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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.
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.
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.
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
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.
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