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Oxidation of rubbers analysed by HATR/IR spectroscopy

Article  in  Polymer Degradation and Stability · November 1998

DOI: 10.1016/S0141-3910(98)00028-7

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 Polymer Degradation and Stability 62 (1998) 395±401
# 1998 Elsevier Science Limited. All rights reserved
Printed in Great Britain
PII: S0141-3910(98)00028-7 0141-3910/98/$Ðsee front matter

Oxidation of rubbers analysed by HATR/IR

spectroscopy
F. Delor,a* N. Barrois-Oudin,b X. Duteurtre,c C. Cardinet,d J. Lemairea & J. Lacoste a

a
Laboratoire de Photochimie MoleÂculaire et MacromoleÂculaire UMR CNRS 6505, Universite Blaise Pascal et Ensonimie
(Clermont-Ferrand) F-63177 Aubiere Cedex, France
b
Renault, Direction de la Recherche F-92508 Rueil-Malmaison Cedex, France
c
Renault, Direction de l'lngenieÂrie des MateÂriaux F-92508 Rueil-Malmaison Cedex, France
d
Hutchinson, Centre de Recherche F-45120 Chalette/Loing, France

(Received 12 January 1998; accepted 27 January 1998)

The presence of large amounts of carbon black in number of industrial applica-

tions of rubbers makes their analytical study by infrared spectroscopy dicult,
particularly their chemical evolution upon ageing . The present paper reports the
use of a Horizontal Attenuated Total Re¯ectance accessory equipped with a
germanium crystal. HATR (Ge) /FTIR analysis of both thermal-and photo-
oxidations of EPDM, CR and NBR were ®rst validated by conventional transmis-
sion spectroscopy in the absence of carbon black. Then, HATR (Ge) was used
with fully formulated rubbers with the aim of studying their long term behaviour.
In¯uence of temperature, UV exposure, carbon black or stress as well as the
oxidation pro®le across the materials or the identi®cation of carboxylic acids/
carboxylates groups have been examined. # 1998 Elsevier Science Limited. All
rights reserved

1 INTRODUCTION The changes in chemical properties are usually fol-

Many elastomers, especially those containing dou-
ble bonds, have very low stability to oxidation
initiated by thermal, UV or g-radiations. However
in most applications, these materials are strongly
modi®ed by vulcanisation and by the addition of
large amounts of carbon black (reinforcing agent).
This generally results in a large improvement of
ageing properties which can be further improved
by the addition of stabilizers.
Ageing (oxidation) generally results in dra-
matic changes of physical properties like crack-
ing or loss of tensile properties. In fact, these
modi®cations are a consequence of a chemical
evolution of the material and the speci®c study of
chemical changes in the ®rst stages of the reaction
is one of the best ways to predict the long term
behaviour.
*To whom correspondence should be addressed. E-mail:
lacoste@cicsun.univ-bpclermont.fr
.
lowed by FTIR spectroscopy which is a very sen-
sitive and non-destructive technique. However, the
large content in carbon black (up to 50 wt%) in
most elastomer formulations limits conventional
transmission IR spectroscopy (TIR) to the study of
very thin samples (few microns) obtained with a
cryogenic microtome.1 Analyses involving photo-
acoustic detection (PAS) or re¯exion techniques
based on the use of crystals with high refractive
indexes (ATR) are probably suitable alternatives
but the analysis is then limited to the surface of the
sample.
The present paper reports on the comparison of
FTIR techniques (TIR, PAS, ATR) on transparent
materials in order to validate the use of horizontal
ATR with germanium crystal (HATR (Ge)) for the
study of industrial formulations (based on
EPDM, NBR and CR) found in automotive
applications (hoses, belts, weatherstrips etc.). In a
second study this technique will be applied to the
study of parameters acting on ageing process
396 F. Delor et al.
(UV or thermal exposure, in¯uence of stress,
oxidation pro®le across the materials...).
2 EXPERIMENTAL
Two formulations based on EPDM* (MI, peroxide
=2ncryst sin2  ÿ …nsample =ncryst †2 †
crosslinked, for engine applications (hoses, belts,...)
and M2, sulfur vulcanized, for outdoor applica-
tions (weatherstrips) and two formulations M3 and
M4 based respectively on chloroprene rubber (CR)
and nitrile butadiene rubber (NBR) for engine
applications were provided by Hutchinson, France.
For each material, simpli®ed formulations (without
carbon black, without stabilizer...) were also avail-
able. Typical formulation contained: the polymer
matrix (30±50 wt%), carbon black (30±50 wt%),
zinc oxide (2±6 wt%), curing system (1.5±6 wt%),
softeners (8±20 wt%) and stabilizers (0-2 wt%).
Thermal ageing was performed at 100 and 150 C
in ventilated air oven with natural convection.
Photoageing was performed at 60 C in a
SEPAP-MPC chamber already described else-
where.2 This device is characterized by its sources:
four medium pressure mercury lamps ®ltered with
borosilicate envelopes (g5300 nm) and by careful
control of the exposed surface temperature with a
thermocouple in close contact with one of the
samples. Samples were rotated at a constant dis-
tance from the sources.
FTIR analysis were performed in transmission
(TIR), emission (PAS) and re¯exion (ATR) modes
on Nicolet instruments (205, 800 and Impact 400
spectrometers)
. transmission analyses were made on ®lms (90±
100 m) molded by compression in a heated
press or cut with a cryogenic microtome
(Reichert Jung LN20) (few microns);
. photoacoustic analyses were made by using a
MTEC chamber (Nicolet) ®lled with helium,
samples were cut into 9 mm discs. Details of
this technique for photooxidation studies are
reported elsewhere;3
. horizontal attenuated total re¯ectance ana-
lyses were performed by using a Spectratech
accessory (Baseline) equipped with 45 ZnSe
(n=2.4) or Ge (n=4) crystals (5x5O mm).
The pressure on samples was controlled by
using a torque screwdriver adjusted at 0.3
*E=ethylene, P=propylene, DM=ENB=5-ethylidene, 2-
norbornene.
N.m (Facom A200BA). All the spectra were
roughly corrected with conventional software
in order to cancel the variation of the ana-
lysed thickness (dp) with the wavelength (g)
according to the Harrick equation:4
q
…dp ˆ
Oxidation pro®les across materials were
obtained by coupling TIR analysis with a IR-
NIC-plan microscope (analysis of each 15 m)
or by HATR (Ge) analysis with successive
abrasions of the surface with a rotating abra-
simeter (Presi) equipped with SiC discs (each
15 m). In that case the rotation speed of the
discs (on samples) was low enough to avoid
overheating of samples.
In addition, a gas treatment with SF4
allowed us to characterize carboxylic acids
and zinc carboxylate groups deriving from
oxidation:
RCOOH SF4
ÿÿ
ÿ! RCOF
RCOOÿ
The resulting acid ¯uorides absorb close to 1840
cmÿ1.
3 RESULTS AND DISCUSSION
3.1 Comparison of FTIR methods (TIR, PAS, HA
TR)
Films with di€erent thicknesses used from EPDM
(MI and M2) and CR (M3) without carbon black
and softeners were analysed with the three meth-
ods. The variations of absorption bands following
the Beer Law are reported in Fig. 1. It can be
deduced that the thicknesses analysed by each
technique are in the range: 0 to 80±100 m in
transmission, 15±20 m in PAS, 22±27 m in
HATR (ZnSe) and 3±5 m in HATR (Ge), respec-
tively.
Figure 2 shows a comparison of spectroscopic
changes upon the thermal oxidation at 150 C of
EPDM (MI) ®lms (carbon black un®lled) with the
three methods. The general shape is very similar
for the three spectra including the fast dis-
appearance of the initial band at 1690 cmÿ1 (resi-
dual ENB unsaturation). However, the band at
1580±1610 cmÿ1 (assigned to zinc carboxylates
resulting from the neutralization of carboxylic
 Oxidation of rubbers analysed by HATR/IR spectroscopy 397

Fig. 1. Calibration curves for EPDM (MI and M2) and CR

(M3). Evaluation of the thickness analysed by di€erent IR
methods. (PAS, ATR (ZnSe) and ATR (Ge)).

acids by ZnO) is more intense when a surface ana-

lysis is performed (HATR (ZnSe) and HATR
(Ge)). This accumulation of zinc carboxylates at
the sample surface was also con®rmed on other
thermo-oxidized samples (M2, M3 and M4).

3.2 Oxidation of fully formulated EPDM, CR and

NBR by HATR (Ge)

The preceding results con®rm that HATR (Ge) is

in good correlation with other conventional
methods using thicker samples; only some antici-
pated stoichiometric di€erences can be expected in
thermal oxidation. Compared with other methods,
an advantage of HATR (Ge) is the possibility to
analyse correctly the polymer matrix even in the
presence of large amounts of carbon black as is the
case in formulations used in most industrial appli-
cations (tires, weatherstrips, hoses, belts, ...). The
following examples will show the versatility of this
technique for the study of the rubber durability.

3.2.1 In¯uence of stabilizer, carbon black and

temperature on the thermal oxidation of EPDM
(MI) and the photooxidation of EPDM (M2)
Results are reported in Table 1(The induction per-
iod is the minimum exposure duration for detec-
tion of oxidation in the carbonyl region of the IR
spectra (usually at 1715 and 1590 cmÿ1).
In the absence of carbon black, the oxidation is
very fast even at 100 C and softeners have a small
stabilizing e€ect. Carbon black is very ecient in
improving the durability both at 100 and 150 C.
The stabilizer is only ecient up to 100 C which is
enough regarding the usual temperature range for
Fig. 2. Thermal oxidation of EPDM at 150 C. Comparison of
most applications. In the case of photooxidation, di€erent IR analysis (A, transmission; B, photoacoustic; C,
carbon black also has a positive in¯uence on the ATR (ZnSe); D, ATR (Ge)).
398 F. Delor et al.

durability of EPDM (M2) (®lter e€ect). A thermal
coalescence phenomenon was suggested to occur5
for high carbon black contents.
3.2.2 In¯uence of stress on thermal and
photoageing
Figure 3 shows a signi®cant increase of thermal
and photooxidation rates when samples are
submitted to a constant stress corresponding to an
elongation of 20% (static). Similar results were
obtained when the elongation (20 and 30%) was
not constant but repeated each 5 to 15 s during
photooxidation (dynamic elongation).

Table 1. Induction period (in h) for the thermal oxidation at 100

and 150 C of EPDM (MI)
100 C 150 C
Ml (1) 30 0
M1 (2) 120 0
M1 (3) 200 150
Ml (4) 300 150

(1) Vulcanised EPDM alone.

(2) Vulcanised EPDM+softeners.
(3) Vulcanised EPDM+softeners+carbon black. Fig. 4. Use of HATR (Ge) for the study of the seasonal e€ect
(4) Vulcanised EPDM+softeners+carbon black+stabilizer. on the EPDM (M2) ageing.

Fig. 3. Use of HATR (Ge) for the evaluation of the stress e€ect on the thermal (A, at 100 C; B, at 150 C) and the photooxidation
(g>300 nm, 60 C) of EPDM M1 and M2, respectively.
 Oxidation of rubbers analysed by HATR/IR spectroscopy 399

Fig. 5. Use of HATR (Ge) coupled with surface abrasion for the study of the oxidation pro®le across thermooxidized (MI, M3,
M4) and photooxidized (M2, M3) rubbers. A, B, C, D, E, respectively.

Fig. 6. Use of HATR (Ge) for the study of the correlation between the chemical evolution and the elongation at break of thermo-
oxidized EPDM (Ml) (A), CR (M3) (B) and NBR (M4) (4), thickness 2 mm.
400 F. Delor et al.

Fig. 7. Use of ATR (Ge) for the identi®cation of carboxylic acids and carboxylates by SF4 treatment of thermooxidized EPDM
(Ml) at 150 C. Formulation with (A) and without (B) zinc oxide.

3.2.3 Analysis of outdoor exposure ageing of con®rmed by submitting oxidized samples to a

EPDM (M2)
Figure 4 shows the evolution of surface oxidation
of samples sun exposed at 45 inclined in the south
of France (Bandol). Samples show a fast oxida-
tion during summers 1 and 2 but a signi®cant
decrease of the carboxylate absorbance during
automn and winter. The evolution of EPDM upon
SEPAP exposure was not similar to those obtained
by outdoor ageing. This unexpected result is prob-
ably due to the disappearance of the small oxidized
layer (few m) during the rainy seasons, samples
being washed by rain. This phenomenon was
water extraction.
3.2.4 Oxidation pro®les across rubber samples
(M1, M2, M3, M4)
ATR (Ge) analysis of oxidized rubbers can be
performed after abrasion of successive layers
(15 m thick). The results, shown on Fig. 5,
clearly demonstrate that both thermal and
photo-oxidation are located in the ®rst hundred
microns of samples (2 or 5 mm thick). However
no carboxylate groups are detected in the core
of photooxidized samples (®lter e€ect of carbon
 Oxidation of rubbers analysed by HATR/IR spectroscopy
black) while small but signi®cant oxidation is
detected in the core of thermooxidized rubbers.
3.2.5 Correlation of carboxylate index (chemical
oxidation) with mechnical property evolutions
Some results are reported in Fig. 6. They clearly
show that the decrease of mechanical properties as
elongation at break is well correlated with the
thermal oxidation of the polymer matrix (CR
and NBR) even if a small part of the sample is
concerned by an important oxidation (see before).
When a strong evolution of carbonyl products is
observed, the loss of mechanical properties is also
important. For EPDM materials, the loss of ten-
sile strength is observed at the beginning of the
exposure and is less important than in the case of
CR and NBR. For photooxidized samples, because
of the limitation of oxidation to the extreme sur-
face (®rst 25 m) no correlations with elongations
at break were established.
3.2.6 Identi®cation of carboxylic acids and
carboxylate groups
Gas treatment coupled with transmission IR ana-
lysis is now commonly used for the identi®cation of
oxidized groups appearing during the photo or the
thermal oxidation of number of polymers.6±8
Spectra from Fig. 7 (after and before SF4 treat-
ment) clearly show that this identi®cation method
also works in the case of surface analysis by ATR
(Ge) of carbon black ®lled elastomers. Zinc car-
boxylates (1590 cmÿ1) and carboxylic acids
(1715 cmÿ1) are converted into acid ¯uorides
absorbing at 1840 cmÿ1. When zinc oxide is not
introduced in the formulation (Fig. 7(B)) only car-
boxylic acids are detected, they overlap with
ketonic group at 1710±1730 cmÿ1
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401
4 CONCLUSION
In conclusion, Attenuated Total Re¯ectance is a
reliable method for the study of the chemical evo-
lution of elastomers by infra-red spectroscopy.
With this method, the ageing can be studied
directly on industrial formulations i.e. containing
large amounts of carbon black which prevent the
use of transmission or photoacoustic methods. In
that case, an ATR crystal with high refractive
index, like germanium, has to be used to limit the
absorption of the infrared beam in the ®rst few
microns of the surface. However, the analysis of
such a thin layer of the sample can be disrupted by
low molecular weight compounds (vulcanisation
agents or their derived products) migrating from
the core of the sample. This was sometimes the
case during the photoageing of sulfur vulcanized
samples.
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