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Polymer Degradation and Stability 98 (2013) 682e690

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Polymer Degradation and Stability


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

Radiochemical ageing of butyl rubbers for space applications


M. Smith a, b, *, S. Berlioz a,1, J.F. Chailan a, 2
a
Laboratoire Matriaux Polymres Interfaces Environnement Marin (MAPIEM EA 4323), Universit du Sud Toulon Var, ISITV, BP 56, 83162 La Valette du Var Cedex, France
b
CNES (Centre National dEtudes Spatiales), 18 Av. Edouard Belin, 31401 Toulouse Cedex 9, France

a r t i c l e i n f o a b s t r a c t

Article history: The effect of 60Co gamma irradiation in inert atmosphere at 25  C and 70  C on a butyl elastomer lled
Received 10 July 2012 with carbon blacks has been investigated by SEM, 13C NMR, swelling measurements and mechanical
Received in revised form tests.
12 October 2012
An increase of the tensile strength of the material was observed during ageing. This increase of the
Accepted 14 October 2012
Available online 5 November 2012
mechanical properties is due to a modication of the rubber network structure. This hypothesis was
conrmed by swelling measurements done before and after ageing at various irradiation doses associ-
ated with an estimation of the crosslink density by the FloryeRehner equation. Crosslinking and chains
Keywords:
Butyl rubber
scission reactions occurred under irradiation and the contribution of both processes was estimated
Gamma irradiation thanks to the CharlesbyePinner equation. The high level of carbon blacks in the butyl rubber formulation
Temperature plays also an important role in the degradation process. Correlations between mechanical properties and
Inert atmosphere crosslink density are also presented. The modication of the rubber mechanical properties underlines
Mechanical properties that the degradation mechanism is strongly inuenced by the temperature especially at high irradiation
13
C NMR doses. At 25  C, the chain crosslinking process predominates over the chain scission reactions whereas
the two phenomena are in competition at the ageing temperature of 70  C.
2012 Elsevier Ltd. All rights reserved.

1. Introduction properties. Damaging effects can obviously be aggravated by the


other environmental factors (temperature, vacuum.). The use of
Over the years, synthetic rubbers have being used in a variety of rubbers in so severe conditions requires to have a reliable experi-
technical applications and so in different conditions which widely mental method to obtain detailed data concerning the evolution of
vary and are often complex due to the number of potential stresses. the material properties arising from this environment and so insure
Butyl rubber is a copolymer of isobutene and isoprene which is well the durability of the satellites components. This necessitates
known for its strong capability of energy dissipating combined with accelerated degradation tests at laboratory scale in order to predict
a good chemical stability and a good moisture ozone resistance the material properties changes in service conditions.
[1,2]. Butyl rubbers and particularly their halogenated derivatives In oxidative atmosphere, radiation effects on butyl rubbers have
have recently received increasing interests thanks to their been studied by various authors [7e11], but only a limited number
remarkable damping properties. Halogenated butyl rubbers could of works has been reported on the irradiation of butyl rubbers in
also be used for anti-vibrational systems in satellite applications. inert atmosphere [9].
Therefore, these rubbers should fulll the space technology When polymers are subjected to gamma radiations, many
requirements during all the satellite lifetime, which varies between chemical reactions may occur affecting the physical and mechanical
5 and 10 years. The space environment is especially harsh towards properties of the material [10,12,13]. The primary event which
elastomers [3e6]. In most cases, radiations can be considered as the occurs when a molecule interacts with ionizing radiation involves
most important factor leading to the degradation of the rubber the ejection of an electron to form a radical which could lead to
macromolecular chain scissions, crosslinkings, changes in stereo-
chemistry or formation of grafts through complex chemical reac-
* Corresponding author. Laboratoire Matriaux Polymres Interfaces Environne- tions processes. The role of the temperature on the degradation
ment Marin (MAPIEM EA 4323), Universit du Sud Toulon Var, ISITV, BP 56, 83162 process is crucial for exposed materials [12] and should be
La Valette du Var Cedex, France. Tel.: 33 494142628. considered carefully. The simultaneous action of high temperature
E-mail addresses: meryll.smith@univ-tln.fr (M. Smith), sophie.berlioz@univ-tln.fr
and radiations on rubber materials could lead to dramatic modi-
(S. Berlioz), chailan@univ-tln.fr (J.F. Chailan).
1
Tel.: 33 494142976. cations of the material properties since the heat treatment alone
2
Tel.: 33 494142462. leads to thermal degradation in many cases [14]. Concerning the

0141-3910/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.polymdegradstab.2012.10.013
M. Smith et al. / Polymer Degradation and Stability 98 (2013) 682e690 683

extent of degradation, it is difcult to make predictions since all the ageing. The morphological, chemical and mechanical properties
reactions which occur at room temperature, benec as well as modications are studied using classic tensile tests, Dynamic
detrimental, may occur at elevated temperatures with higher rates. Mechanical Analysis (DMA), Scanning Electron Microscopy (SEM)
Hence, there is no general rule to predict the behavior of a specic and Nuclear Magnetic Resonance (NMR) investigations. A better
rubber submits simultaneously to radiation and temperature and comprehension of the physico-chemical mechanisms involved
each case must be studied independently. Many techniques are during ageing under simultaneous action of ionizing radiation and
used in order to investigate the resulting changes of the material temperature is targeted.
and particularly the molecular structure (FTIR) [15,16], the thermal
stability and the glass transition behavior (DSC, TGA) [17,18] or the
mechanical properties (Dynamic Mechanical Analyses (DMA), 2. Experimental
tensile tests.) [19e21].
The chain scission process usually leads to a reduction of the 2.1. Material
tensile strength whereas the crosslinking process results in an
increased tensile strength and a reduced elongation at break [22]. A butyl rubber (Lanxess) was mixed with 66 phr of reinforcing
The predominance of one phenomenon above the other depends carbon blacks (Cabot). Two carbon blacks were used: 60 phr of
on several factors among them macromolecular structure, material Medium Thermal (MT) and 6 phr of Semi Reinforcing Furnace (SRF)
composition, irradiation conditions (absorbed dose, dose rate and with an average particle radius of 201e500 nm and 61e100 nm
exposure environment), temperature, atmosphere . respectively. Chemical processing additives were added to the
Butyl rubber is a copolymer composed of isobutylene units with compound and the mixture was then cured with sulfur as vulca-
a small percentage (1%) of isoprene units. It is known that poly- nizing agent.
isobutylene undergoes predominantly scission under irradiation The glass transition temperature of vulcanizated rubber
[14,23,24]. In butyl rubber, crosslinking would be expected trough was 64  C  0.5  C, measured by Differential Scanning Calorim-
the isolated isoprene units but Hill al. pointed out that scissions of etry (DSC).
the isobutylene sequences predominate [23]. Chandra et al. [25] The sheets were compression molded in an electrically heated
observed the same effect of ionizing radiations and reported the press at a temperature of 170  C for 14 min.
evolution of the molar mass, tensile strengths and density of butyl
rubbers submit to gamma irradiation at 25  C. However, the mech-
2.2. Irradiation of the sample
anism of radiation-induced scission of this polymer is not completely
understood. FTIR spectroscopic studies carried out by Turner and
A series of gamma irradiation experiments were performed
Higgins indicated the formation of vinylidene double bonds, ethyl
using a 60Co source at the SCK. CEN. Center (Belgium). Five different
groups and tri-substituted double bonds, accompanied by a drop in
doses (5, 10, 50 and 100 kGy) were applied under argon atmosphere
the substituent methyl groups content, indicating a methyl
at room temperature and at 70  C. The dose rate was xed at
abstraction. They proposed a mechanism for the chain scission
500 Gy/h for all selected doses. These conditions were chosen in
which implies that one vinyl group is formed for each scission [26].
order to extrapolate the effects of irradiations to which the material
This mechanism was conrmed by Bremer [24] who carried out
will be subjected during its service life.
Quantitative NMR analyses to determine the radiation yield of scis-
sion and assumed that every main chain scission results ultimately
in both an unsaturated and a saturated chain end. However, it 2.3. Scanning Electron Microscopy (SEM)
restrains this conclusion to relatively low radiation dose.
While butyl rubber is known to undergo predominantly chain The dispersion of the carbon black llers and other additives
scission during exposure to high energy radiation, a drastically before and after irradiation ageing was studied by Scanning Elec-
different response towards high energy radiation has been found for tron Microscopy.
bromobutyl rubbers [23]. In bromobutyl rubber, carbonehalogen Samples were freeze-fractured before analysis and coated with
bonds are weaker than carbonecarbon and carbonehydrogen gold to increase the conductivity. They were examined using a Zeiss
bonds, and the main effect of radiation is the carbonehalogen Supra 40 VP Field Emission Scanning Electron Microscope with
bond break, giving an organic free radical. Carswell-Pomerantz et a low acceleration voltage (1e5 keV) in order to minimize the
al. [27] who studied the degradation of bromobutyl rubbers irradi- degradation caused by the electron beam on the rubber.
ated with high energy radiation through Electron Spin resonance
characterizations pointed out that most of the radicals are generated
on the halogenated isoprene units, due to the labile CeBr bound and 2.4. Mechanical and dynamic mechanical properties
they observed that crosslinking predominates over chain scission up
to a limiting dose of 50e100 kGy. The tensile properties of unaged and irradiated rubbers were
The studies concerning the degradation of bromobutyl rubber carried out on an MTS DY35 testing machine at 25  2  C according
under radiation found in the literature reported complex to the NF T46-002 specications. The crosshead speed was xed to
phenomena with radicals formation which could lead to chains 500 mm min-1 and ve separate measurements were recorded and
scissions, crosslinking or other reactions [27]. These reactions occur averaged to assure the reliability of the results and to obtain mean
simultaneously and make difcult to visualize a distinct trend as values of the tensile strengths at 50 and 100% of elongation and of
many parameters are implied in the predominance of one reaction the stresses and strains at break.
above the others: environment, dose, additives, temperature, Dynamic mechanical analysis was performed on a TA Instru-
curing agents and curing conditions (number of sulfur per bridge). ments DMA 2980 analyzer. A single cantilever tool was used at
Moreover, the materials properties as tensile strength for example a frequency of 10 Hz with oscillation amplitude of 6 mm. The
are a complex function of crosslink chemical density and crosslink temperature range was from 100 to 40  C with a 3  C min1
nature, both chemical and physical interactions involved. heating rate. The sample dimensions were approximately 4e5 mm
The aim of this paper is to evaluate the behavior of a haloge- thick, 17.5 mm long and 15 mm wide. The evolutions of tan d and
nated butyl rubber submit to gamma radiations and temperature storage modulus G0 versus temperature were recorded.
684 M. Smith et al. / Polymer Degradation and Stability 98 (2013) 682e690

2.5. Crosslink density measurement The CharlesbyePinner theory relates the sol fraction with the
radiation dose by the following Eq. (8):
Small fractions of rubber samples exposed at different ageing
levels were immersed in cyclohexane at 25  2  C in order to p p 10
s s (8)
evaluate the crosslink density. Unaged samples were also tested q qDu1
in order to have a reference value. Each presented value was
obtained by the measurement of ve samples with nearly equal where p is the scission density per unit dose in kGy, q is the density
dimensions and weights. At various intervals, specimens were of crosslinks per unit dose in kGy, D is the radiation dose in kGy and
removed, gently wiped with a dry paper to remove solvent excess u1 is the number of average degree of polymerization. p/q is the
at the sample surface and reweighted after 30 s. Swelling ratios intercept of the straight line in the plot and gives an idea of the ratio
were calculated after an immersion of one week, which corre- of chain scission to crosslinking [31].
sponds to the equilibrium swelling time. For the solegel fractions
estimation, samples weights were also measured after drying at 2.6. Nuclear Magnetic Resonance (NMR)
60  C in vacuum.
The swelling ratios were calculated using Eq. (1): Solid State NMR spectra were carried out on a Brucker Avance
400 MHz spectrometrer with a standard CP/MAS probe for 4 mm
swollensample weightinitial sample weight external diameter rotors using magic angle spinning rotation
Dm% 100 frequency of 10 kHz. The crosspolarization technique was applied
initial sample weight
with short contact times (1 ms).
(1)
Small squares (0.5e1 mm2) of rubber were cut and set in NMR
The crosslink density is dened as the number of elastically rotor tube. All tests were performed at room temperature.
active network chains totally included in a perfect network per unit The contribution of each different carbon was determined as the
volume and evaluated according to the following FloryeRehner Eq. integration of the corresponding NMR peaks normalized by the
(2) [28]: whole spectra area.
h i
 ln 1  Vr Vr cVr2 3. Results
n (2)
 1  3.1. SEM
Vr
V  Vr3 
2
SEM was used in order to evaluate the surface morphological and
where Vr is the volume fraction of the rubber in the swollen sample, aggregates dispersion modications during ageing. An SEM image
c is the interaction constant characteristic between butyl rubber of unaged butyl rubber cross-section showing the good llers
and cyclohexane, which is 0.44 [29], V is the molar volume of distribution in the matrix before ageing is presented in Fig. 1A. The
cyclohexane (108,03 cm3 mol1) and n is the crosslink concentra- samples irradiated at 25  C (Fig. 1B) showed minor cracks of
tion (mol cm3). submicron size in one or two places. The samples exposed to radi-
To solve Eq. (2) [30], the rubber volume fraction in the swollen ation at 70  C (1 C) present a surface texture quietly different from
sample, Vr, is calculated by the following Eq. (3): the samples irradiated at room temperature with major cracks,
wrinkles and fractures. In other studies, the same damages were
  observed on bromobutyl rubber submit to thermal ageing [32].
Xr
rr Concerning the llers, no measurable changes of their size or
Vr     (3) their distribution in the matrix were detected by SEM.
Xr Xs

rr rs
3.2. Mechanical properties
where Xr is the mass fraction of rubber, rr is the density of raw
rubber (1062 g cm3), Xs is the mass fraction of cyclohexane and rs 3.2.1. Effect of radiation dose and temperature
is the density of cyclohexane (0.779 g cm3). Typical stress/strain curves obtained for unaged sample (t0) and
Xr and Xs can be obtained using Eqs. (4) and (5): samples irradiated at 100 kGy under 25 and 70  C are presented in
Fig. 2 and the averaged values of tensile strengths at 50% and 100%
swollen sample weightg  original sample weightg of elongation are given in Table 1.
Xs The mechanical properties of polymers are considerably modi-
swollen sample weightg
ed by high energy radiations. The strains and stresses at break
(4) decrease deeply with the irradiation dose, especially at the highest
ageing temperature. Hence, the unaged sample and samples irra-
Xr 1  Xs (5) diated at 100 kGy at 25 and 70  C present stresses of respectively
9.4 MPa, 4.1 MPa and 2.5 MPa. The presence of cracks and fractures
In order to quantitatively evaluate the crosslinking and chain
revealed by SEM analyses could be one of the explanations for this
scission yields of irradiated samples, [s s1/2] vs. [1/absorbed dose]
decrease.
from the CharlesbyePinner equation (Eq. (8)) were plotted for the
Fig. 3 illustrates the variation of the tensile stresses at 50 and
different aged samples. The sol (s) and gel (g) fractions of the
100% of elongation as a function of the irradiation dose for ageing
irradiated rubbers were calculated by Eqs. (6) and (7):
performed at 25  C and 70  C. Between 0 and 5 kGy, the variation of
the stresses for both levels of strain are in the standard deviation
s 1g (6)
whatever the temperature of ageing whereas at higher gamma
irradiation doses stresses were greatly increased. Hence, at
dry sample weight 100 kGy, the stress at 100% of elongation goes up by 137%. At 70  C,
g (7)
initial sample weight the increment of the stress is lower (less than 25%).
M. Smith et al. / Polymer Degradation and Stability 98 (2013) 682e690 685

Fig. 2. Tensile stresses vs strains for unaged and 100 kGy irradiated under 25 and 70  C
samples.

The main relaxation peak (a relaxation) is associated with the butyl


rubber glass transition, while the shoulder corresponds to a sub-
glass relaxation (so-called b relaxation) due to the rotation of
methyl groups, directly attached to the polymer backbone [20,33].
The gure revealed a shift of the Ta peak towards higher temper-
atures (18  C to 15  C) for 100 kGy irradiated sample at 25  C.
No signicant difference between the glassy G0 values (90  C)
of the unaged and 100 kGy/25  C irradiated samples is observed
whereas the G0 value of sample irradiated at 70  C is lowered by
40%. At the rubbery state (above 20  C), the rubber modulus does
not seem to be affected by ageing. This last observation is consistent
with the results of tensile tests done at room temperature which
show a superposition of the stress/strain curves at low deformation
(<0.5%) for all the samples (Fig. 2).

3.2.2. Failure envelope, stress at breakestrain at break (srer)


Tensile tests have been widely used by a number of workers in
order to study the mechanical properties of rubber materials. From
these investigations, Lassiaz [34] proposed the concept of a failure
envelope specic to each rubber. In this concept, the locus of the
stress at break versus strain at break can be represented as a unique
curve independent of the material history.
Fig. 5 shows that the locus of the stress and strains at break of
the aged samples are superimposed on the tensile curve obtained
for the unaged one, that is conform to the failure envelope concept.
The failure envelope (sr f(r)) shows two distinct zones
designed as A and B (Fig. 6) [34]. The A zone represents the incu-
bation phase where the rubber properties do not change signi-
cantly compared to the unaged sample. The B zone so-called the
terminal phase corresponds to samples exposed at higher doses. In
this terminal phase, the stresses and strains at break of the material
are dramatically lowered.
The accumulation of defects (fracture, porosity, cracks.) and
damages induced by irradiation leads to an earlier failure of rubber
that corresponds to a transition from a plastic to a brittle behavior.
Radiations transform the exible samples to brittle and rigid ones
Fig. 1. SEM micrograph of unaged (A), irradiated at 100 kGy under 25  C (B) and 70  C
(C) butyl rubbers. especially when high doses are applied. The temperature at which

The dynamic mechanical properties are also inuenced by the Table 1


Averaged values of tensile strength at 50% and 100% of elongation (MPa).
radiation/temperature ageing, but to a lesser extent than tensile
properties. Fig. 4 shows the tan d and G0 versus temperature curves Unaged 5 kGy 10 kGy 50 kGy 100 kGy
for the unaged sample and for the 100 kGy irradiated samples at 50% 25 
C 0.59  0.01 0.6  0.02 0.7  0.01 0.8  0.01 0.9  0.02
25  C and 70  C. The tan d peak of unaged butyl rubber is pretty 70 
C 0.6  0.01 0.6  0.01 0.6  0.01 0.5  0.01

wide covering a temperature range between 50 and 50  C, with 100% 25 C 0.79  0.01 0.9  0.01 1.0  0.01 1.6  0.02 1.9  0.06

70 C 0.8  0.01 0.8  0.03 0.9  0.02 1.0  0.02
a maximum at 18  C (Ta) and a shoulder peak near 35  C (Tb).
686 M. Smith et al. / Polymer Degradation and Stability 98 (2013) 682e690

Fig. 5. Tensile curve of unaged sample and failure envelope (se).

Fig. 3. Evolution of stresses at 50% and 100% of elongation with irradiation dose (kGy)
3.3. Network structure studies
under 25  C (blue: d d) and 70  C (red: d). (For interpretation of the references to
colour in this gure legend, the reader is referred to the web version of this article.)
The calculation of the crosslink density from the swelling test is
radiations were performed does not play a major role in this one of the most used methods to characterize the morphology of
mechanical behavior transition. a vulcanizated elastomer. Fig. 6 presents the swelling ratios and the
Similar drop in the mechanical properties were observed by resulted crosslink densities obtained by the FloryeRehner equation
Scagliusi et al. [35] when gamma irradiation were performed on as a function of the dose for samples irradiated at 25  C and 70  C.
a sulfur cured chloro butyl rubber. The swelling ratios are found to decrease for both studied
temperatures with increasing the irradiation dose. Fig. 6 reveals
that the swelling ratio of samples irradiated at 25  C decreases
sharply up to 10 kGy. Above this absorbed dose, the decreasing
trend becomes slower with the additional irradiation dose. Con-
cerning the samples irradiated at 70  C, the swelling ratio decreases
gradually with the irradiation dose. The comparison between the
swelling ratios evolutions for both temperatures suggests a faster
and greater crosslinking phenomenon at 25  C than at 70  C.

3.4. Structure/properties relationships

The comparison between Table 1 and Fig. 6 shows an apparent


qualitative dependence of the mechanical properties with the
crosslinking density and various correlations might be deduced.
Hence, Fig. 7 illustrates the relationships between the measured
tensile stresses and the crosslink density n. The experimental data
could be tted with a good yield (R2  0.91) by analytical curves of
the following form:

s a  ln n b (9)
where a and b are constants.

Fig. 4. Plot of dynamic mechanical properties (tan d and G0 ) vs temperature for unaged Fig. 6. Swelling content and crosslink density (n) measured for samples irradiated at
sample (black: d) and 100 kGy irradiated samples at 25  C (blue: d d) and 70  C (red: different dose levels under 25  C (blue: d d) and 70  C (red: d). (For interpretation of
- - -). (For interpretation of the references to colour in this gure legend, the reader is the references to colour in this gure legend, the reader is referred to the web version
referred to the web version of this article.) of this article.)
M. Smith et al. / Polymer Degradation and Stability 98 (2013) 682e690 687

note that these results should be considered with precaution due to


the shortage of the experimental datas at high doses for Char-
lesbyePinner extrapolation. Moreover, these calculations are based
on several assumptions, including random spatial distribution of
the scission and crosslinking and absence of intramolecular cross-
linking or cyclization.
According to the CharlesbyePinner results, the density of the
elastomeric network seems not to be deeply modied as a result of
the strong competition between crosslinking and chains scissions.
However, the mechanical properties at high level of deformation
are greatly affected by irradiation. As discusses previously (x 2.4),
other phenomena could lead to modication of the material
mechanical properties. At this stage, it should be reminded that the
macroscopic properties of a lled rubber and especially the
Fig. 7. Evolution of stress at 50% and 100% of elongation vs logarithm of crosslink
mechanical properties are not only due to the chemical elastomer
density (n) at 25  C (blue: d d) and 70  C (red: d). (For interpretation of the refer-
ences to colour in this gure legend, the reader is referred to the web version of this network but also to the presence of physical or chemical bonds
article.) between llers and macromolecular chains of elastomer. The high
content of carbon blacks in the studied samples (66 phr) allows
thinking that these interactions should have an important role.
This empirical equation shows that there is a strong correlation
Hence, the modication of the llers/polymer interactions during
between the stresses measured at different levels of elongation and
irradiation could be one of the major explanations of the observed
the morphological properties of the rubber. Although correlation
loss of the mechanical properties. The degradation by creation of
does not imply causality, this fact seems to suggest that the incre-
cracks, fractures and porosity as shown in SEM images (Fig. 1) is
ment of the mechanical properties could be partly due to the
another hypothetic explanation.
increment of the crosslink density. The comparison between the a
values indicates that the effect of the crosslink density is greater at
100% of elongation compared to 50% of elongation Besides, the 3.6. NMR results
stresses measured for samples irradiated at 25  C, are higher than
those measured for samples irradiated at 70  C if we consider the The NMR spectrum of bromobutyl rubber has been assigned
same crosslinking density. This last observation suggests that the previously by Chu et al. [36]. As the majority of the monomer units
modication of the crosslinking density is not the only explanation are isobutylene, the 13C NMR spectrum (Fig. 9) is practically similar
for the evolutions of the mechanical properties during ageing at those of a polyisobutylene and no signal related to isoprene units
(Fig. 2 and Table 1). Other phenomena such as defects accumulation could be seen in our spectrum. The chemical shifts of the main
in the sample or increment of the network heterogeneity with peaks are reported in Table 2.
ageing could explain the observed differences between the two As presented in Table 2, an increase of the vinyl carbon content
ageing temperature results. (located between 110 and 150 ppm) accompanied by a decrease of
the intensities of the signals assigned to quaternary (36 ppm) and
3.5. CharlesbyePinner theory methyl carbons (58 ppm) have been measured (Fig. 10). According
to the previous reported studies, these evolutions suggest that
The scission/crosslinking ratio was analyzed using the chain scissions of the isobutylene units occurred during irradiation
CharlesbyePinner equation. The values of p/q could be measured (Fig. 11) [24].
from the CharlesbyePinner plot (Fig. 8): 0.7 and 1.33 were found
respectively for ageing at 25  C and 70  C. These values are close to 4. Discussion
1 that implies that competitive chain scissions occur in parallel to
crosslinking during irradiation. However, the crosslinking The data obtained by mechanical analyses indicate clearly that
phenomenon seems to predominate over chain scission at 25  C the irradiation process at room temperature acted effectively in
whereas the opposite trend seems to occur at 70  C. It is worth to

Fig. 8. CharlesbyePinner plot for ageing at 25  C (blue: d d) and 70  C (red: d). (For Fig. 9. NMR spectra of unaged butyl rubber (black: d) and 100 kGy irradiated butyl
interpretation of the references to colour in this gure legend, the reader is referred to rubber at 25  C (blue: d) and 70  C (red: d). (For interpretation of the references to
the web version of this article.) colour in this gure legend, the reader is referred to the web version of this article.)
688 M. Smith et al. / Polymer Degradation and Stability 98 (2013) 682e690

Table 2
13
C NMR signal assignments for butyl rubber.

Signal (ppm) Band assignment


150e110 Unsaturation (C]C)
58 Carbon atom of the methyl group
36 Quaternary carbon atom bearing two methyl groups
Fig. 11. Chain scission reaction between two isobutylene units.
31.6 Vulcanization control band
30 Carbon atom of the methylene group

deformation levels compared to a more aggregated structure


raising up the tensile stress values of the butyl rubber (Fig. 3) observed without stress [42]. The observed decrease of the elon-
whereas, the evolution of the tensile stresses for samples irradiated gation at break could hence be explained by an additional bounding
at 70  C is less marked. As regards the elongations at break, they are between rubber and llers initiated by the formation of free radi-
deeply diminished during ageing whatever the temperature cals during radiation.
considered (Fig. 5). These evolutions of stresses and strains at Concerning swelling results, the restriction of the amount of
failure are classically observed when an increment of the crosslink solvent which could be absorbed by an elastomeric network is due
density of the materials is observed. However, the results of NMR to the formation of new crosslinks in the elastomer network or new
presented previously seem to turn in favor of chains scissions. So interactions between rubber and llers during radiation. The more
another explanation must be proposed. signicant swelling ratio drop for ageing at 25  C is a sign of
The mechanical properties of a lled rubber are strongly a higher increase of the crosslink density at this temperature. This
dependant not only on the chemical crosslink density ratio but also result is consistent with the higher tensile stresses measured for
on the physical and chemical attachments of the molecular chains samples aged at 25  C than those of samples aged at 70  C (Fig. 2).
to the ller surface. Hence, a poor dispersion of particles in a poly- As regard the dynamic mechanical properties, the Ta shift
meric matrix with large agglomerates leading to low specic towards higher temperatures associated with a diminution of
surfaces could be responsible of the decrease of mechanical prop- a peak amplitude indicates that the macromolecular chains
erties such as ultimate stresses [37] and have certain other detri- mobility was diminished with irradiation. This phenomenon is
mental effects (reduced product life, poor performance in consistent with the decrease of the swelling content values (Fig. 6)
service.). This hypothesis as an explanation of the mechanical and could be explained by an increase of the chemical crosslink
properties drop should be rejected in our study as a good level of density or an increase of the physical attachment between matrix
dispersion of llers was observed by SEM for irradiated samples and llers during irradiation. Indeed, crosslinking or bonds
(Fig. 2). between carbon black particles and rubber hamper the segmental
However a modication of the number and/or the intensity of motion leading to a higher temperature to initiate movements. At
the interactions between carbon black particles and rubber is ex- the rubbery plateau, the G0 values for samples irradiated at 25 and
pected under radiation [38e40]. Although there is no complete 70  C are similar to the one of the unaged sample. In revenge, at the
knowledge of the exact nature of rubbereller interactions at glassy state, a slight decrease of the G0 modulus is observed for
present, the different types of chemical groups that exist at the samples irradiated at 70  C. The predominance of macromolecular
carbon black surface such as carboxylic, phenolic, hydroxylic, chains scission phenomenon vs crosslinking at this temperature is
aldehydic and ketonic, could participate in the formation of phys- probably an explanation for this lower value, and consistent with
ical as well as chemical attachments at the ller/rubber interface. the difference of crosslinking/chains scissions ratio between the
Under high energy irradiation, the surface chemistry of carbon two temperatures estimated by CharlesbyePinner equation.
blacks are greatly modied with among others things, the forma- Whereas the tensile tests show great effect of the temperature
tion of a large number of free radicals, that could induce major under which the irradiation was carried out, the DMA analyses do
changes in the nature of the llers/rubber bonds [41]. It is worth to not show a great difference between the two ageing temperatures.
note that these bonds play a more important role at high levels of This could be attributed to the level of solicitation amplitude
elongation i) where the llers maybe undergo a damage mecha- between the two techniques. A high deformation level (and so
nism leading to carbon black decohesion and ii) because of the a strong solicitation of the bonds between carbon blacks and
better distribution of the carbon black llers under high polymer chains) is imposed to the samples during tensile tests
while the deformation applied in DMA is very small (z0.15%). This
remark supports the hypothesis that the nature of interactions
between carbon black llers and rubber are greatly modied under
radiation whereas the modication of the macromolecular rubber
network is less important.
The NMR results show an increase of the unsaturated carbon
which could be undoubtly attributed to isobutylene chains scis-
sions because a simultaneous decrease of the signals assigned to
quaternary carbons and methyl carbons of the isobutylene units
was observed. One can note here that the decrease of the methyl
groups is in agreement with the b relaxation extinction with ageing
observed in DMA results (Fig. 10).
These chain scissions are in competition with crosslinks which
could occur via the halogen isoprene units. However, this last
phenomenon is limited because only 1e2% of isoprene units are
present in the butyl rubber. The competition between these two
Fig. 10. Evolution of CH2 groups, CH3 groups, quaternary carbon and unsaturation
during radiochemical ageing at 25  C (blue: d d) and 70  C (red: d). (For interpre-
phenomena results in a very slight variation of the mechanical
tation of the references to colour in this gure legend, the reader is referred to the web properties at low deformation level. Young modulus values calcu-
version of this article.) lated from the tensile tests at the rubbery state are similar for
M. Smith et al. / Polymer Degradation and Stability 98 (2013) 682e690 689

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