on cleaned rubber 14 days after deposition
shows intense bands at 2915 and 2848 cm  1 due to parafn
wax (Fig. 11b), indicating the migration of the parafn wax
from the rubber bulk to the rubberpolyurethane interface and
then the diffusion into the polyurethane coating on the cleaned
rubber.

Fig. 9. ATR-IR spectrum obtained with ZnSe prism of the polyurethane lm.

R. Torregrosa-Coque et al. / International Journal of Adhesion & Adhesives 31 (2011) 389397

395

Fig. 10. (a) ATR-IR spectra obtained with ZnSe prism of the polyurethane coating on MEK surface cleaned rubber for different time after polyurethane coating deposition.
(b) 31002700 cm  1 region of the ATR-IR spectra.

The presence of parafn wax on the polyurethane coating


surface was conrmed by water contact angle measurements
(Fig. 4). By increasing the time, the water contact angle value
neither varies on the MEK cleaned rubber (85172) nor on the
polyurethane lm (66172) (Fig. 12). The water contact angle
value on the polyurethane coating on cleaned rubber measured
immediately after coating deposition is 661 72, the same as that
for the polyurethane lm; however, one day after polyurethane
coating deposition, an increase in water contact angle value to
751 72 is produced. By increasing the time for 7 and 14 days, the
water contact angle values still increase to 801 and 861 72,
respectively, indicating the existence of parafn wax on the
polyurethane coating surface. The only way to have the parafn
wax on the polyurethane coating surface is the diffusion from the

rubberpolyurethane interface, conrming the validity of the


procedure proposed in this study consisting in combining the
ATR-IR spectra with two prisms of different depth of penetration
obtained in thin coating on substrates. In our opinion, this
procedure can be used in other polymeric coatings on polymer
substrates.

4. Conclusions
The interface between polyurethane coating and rubber surface can be analyzed by ATR-IR spectroscopy using two prisms of
different depth of penetration. Thin polyurethane coatings of
about 2 mm thickness on rubber substrate can be analyzed by

396

R. Torregrosa-Coque et al. / International Journal of Adhesion & Adhesives 31 (2011) 389397

Fig. 11. (a) ATR-IR spectra obtained with Ge prism of the polyurethane coating on MEK surface cleaned rubber for different time after polyurethane coating deposition.
(b) 31002700 cm  1 region of the ATR-IR spectra.

ATR-IR spectroscopy using Ge and ZnSe prism. The ATR-IR


spectrum obtained with Ge prism will provide the analysis of
only the polyurethane coating whereas the ATR-IR spectrum
obtained with ZnSe prism allowed the analysis of both, the
polyurethane coating and the rubber. The distinct information
provided by both ATR-IR spectra allowed the analysis of
polyurethanerubber interfaces.
The procedure proposed in this study was assessed by analyzing the migration of low molecular moieties to rubber surfaces.
The ATR-IR spectroscopy results were corroborated by SEM
micrographs and water contact angle measurements. It was
conrmed that parafn wax and zinc stearate were concentrated
in a layer covering the as-received rubber surface with a thickness
of about 2.0 mm. Furthermore, the parafn wax migrated from the

rubber bulk to the polyurethanerubber interface and, then, it


diffused across the polyurethane coating and migrated later to the
polyurethane coating surface. On the other hand, the extent of
migration of the parafn wax depended on the time after coating
deposition; the faster migration was produced one hour after
applying the polyurethane coating.
Moreover, the results obtained using two different prisms in
ATR-IR spectroscopy evidenced the removal of parafn wax from
the rubber surface cleaned by immersion in MEK in ultrasonic
bath. In the cleaned rubber, zinc stearate was located close to the
rubber surface, in a layer located 2 mm below the external surface.
Finally, the combined use of two prisms with different depths
of penetration in ATR-IR spectroscopy allowed the analysis of the
polyurethanerubber interface.

R. Torregrosa-Coque et al. / International Journal of Adhesion & Adhesives 31 (2011) 389397

Fig. 12. Variation of the water contact angle values (25 1C) on MEK surface
cleaned rubber, on polyurethane lm and on the polyurethane coating on MEK
surface cleaned rubber, as function of time after polyurethane coating deposition.

Acknowledgment
S. Alvarez-Garca thanks the Spanish Ministry of Education and
Innovation (MICINN) for her Juan de la Cierva postdoctoral contract
and R. Torregrosa-Coque thanks the University of Alicante for his PhD
grant. The nancial support provided by the Spanish Research Council
(MAT 2009-10234 and MAT 2010-19904 projects) and the Spanish
Technology Development AgencyCDTI (project entitled Development of an integral system for joining rubber-based materials
(20072009)) is gratefully acknowledged.
References
[1] Koenig JL. Spectroscopy of Polymers. 2nd edition. New York, USA: Elsevier;
1999. p. 77145.
[2] Pettit D, Carter AR. Adhesion of translucent rubber: application of infra-red
spectrometry to the problem. SATRA Bull 1964;1:165.
[3] Harrick NJ. Internal Reection Spectroscopy. New York: Harrick Scientic
Corporation; 1987.

397

[4] Pastor-Blas MM, Sanchez-Adsuar MS, Martn-Martnez JM. Weak boundary


layers in styrene-butadiene rubber. J Adhes 1995;50:191210.
[5] Ohm RF. In: Vanderbilt RT, editor. The Vanderbilt Rubber Handbook. 13th
edition. Norwalk: Company; 1990. p. 54.
[6] Nah SH, Thomas AG. Migration and blooming of waxes to the surface of
rubber vulcanizates. Rubber Chem Technol 1981;54(2):25565.
[7] Diamuro PJ, Paris HL, Fath MA. Wax protection. Rubber Chem Technol
1979;52:97384.
[8] Cataldo F. On the ozone protection of polymer having non-conjugated
unsaturations. Polym Degradation and Stability 2001;72:28796.
[9] Martn-Martinez JM. Improving adhesion of rubber. In: Bhowmick AK, editor.
Current Topics in Elastomer Research. Boca Raton: CRC Press; 2008. p. 761.
(Chapter 27).
[10] Choi S-S, Im S-H, Park J-H, Kim JS. Analysis of wax solubility of rubber
vulcanizates using wax solution in toluene and molten wax. Polym Test
2009;28:696701.
[11] Heyding RD, Russel KE, Varty TL, St-Cyr D. The normal parafns revisited.
Powder Diffr 1990;5:93100.
[12] Andries JC, Ross DB, Diem HE. Ozone attack and antiozonant protection of
vulcanized natural rubber; a surface study by attenuated total reectance
spectroscopy. Rubber Chem Technol 1975;48:419.
[13] Ansarifar A, Critchlow GW, Guo R, Ellis RJ, Haile-Meskel Y, Doyle B. Assessing
effect of the migration of a parafn wax on the surface free energy of natural
rubber. Rubber Chem Technol 2009;82:11330.
[14] Pushpa SA, Goonetilleke P, Billingham NC. Solubility of antioxidants in
rubber. Rubber Chem Technol 1996;69:88596.
[15] Torregrosa-Coque R, Alvarez-Garca S, Martn Martnez JM. Effect of temperature on the extent of migration of low molecular weight moieties to
rubber surface. Int J Adhes Adhes 2011;31:208.
[16] Lederer DA, Fath MA. Effects of wax and substituted p-phenylenediamine
antiozonants in rubber. Rubber Chem Technol 1981;54:41522.
[17] Van Ooij WJ, Nahmias M. Surface characterization of rubber by secondary ion
mass spectrometry. Rubber Chem Technol 1989;62:65682.
[18] Choi S-S. Migration behaviours of antiozonants to the surface in NR
vulcanizates, depending on the season: the effect of wax. J Appl Polym Sci
1999;71:198793.
[19] Choi S-S. Migration of antidegradants to the surface in nr vulcanizates:
inuence of content of carbon black. Bull Korean Chem Soc
1998;19(2):1704.
[20] Choi S-S. Migration behaviours of wax to the surface in rubber vulcanizates. J
Appl Polym Sci 1999;73:258793.
[21] Choi S-S. Strain and anisotropic effects on migration behaviours of antiozonant in carbon black-lled natural rubber vulcanizates. Polym Test
2002;21:7414.
[22] Ansarifar A, Critchlow GW, Guo R, Ellis RJ, Kirtley SP, Seymour B. Effect of
rubber chemicals on the surface free energy of NR and NR-SBR rubber blends.
J Rubber Res 2007;10(3):14860.
[23] Buffeteau B, Desbat D, Eyquem D. Attenuated total reection Fourier transform infrared microspectroscopy: theory and application to polymer samples. Vib Spectrosc 1996;1:2936.