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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
0143-7496/$ - see front matter & 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijadhadh.2011.03.003
l
2pnc sin2 yns =nc 2 1=2
390
Content (phr)
60
40
33
1.7
1.0
1.7
0.7
3.3
2.3
1.5
0.3
391
392
Fig. 5. ATR-IR spectra obtained with ZnSe prism of the rubber bulk and parafn wax lm.
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
As-received rubber
Bulk rubber
Cleaned rubber
Polyurethane lm
Parafn wax lm
107
83
85
66
110
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Fig. 8. SEM micrograph showing the polyurethane coating on the MEK surface
cleaned rubber.
Fig. 9. ATR-IR spectrum obtained with ZnSe prism of the polyurethane lm.
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.
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
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.
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.
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