Wax in Styrene

This article was downloaded by: [University of Otago]
On: 26 December 2014, At: 11:39

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954
Registered office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Journal of Adhesion Science and

Technology
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/tast20
Migration of Paraffin Wax to Sulfur

Vulcanized Styrene–Butadiene
Rubber (SBR) Surface: Effect of
Temperature
a a
Rafael Torregrosa-Coque , Sonia Álvarez-García & José
a
Miguel Martín-Martinez
a
Adhesion and Adhesives Laboratory , University of
Alicante , 03080 , Alicante , Spain
Published online: 24 Jul 2012.
To cite this article: Rafael Torregrosa-Coque , Sonia Álvarez-García & José Miguel Martín-
Martinez (2012) Migration of Paraffin Wax to Sulfur Vulcanized Styrene–Butadiene Rubber
(SBR) Surface: Effect of Temperature, Journal of Adhesion Science and Technology, 26:6,
813-826
To link to this article: http://dx.doi.org/10.1163/016942411X580027
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information
(the “Content”) contained in the publications on our platform. However, Taylor
& Francis, our agents, and our licensors make no representations or warranties
whatsoever as to the accuracy, completeness, or suitability for any purpose
of the Content. Any opinions and views expressed in this publication are the
opinions and views of the authors, and are not the views of or endorsed by
Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and
Francis shall not be liable for any losses, actions, claims, proceedings, demands,
costs, expenses, damages, and other liabilities whatsoever or howsoever caused
arising directly or indirectly in connection with, in relation to or arising out of the
use of the Content.
This article may be used for research, teaching, and private study purposes.
Any substantial or systematic reproduction, redistribution, reselling, loan, sub-
licensing, systematic supply, or distribution in any form to anyone is expressly
forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
Downloaded by [University of Otago] at 11:39 26 December 2014
Journal of Adhesion Science and Technology 26 (2012) 813–826
brill.nl/jast
Migration of Paraffin Wax to Sulfur Vulcanized

Styrene–Butadiene Rubber (SBR) Surface: Effect of
Temperature
Rafael Torregrosa-Coque, Sonia Álvarez-García and José Miguel Martín-Martinez ∗

Adhesion and Adhesives Laboratory, University of Alicante, 03080 Alicante, Spain
Received on 20 March 2011
Abstract
Because of the low molecular weight of some additives (e.g., antiozonants) in the vulcanized styrene–
butadiene rubber (SBR) formulation, they are able to migrate and diffuse to the surface creating a weak
boundary layer which is deleterious to adhesion. However, the factors favouring or inhibiting the migration
of antiozonants to the vulcanized SBR surface have not been fully understood. This work was conducted
to determine the influence of the temperature on the migration of antiozonant paraffin wax to the surface
of a commercial sulphur vulcanized styrene–butadiene rubber. The antiozonant migration experiments were
performed for 15 hours in an oven at different temperatures ranging from 40° to 90°C. The changes in the
vulcanized SBR surface were monitored by ethylene glycol contact angle measurements, ATR–IR spec-
troscopy and scanning electron microscopy (SEM). Additionally, the weight loss of the vulcanized SBR
after each heat treatment was recorded.
The heating of vulcanized SBR at different temperatures for 15 hours caused a partial removal of paraffin
wax from the surface. By heating at a temperature close to the paraffin wax melting point, the crystals of
paraffin wax on the vulcanized SBR surface were melted, causing a decrease in the thickness of the paraffin
wax film on the surface, which became smoother too. Furthermore, some paraffin wax was evaporated
during heat treatment, especially for the vulcanized SBR heated at 90°C. However, even after heating at
90°C, a thin film of paraffin wax always remained on the vulcanized SBR surface. Finally, the migration of
zinc stearate to the paraffin wax layer on the vulcanized SBR surface occurred by heating at 90°C for 15 h.
© Koninklijke Brill NV, Leiden, 2012
Keywords
Styrene butadiene rubber, paraffin wax, zinc stearate, weak boundary layer, ATR–IR spectroscopy, contact
angle measurements, scanning electron microscopy
*To whom correspondence should be addressed. Tel.: +34 965 90 39 77; Fax: +34 965 903454; e-mail:
jm.martin@ua.es
© Koninklijke Brill NV, Leiden, 2012 DOI:10.1163/016942411X580027

814 R. Torregrosa-Coque et al. / J. Adhesion Sci. Technol. 26 (2012) 813–826
1. Introduction
Rubbers are polymeric materials with high elasticity commonly used in automo-
tive, footwear and construction industries. Rubber polymers by themselves have
poor mechanical properties but by using a variety of fillers (e.g., carbon black and
silica) and other additives, it is possible to improve their properties in order to ob-
tain the best achievable materials for different applications. The nature and number
of additives in the formulations depends on the chemical nature of the base rubber
polymer and the properties expected in the finished products [1].
The sulfur-vulcanized styrene-butadiene rubbers (SBR) are the most widely used
in the world, constituting about 40–50% of the total synthetic rubber consumed
presently. They are widely used in footwear, adhesives manufacturing, moulded or
extruded goods, and as modifiers for asphalt and thermoplastic resins. Once their
desired properties are attained by proper compounding and curing the rubber prod-
ucts, it becomes necessary to prevent these properties from changing during service,
especially from oxidation and ozone attack. This is usually achieved by adding ap-
propriate antioxidant and antiozonant moieties (mainly paraffin wax) in the SBR
formulation. In this way, the processing of SBR compounds includes generally the
addition of fillers, plasticizers, antioxidants, vulcanizing agent and activators. It is
known that during the rubber vulcanization, zinc oxide and stearic acid react to
produce zinc stearate, which is combined with hexamethylene tetramine to form
an unstable complex [2]. After vulcanization, the decomposition of this complex
can occur and zinc stearate can migrate to the vulcanized SBR surface, giving anti-
adhesion property.
Some additives in the vulcanized SBR formulation, especially petroleum waxes
antiozonants, may show a phenomenon which is known as blooming. By bloom-
ing, the waxes incorporated into the rubber during the mixing process are able of
migrating to the vulcanized SBR surface during vulcanization (and even after vul-
canization) and with time the surface can be covered by a thin wax film [3]. In this
way, the wax blooming allows to protect the vulcanized SBR against ozone attack
by formation of an impervious physical barrier [4, 5]. This migration is supposed
to occur continuously until equilibrium is reached between the wax on the surface
and in the vulcanized SBR bulk. Therefore, the balance between solubility and mi-
gration would govern the ability of the wax to protect the vulcanized SBR against
ozone attack. Furthermore, the extent of migration of the wax to the vulcanized
SBR surface is a function of the solubility and mobility of the wax, which depends
on the rubber composition, the specific wax nature, and the exposure to ozone con-
ditions (e.g., temperature, time, etc.) [6]. Furthermore, this migration of the wax
depends on the density and adhesion of the vulcanized SBR [4].
Nowadays, two types of waxes are used to protect rubber against ozone, paraf-
finic and microcrystalline. Paraffinic waxes are mainly composed of straight car-
bon chains (normal alkanes) whose chemical structures and melting points depend
mainly on their size. In general, the melting point of the wax increases with the
hydrocarbon length from 30°C (n-C21 H44 ) to 79°C (n-C40 H82 ) [7]. The most com-
R. Torregrosa-Coque et al. / J. Adhesion Sci. Technol. 26 (2012) 813–826 815
monly used waxes have melting points of 50–60°C and, for this reason, during
mixing and vulcanization (in which the rubber temperature reaches well above
200°C), 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 rubber becomes supersaturated with the wax [8]. As a re-
sult, some crystallization of the wax occurs on the rubber surface to reduce the
concentration of the dissolved wax to its equilibrium value. Furthermore, the mi-
gration of the wax to the rubber surface is influenced by the solubility of the wax
below its melting point [9].
Although blooming is expected to protect the vulcanized SBR surface, however
the wax film on the surface affects its interfacial and adhesion properties. In fact,
the presence of the wax film implies a reduction in vulcanized SBR surface free
energy, which could adversely affect the rubber adhesion to itself as well as to other
materials.
The existence of weak boundary layer of antiozonant paraffin wax on the surface
of vulcanized SBR has been recognized as one of the main causes of its poor adhe-
sion to adhesives [10]. Additionally, the zinc stearate produced during vulcanization
by reaction of stearic acid and zinc oxide can migrate also to the vulcanized SBR
surface and may affect the rubber adhesion also. Nevertheless, the blooming of zinc
stearate is not as detrimental as paraffin wax on adhesion properties of vulcanized
SBR [11].
The first study on the diffusion and blooming of antiozonant wax to the rubber
surface was carried out by carbon-14 tracing in synthetic and natural rubber con-
taining an oil extender [12]. Lederer and Fath [13] confirmed blooming of wax on
rubber surface by scanning electron microscopy (SEM) and they stated that a sig-
nificant increase in rubber ozone protection was achieved by only a small increase
in bloomed wax concentration. Choi [14–16] reported several studies on the mi-
gration behaviour of wax to rubber surfaces. He found that the amount of wax that
migrated to the surface decreased as the length of the carbon chain increased, until
reaching n-C28 H58 [14], and also that the wax film on the rubber surface influenced
the migration of the wax [15]. However, the thickness of the wax film on the rubber
surface had only little effect on the extent of the migration of wax from the bulk to
the rubber surface [16, 17].
More recently, Ansarifar et al. [9] measured the surface energy of natural rubber
compounded with different ingredients, using contact angle measurements. They
also used SSIMS (Static Secondary Ion Mass Spectrometry) and found significant
changes because of the migration of the additives to the natural rubber surface. They
reported that the stearic acid decreased the surface energy of the rubber. In fact, they
noted that when rubber compounded with wax was stored at ambient temperature
for a few days, the surface energy decreased because of the migration of the wax
to the natural rubber surface. The highest rate of surface energy reduction was pro-
duced during the first three hours, and after that, it decreased at a much slower rate;
after two days, the surface energy of the natural rubber remained constant. SSIMS
measurements were useful to confirm the presence of paraffin wax on the natural
rubber surface [18].
Even considering the above studies, the wax migration process in vulcanized
SBR has not been sufficiently studied and factors favouring or inhibiting the migra-
tion of antiozonants to the vulcanized SBR surface have not been fully understood.
An adequate knowledge of these factors will avoid or prevent the creation of weak
boundary layers.
In this study a new insight into the influence of the temperature on the migration
of low molecular weight substances, particularly paraffin wax and zinc stearate,
to the surface of a vulcanized SBR formulation was gained using ATR–IR spec-
troscopy, contact angle measurements and scanning electron microscopy (SEM).
Besides, weight losses after heat treatment of the vulcanized SBR at different tem-
peratures have been recorded.
2. Experimental
2.1. Materials
A sulfur vulcanized styrene butadiene rubber (R2) provided by Iresa Consul-
tores S.L. (Elda, Spain) was used. This rubber is used in the manufacture of soles
in the footwear industry. The generic R2 rubber composition is given in Table 1,
but the specific compounding and vulcanization procedure was not disclosed by the
manufacturer. R2 rubber is a mixture of synthetic styrene–butadiene rubber (SBR
1502) and natural rubber (NR pale crepe grade) and contains precipitated silica as
filler. During vulcanization, the zinc oxide reacts with the stearic acid producing
zinc stearate. The R2 rubber composition also includes a microcrystalline paraffin
wax as antiozonant (Tiozone 2000 provided by Iberceras, Madrid, Spain). The wax
melting point is 64–69°C (measured according to ASTM D.938) and its viscosity
Table 1.
Composition of the vulcanized styrene–butadiene rubber R2. Contents
are given in phr (parts per hundred parts of rubber)
Ingredient Content (phr)
SBR 1502 60
NR (pale crepe grade) 40
Precipitated silica 33
Zinc oxide 1.7
Stearic acid 1.0
Poly(ethylene glycol) 1.7
Paraffin wax 0.7
Plasticizer 3.3
Sulfur 2.3
2-Mercaptobenzothiazol disulfide 1.5
Tetramethylthiuram disulfide 0.3
at 100°C is 5 mPa s (ASTM D.3236). It has been established that both the micro-
crystalline paraffin wax and the zinc stearate are responsible for the poor adhesion
of the vulcanized SBR [19].
2.2. Experimental Techniques
With the aim to investigate the changes produced on the as-received R2 rubber
surface and the migration from the bulk to the surface of both paraffin wax and zinc
stearate, several pieces of the as-received R2 rubber were heat treated in an oven
between 40 and 90°C for 15 h. The dimensions of the R2 rubber test pieces were
26 × 10 × 5 mm. The experiments were designed in such a way that a uniform
temperature was reached on the whole R2 rubber sample during heat treatment.
Since the properties of the bulk and the surface of the as-received R2 rubber are
different, the properties of the bulk R2 were also studied. Fresh bulk R2 rubber
pieces were obtained by cutting the as-received R2 rubber pieces in half longitudi-
nally using a scalpel blade. To avoid low molecular weight substances migration,
the fresh cut bulk R2 rubber pieces were immediately analyzed by contact angle
measurement and ATR–IR spectroscopy. On the other hand, the solid Tiozone 2000
wax (used in the R2 rubber formulation) was melted and placed on a Teflon plate
in order to obtain a paraffin wax film. The wax film obtained was cooled down for
48 h at room temperature before analysis.
2.2.1. Contact Angle Measurements
The wettability of the as-received and heat treated R2 rubber surfaces was evaluated
by contact angle measurements using a Ramé–Hart 100 goniometer (Ramé–Hart,
Netcong, NJ, USA). The rubber test pieces were placed into the hermetic and
isothermal (25°C) chamber of the goniometer previously saturated with ethylene
glycol vapour for at least 10 min before placing the drop. Drops (4 µl) of ethy-
lene glycol (test liquid) were placed on the rubber surface using a micro-syringe
(Hamilton Instruments) provided with a flat end needle. Contact angle values were
obtained 10 min after ethylene glycol drop deposition on the rubber surface. The
experimental error was ±2°.
2.2.2. ATR–IR Spectroscopy
The chemical changes in the as-received and heat treated R2 rubber were monitored
by IR spectroscopy using Tensor 27 equipment (Bruker Optik, Madrid, Spain). To
avoid deep penetration of the IR radiation into the sample, the attenuated total re-
flectance (ATR–IR) method was employed This technique allows to analyze the
chemical modifications produced in about 4 µm depth of the rubber under the ex-
perimental conditions used in this study: zinc selenide prism, angle of incidence of
the IR radiation of 45°, 200 scans averaged at a resolution of 4 cm−1 .
2.2.3. Scanning Electron Microscopy (SEM)
The modifications in the topography of the as-received and heat treated R2 rub-
ber surfaces were analyzed using a JEOL JSM-840 (Peabody, MA, USA) scanning
electron microscope. The rubber samples were gold-coated before analysis and the
energy of the electron beam was 30 kV.
2.2.4. Weight Loss Measurements
The weight losses of the R2 rubber samples during heating were determined as:
Wloss (%) = 100 × (Wbh − Wah )/Wbh , (1)
where Wah and Wbh are the weights of the rubber samples after and before heating,
respectively.
3. Results and Discussion

Figure 1 shows the ATR–IR spectrum of the external surface of the as-received R2
rubber. The ATR–IR spectrum of the as-received R2 rubber shows the absorption
bands due to butadiene and styrene. Bands at 1645 and 963 cm−1 correspond to
acyclic C–C bond and trans-1,4-C=C stretching in butadiene, respectively. Other
Figure 1. ATR–IR spectra of the bulk and as-received R2 rubber, and the paraffin wax.
butadiene absorption bands are CH2 wagging motion (1379 and 1260 cm−1 ) and
CH2 in-plane deformation (1645 cm−1 ). Styrene absorptions occur at 698 (C–H
out-of-plane deformation), and 912, 795 and 755 cm−1 (aromatic C–H stretch-
ing). The ATR–IR spectrum of the as-received R2 rubber also shows a broad and
moderately intense band at 1062 cm−1 due to the silica filler (Si–O stretching). In
addition, the absorption band at 1537 cm−1 corresponds to zinc stearate. The most
intense IR absorption bands in the ATR–IR spectrum of the as-received R2 rubber
(2915, 2845, 1473, 730 and 719 cm−1 ) correspond to the characteristics CH2 rock-
ing bands observed in the ATR–IR spectrum of the paraffin wax (Fig. 1) indicating
that in the surface and/or near the surface a film of paraffin wax was covering the
rubber [20]. As the paraffin wax possesses a reduced number of CH3 end-groups,
the CH3 absorption at 2950 cm−1 may also indicate the presence of paraffin wax.
To confirm the presence of paraffin wax in the vicinity of the as-received R2 rub-
ber surface, the ATR–IR spectrum of the as-received bulk R2 rubber was obtained
(Fig. 1). The ATR–IR spectrum of the bulk R2 rubber shows a significant decrease
in the relative intensity of the bands at 2965, 2919 and 2851 cm−1 (due to CH3
and CH2 groups of the paraffin wax) and of the band at 1537 cm−1 (zinc stearate).
Furthermore, with respect to the ATR–IR spectrum of the as-received R2 rubber,
the relative intensities of the bands due to rubber polymer (1645, 1379, 1260, 912,
963, 698 cm−1 ) and silica filler (1062 cm−1 ) increase. Therefore, the presence of
paraffin wax and zinc stearate close to the surface of the as-received R2 rubber is
confirmed, indicating that there is a concentration gradient of these moieties be-
tween the bulk and the R2 rubber surface.
The wettability of the as-received R2 rubber (surface and bulk) and paraffin wax
surfaces was analyzed. The contact angle value on the as-received R2 rubber (85° ±
2) was comparable to that of the paraffin wax (88° ± 2) and clearly higher than the
contact angle value on the bulk R2 rubber (62° ± 2). This confirmed that a wax film
was covering the as-received R2 rubber surface.
The topography of the as-received R2 rubber surface was studied by SEM
(Fig. 2). The SEM micrograph of the as-received R2 rubber surface shows that
it is quite flat and is fully covered with patches of paraffin wax crystals. Therefore,
the paraffin wax layer on the as-received R2 rubber is constituted of agglomerates
of wax crystals of crumbly aspect.
The chemistry of the as-received R2 rubber was modified by heat treatment at
different temperatures for 15 hours. The ATR–IR spectrum of the 45°C heat treated
R2 rubber (Figure 3) shows several changes as compared to as-received R2 rub-
ber: (i) significant decreases in the relative intensities of the bands at 2950, 2915
and 2845 cm−1 due to CH3 and CH2 groups of the paraffin wax; (ii) the almost
complete disappearance of the band at 719 cm−1 ascribed to paraffin wax; and (iii)
increases in the relative intensities of the bands at 1062 (due to the silica), 963 (due
to butadiene) and 698 cm−1 (due to styrene). These modifications indicate that the
paraffin wax covering the as-received R2 rubber surface is partially removed by
heating at 45°C for 15 hours. On the other hand, a higher relative intensity of the
Figure 2. SEM micrograph of the as-received R2 rubber. Higher magnification micrograph is also
given (inset).
(a)
Figure 3. (a) ATR–IR spectra of the R2 rubber after heat treatment at different temperatures for 15 h,
and (b) 1550–700 cm−1 region in the ATR–IR spectra.
band due to the C–O stretching of zinc stearate (1537 cm−1 ) is clearly observed
in the 45°C treated sample. This would point toward the presence of a higher con-
centration of zinc stearate near the R2 rubber surface when the sample is heated
at 45°C. Taking into account that the ATR–IR spectra were obtained with a ZnSe
(b)
Figure 3. (Continued.)
prism, a penetration of about 4 µm into the rubber can be expected [21, 22], so it
would be reasonable to assume that the higher intensity of the zinc stearate band
in the 45°C treated R2 rubber is due to the removal of paraffin wax from the sur-
face. In fact, it has been shown [16] that the amount of wax migrating to vulcanized
SBR surface is sensitive to the molecular weight, melting point and the end-to-end
distances of the normal alkanes in the wax. According to Choi [17], for a vulcan-
ized rubber containing wax of similar nature as the R2 rubber, the thickness of
the wax layer in the rubber surface would be about 2 µm. Therefore, the IR beam
could only penetrate and analyze the film of wax and a bit of stearate layer situ-
ated under the wax in the as-received R2 rubber. Nevertheless, after heat treatment
at 45°C, by partial melting of the wax on the R2 rubber surface, the thickness of
the wax film is reduced and becomes more homogeneous. As a consequence, the
zinc stearate and the rubber polymer underneath the wax layer can be analyzed by
ATR–IR spectroscopy. This is confirmed by the topographical changes observed in
the SEM micrograph of Fig. 4(a), in which it is shown that the crumbly surface of
the as-received R2 rubber surface turns into a smoother layer after heating at 45°C.
Moreover, silica particles can be seen as they are exposed to the R2 rubber surface
after heating at 45°C.
(a) (b)
(c)
Figure 4. SEM micrographs of the R2 rubber heat treated at (a) 45°C, (b) 68°C and (c) 90°C. Higher
magnification micrographs are also given (inset).
By increasing the heat treatment temperature above 45°C, the intensities of the
IR bands due to paraffin wax in the R2 rubber are strongly reduced and at the same
time the intensities of the rubber bands are increased (Fig. 3). Thus, by treatment
at 68°C, the ATR–IR spectrum of the R2 rubber showed additional decreases in
the relative intensities of the paraffin wax bands and an increase in the intensity of
the zinc stearate band, with respect to the as-received R2 rubber (Fig. 3(b)). This
temperature, i.e., 68°C, is close to the paraffin wax melting point, so the melting of
the paraffin wax film on the R2 rubber surface can be anticipated, giving a thinner
film. As a result of the decrease in paraffin wax thickness, the penetration of the IR
beam into the R2 rubber is higher and the ATR–IR spectrum of the 68°C heated R2
rubber shows more intense butadiene, styrene, silica and zinc stearate bands. On the
other hand, the SEM micrograph (Fig. 4(b)) shows that the R2 rubber surface treated
at 68°C becomes irregular, and the homogeneous film of wax observed in the R2
rubber surface treated at 45°C disappears as the temperature increases. Therefore,
when the temperature is close to the paraffin wax melting point, the wax does not
cover the entire R2 rubber surface. Even though the wax concentration is lower
Figure 5. Contact angle values (ethylene glycol, 25°C) on R2 rubber surface as a function of heat
treatment temperature. The dotted line - - - corresponds to the contact angle value on the paraffin wax
surface and the dotted line -··-··- corresponds to the contact angle value on the bulk R2 rubber.
as the temperature increases, a thin layer of wax still remains on the R2 rubber
surface.
This statement is supported by contact angle measurements on the R2 rubber
treated at different temperatures. Figure 5 shows that the contact angle values on the
R2 rubber surface decrease with respect to that of the as-received R2 rubber as the
temperature increases until 68°C. This indicates that the increase in wettability is
likely due to the removal of hydrocarbon moieties (paraffin wax) from the R2 rubber
surface. The decrease in the contact angle value is more noticeable particularly on
the rubber treated at 68°C, and this indicates that when the temperature is close to
the paraffin wax melting point, the paraffin wax removal is facilitated. However, all
heat treated R2 rubber samples have higher contact angle values than that of the
bulk rubber, which point toward the presence of some remaining paraffin wax layer
on the R2 rubber surface (Fig. 5).
By considering the results of the ATR–IR spectroscopy, the contact angle mea-
surements and the SEM micrographs, the reduction of the paraffin wax film on the
R2 rubber surface by increasing the temperature between 45–68°C is supported.
Moreover, it would be reasonable to assume that evaporation of the paraffin wax
from the R2 rubber surface occurs during heating below 68°C. This assumption is
supported by the weight losses in the R2 rubber during heating. In fact, after heating
to 68°C a weight loss of 0.3–0.4% in all R2 rubber samples was obtained (Fig. 6).
The higher is the temperature, the lower is the weight loss in the R2 rubber. There-
fore, when the temperature is near the paraffin wax melting point, the weight loss is
lower. This could be explained considering the thinner film of melted paraffin wax
on the R2 rubber surface after heating at 68°C that would inhibit the evaporation of
paraffin wax.
Figure 6. Weight loss of the R2 rubber heat treated at different temperatures for 15 h.
On the other hand, when the treatment temperature is increased well above the
paraffin wax melting point, a completely different behaviour is observed. The ATR–
IR spectrum of the 90°C treated R2 rubber (Fig. 3) shows significant increases in the
relative intensities of the bands at 1062 (due to the silica), 963 (due to butadiene),
and at 912 and 698 cm−1 (corresponding to styrene) with respect to the relative
intensities in the ATR–IR spectrum of the as-received R2 rubber. Moreover, the rel-
ative intensities of the 719 (characteristic of paraffin wax) and 1537 cm−1 (ascribed
to zinc stearate) bands decrease more than in the R2 rubber heated at lower temper-
atures. Therefore, the paraffin wax film covering the as-received R2 rubber surface
is partially removed after heat treatment at high temperature (i.e., 90°C). In fact,
the maximum relative intensity of the 1537 cm−1 band in the ATR–IR spectrum is
observed in the R2 rubber heated at 90°C. Thus, after heating at 90°C the thick-
ness of the paraffin wax layer decreases and the IR beam allows to analyze the zinc
stearate layer present underneath. In fact, according to Fig. 3(b), the zinc stearate
concentration near the R2 rubber surface heated at 90°C increases with respect to
the as-received rubber, indicating that the zinc stearate migration is favoured at
temperature close to 90°C.
Figure 4(c) shows the SEM micrograph of the R2 rubber heated at 90°C. The
patches of paraffin wax covering the as-received R2 rubber surface have virtually
disappeared upon heating at 90°C for 15 h. This is in good agreement with the de-
creases in the relative intensities of the paraffin wax bands in the ATR–IR spectrum
in Fig. 3. Moreover, after heating above 70°C, the weight loss of the R2 rubber
increases up to 0.85%. The higher is the temperature, the higher is the weight loss
of the R2 rubber. Therefore, by heating at temperatures higher than the paraffin
wax melting point, some patches of wax on the as-received R2 rubber surface are
removed by sublimation, instead of melting. Thereafter, paraffin wax layer was thin-
ner and zinc stearate migration to the R2 rubber surface was favoured.
Furthermore, the contact angle value on the R2 rubber heated at 90°C, i.e.
78 degress (Fig. 5) decreases with respect to that on the as-received R2 rubber
measured at 20°C (85 degrees). This supports the removal of paraffin wax from the
R2 rubber surface. However, the contact angle value on the 90°C heated R2 rubber
is somewhat higher than the values on the R2 rubber treated at lower temperatures,
even though paraffin wax concentration on the rubber surface is less. Thus an in-
creased diffusion of the zinc stearate to the R2 rubber surface occurs. In any case,
all heat treated R2 rubber samples show higher contact angle values than that of
the bulk rubber, which point once more toward the existence of some remaining
paraffin wax layer on the R2 rubber surface.
4. Conclusion
The heating of R2 rubber at different temperatures for 15 hours resulted in partial
removal of paraffin wax from its surface. By heating at temperature close to the
paraffin wax melting point, the crystals of the paraffin wax on the R2 rubber sur-
face were melted, causing a decrease in the thickness of the paraffin wax film on
the rubber surface. Thus, a smoother paraffin wax film was formed. Furthermore,
some paraffin wax was evaporated during heat treatment. Two different behaviours
were observed: (i) for heating performed at temperatures lower than the paraffin
wax melting point, the higher the temperature the lower the weight loss, due to the
melted paraffin wax layer formed that prevented wax evaporation; (ii) for heating
at temperatures higher than 70°C, the weight loss increased with the temperature,
because of the sublimation of paraffin wax instead of melting. However, even after
heating at 90°C, a thin film of paraffin wax still remained on the R2 rubber surface
which was detected by contact angle measurements. Finally, a critical temperature
close to 90°C existed at which the migration of zinc stearate present underneath the
paraffin wax layer to the R2 rubber surface was favoured.
Acknowledgements
S. Álvarez-García and R. Torregrosa-Coque thank the Spanish Ministry of Edu-
cation and Innovation (MICINN) for granting Juan de la Cierva postdoctoral con-
tract and the University of Alicante PhD grant, respectively. The financial support
provided by the Spanish Ministry of Education and Innovation (MAT2002-02463
project) and the Spanish Technology Development Agency — CDTI (project enti-
tled “Development of an integral system for joining rubber-based materials (2007–
2009)” is gratefully acknowledged.
References
1. B. Adhikari, S. N. Maiti and T. K. Khanra, in: Polymeric Materials Encyclopedia, Vol. 10,
J. C. Salamone (Ed.), p. 7578. CRC Press, Boca Raton, FL (1996).
2. R. F. Ohm (Ed.), The Vanderbilt Rubber Handbook, 13th edn, p. 54. R. T. Vanderbilt Company,
Norwalk, CT, USA (1990).
3. S. H. Nah and A. G. Thomas, Rubber Chem. Technol. 54, 255 (1981).
4. P. J. Diamuro, H. L. Paris and M. A. Fath, Rubber Chem. Technol. 52, 973 (1979).
5. F. Cataldo, Polym. Degrad. Stabil. 72, 287 (2001).
6. S.-S. Choi, S.-H. Im, J.-H. Park and J. S. Kim, Polym. Testing 28, 696 (2009).
7. R. D. Heyding, K. E. Russel, T. L. Varty and D. St-Cyr, Powder Diffraction 5, 93 (1990).
8. J. C. Andries, D. B. Ross and H. E. Diem, Rubber Chem. Technol. 48, 41 (1975).
9. A. Ansarifar, G. W. Critchlow, R. Gur, R. J. Ellis, Y. Haile-Meskel and B. Doyle, Rubber Chem.
Technol. 82, 113 (2009).
10. J. M. Martín-Martinez, in: Current Topics in Elastomer Research, A. K. Bhowmick (Ed.), Ch. 27,
p. 761. CRC Press, Boca Raton, FL (1998).
11. A. Bernabéu-Gozálvez, M. M. Pastor-Blas and J. M. Martín-Martínez, in: Proceeding of World

Polymer Congress, 37th International Symposium on Macromolecules MACRO 98, Gold Coast,
Australia, p. 70 (1998).
12. J. E. Lewis and M. L. Deviney, Rubber Chem. Technol. 40, 1570 (1967).
13. D. A. Lederer and M. A. Fath, Rubber Chem. Technol. 54, 415 (1981).
14. S.-S. Choi, J. Appl. Polym. Sci. 71, 1987 (1999).
15. S.-S. Choi, Bull. Korean Chem. Soc. 19, 170 (1998).
16. S.-S. Choi, J. Appl. Polym. Sci. 73, 2587 (1999).
17. S.-S. Choi, Polym. Testing 21, 741 (2002).
18. A. Ansarifar, G. W. Critchlow, R. Guo, R. J. Ellis, S. P. Kirtley and B. Seymour, J. Rubber Res.
10, 148 (2007).
19. M. D. Romero-Sánchez and J. M. Martín-Martínez, J. Adhesion Sci. Technol. 22, 147 (2008).
20. D. Lin-Vien, N. B. Colthup, W. G. Fateley and F. G. Grasselli, The Handbook of IR and Raman
Characteristic Frequencies of Organic Molecules. Academic Press, New York (1991).
21. D. Petit and A. R. Carter, J. Adhesion 5, 333 (1973).
22. J. L. Koenig, Spectroscopy of Polymers, 2nd edn, Ch. 3, p. 77. Elsevier, New York (1999).

Wax in Styrene

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Wax in Styrene

Uploaded by

Copyright:

Available Formats

This article was downloaded by: [University of Otago]

On: 26 December 2014, At: 11:39

Journal of Adhesion Science and

Migration of Paraffin Wax to Sulfur

To link to this article: http://dx.doi.org/10.1163/016942411X580027

PLEASE SCROLL DOWN FOR ARTICLE

Migration of Paraffin Wax to Sulfur Vulcanized

Rafael Torregrosa-Coque, Sonia Álvarez-García and José Miguel Martín-Martinez ∗

Received on 20 March 2011

© Koninklijke Brill NV, Leiden, 2012 DOI:10.1163/016942411X580027

Ingredient Content (phr)

3. Results and Discussion

11. A. Bernabéu-Gozálvez, M. M. Pastor-Blas and J. M. Martín-Martínez, in: Proceeding of World

You might also like