J Polym Environ

DOI 10.1007/s10924-017-0966-9

ORIGINAL PAPER

Degradability Characterization of EPDM/IIR Blends

by γ-irradiation
Traian Zaharescu1 · Sandra R. Scagliusi2 · Ana Maria Luchian1 · Ademar B. Lugão2

© Springer Science+Business Media New York 2017

Abstract In this paper the modifications induced in butyl Keywords EPDM · Halogenated IIR · Degradation ·
rubbers (pristine, chlorinated and brominated sorts) by Oxidation · Recycling · γ-Irradiation
γ-irradiation are investigated by swelling, chemilumines-
cence and FT-IR. The susceptibility of butyl rubbers for the
generation of radicals orders their stabilities in the follow- Introduction
ing sequence: IIR > IIR—Cl > IIR—Br. The incorporation
of butyl rubbers into ethylene-propylene terpolymer matrix The dumping of polymer wastes raises the problems of
brings about increased densities of radicals initiating modi- their environmental depollution and valorization by vari-
fications in the oxidation state in respect with recombina- ous procedures including radiation processing [1–3]. The
tion, which are intensified as the processing dose increases. rubber industry would be a main beneficiary of this kind
Based on the variation of carbonyl and hydroxyl indices of technologies, because the intimate processes occurring
the favorable route for the recycling EPDM based formu- during conversion contribute to the modifications of a large
lations would be suggested in this study. The chemilumi- spectrum of industrial and municipal wastes maintaining
nescence spectra proving the formation of peroxyl radicals their functional performances on acceptable limits. From
at about 100 °C prove their availability as reclaiming solu- the environmental standpoint the radiation treatment is
tions. IIR—Br is the recommendable butyl rubber for the applicable even to incompatible polymers due to the radical
recovery procedure by association with EPDM. The suit- mechanisms of recombination [4].
ability of IIRs for recycling purposes is analyzed by the The increase of about 600 times up to the million pounds
variation in their crosslink densities, free volumes and of collected plastics over the period between 1990 and 2013
swelling degrees. The crosslinking behavior of stabilized [5] is a reality. An example for the imperative necessity of
EPDM/IIR blends that runs to the improvement of durabil- waste collection is Europe where the amount of waste plas-
ity is depicted by Charlesby–Pinner representation, which tics attains annually 15.6 Mtonne. A large diversity of plas-
involves the different simultaneous contribution of scission tics subjected to reclaiming [6] and the proportion of 19%
and crosslinking processes. in the recycled materials stream structure [7] demonstrate
that the recovery sector is a pillar for the depollution of
environment and it sustains economic growth.
The durability of plastics wastes, longer than 100 years
especially in the case of resistant and/or stabilized materials
* Traian Zaharescu [8], does not recommend the landfill disposal for their long
traian.zaharescu@icpe‑ca.ro term storage. The other alternative is the radiation process-
1 ing which is intensively promoted by International Atomic
Radiochemistry Center, National Institute for Electrical
Engineering (INCDIE, ICPE-CA), 030138 Bucharest, Energy Agency [9, 10]. The availability of radiation treat-
Romania ment applied to polymers is clearly revealed by several
2
Instituto de Pesquisas Energéticas e Nucleares (IPEN – papers [for example 11–13]. This procedure has consider-
CNEN/SP), São Paulo, SP 05508‑000, Brazil able advantages in comparison with chemical methods:

13
Vol.:(0123456789)
 J Polym Environ

further wastes are not generated, strictly controlled and

suddenly stopped operations can be easily applied, a large
diversity of polymer materials can be processed without
special energy requirements, the presence of solvents is not
usually needed, the addition of peroxides is not demanded
because they are radiolytically generated and their excess
would initiate premature material ageing, several pairs of
polymers that are thermodynamically incompatible can be
intimately structured in engineering products. Fig. 1  Molecular structures of studied polymers
The accumulating elastic rubber wastes (used tires,
pipes, gaskets and seals, wire and cable insulations included
in the large category of recoverable materials by radiation Table 1  Formulations of butyl and halobutyl rubber samples
processing) ask peremptorily their decay. The basic infor- Ingredients Quantities (phr)
mation on the alterations of butyl rubbers (IIR) induced by
Butyl rubber Bromobutyl Chlo-
high energy radiation were earlier reported [14–18]. This
rubber robutyl
bearing was also confirmed by thermal treatment [19] and rubber
photodegradation [20]. In addition, the more resistant poly-
mer under γ-irradiation, ethylene-propylene terpolymer Basic IIR 100 100 100
– EPDM [21–24] may be associated with different elasto- Zinc oxide 5 5 5
mers for the production of versatile blends [25–27]. The Stearic acid 1 1 1
restriction conditions concerning the radiation damaging Parafinic oil 25 25 25
in EPDM blends are related to the achievement of foreseen Carbon black 70 70 70
formation rate for free radicals, which initiate compatibili- Sulfur 2 0.5 0.5
zation by crosslinking [28]. MBTS 0.5 – 0.5
The growing interest on the potential applications of ZMDC – 2 0.1
irradiated blends [29] generates the problem of blends TMTD 1 – –
durability, which is strictly correlated with material sta-
bility. The endurance behavior of blending components is
essential for the convenient preservation of their oxidation Experimental
resistance.
The investigations on radiation treatment of butyl rub- Materials and Sample Preparation
bers were reported for their applications in tire industry.
While the low doses applied to butyl rubber cause a sharp Butyl rubbers (IIRs) as Butyl 268 (pristine IIR) whose
decrease in molecular weight initiating degradation [30], unsaturation degree is initially 1.70 mol%, Bromobu-
ethylene propylene terpolymer can be crosslinked with tyl 2222 (brominated IIR, IIR-Br) containing 1.03 mol%
convenient increase in gel fraction [31, 32]. The use of unsaturation and Chlorobutyl HT 1066 (chlorinated IIR,
ionizing radiation for the compatibilization of EPDM and IIR-Cl)—raw material with 1.26 mol% unsaturation were
IIRs eliminates the addition of peroxide as initiator, whose delivered by Exxon Mobil Chemicals. All polymers were
nonconsumed fraction remains captive in the polymer bulk used as received. The molecular structures of studied pol-
and its spots become the start points of degradation. The ymers are presented in Fig. 1. In Table 1 the formulations
EPDM-based blends can be taken into consideration as the of pre-prepared rubbery samples are listed.
systems in which one component, in our case—IIR, is the The host polymer, ethylene-propylene terpolymer
main donor radical source, while EPDM disposes mac- (EPDM) was manufactured by APRCHIM Piteşti (Roma-
romolecular chains for the grafting process of generated nia) as Terpit C­ ®. It consists of ethylene (64.5 wt%),
radicals. propylene (32 wt%) and ethylidene 2-norbornene,
This work presents the contributions of three sorts of ENB (3.5 wt%). The main initial properties were: num-
butyl rubbers: pristine material (IIR), chlorinated (IIR- ber of C­ H3 for 100 carbon atoms: 0.983, unsaturation
Cl) and brominated (IIR-Br) elastomers to the evolution (C–C/1000 carbon atoms): 0.184, melting index (dl/g):
of radiochemical oxidation in their blends with ethylene- 1.38.
propylene diene monomer (EPDM). The variation in the The films with the same thickness (100 µm) for spec-
IIR loading offers the evidence for the degradation trend, trometric investigation and sheets for chemiluminescence
when EPDM/IIR mixtures are exposed to low dose rate of records were obtained by the solvent (­CCl3) evaporation
γ-radiation. from polymer solutions previously mixed in proper ratios

13
J Polym Environ

according with their concentrations. The IIRs loadings are The values of free volumes were calculated by the divi-
5, 10 and 20 phr. sion of mass variation with material density for each com-
ponent (p means polymer and s means solvent):
Xp
Irradiation
𝜌p
Vr = Xp Xs
(2)
γ-Exposure was performed in air, at room temperature 𝜌p
+ 𝜌s
inside an irradiation machinery provided with 137Cs source.
where mass fraction of polymer is
Dose rate was 0.4 kGy h­ −1. The dose accumulation pro-
cedure was preferred, because it conserves the identity of
[ ]
Xs = (mass of swelled sample, g) − (initial sample mass, g)
sample characteristics. The radiation treatment was applied and mass fraction of solvent is
to unstabilized material formulation and to the blends pre-
viously modified with 0.5 phr antioxidant (Igranox 1010, Xp = 1 − Xs
Ciba ­Geigy®). The equation Flory–Rehner Eq. [35] was applied for the
evaluation of crosslink density:
( )
Characterization ln 1 − Vr + Vr + 𝜒Vr2
n=− ( ) (3)
1∕3 V
V Vr − 2r
Chemiluminescence (CL) determinations were carried out
by nonisothermal measurements over the temperature range where n is crosslink density ­(cm−3), ­Vr is free volume, V is
30–250 °C at heating rate of 5 °C ­min−1. The equipment, molar volume of toluene (106.5 cm3 mol−1), χ is parameter
chemiluminograph LUMIPOL 3 produced by Slovak Acad- of polymer/solvent interaction. For the pair EPDM (main
emy of Sciences (Bratislava), monitored the evolution of component)/toluene 0.58 was applied.
testing temperature with a good error (±0.5 °C). The sam- Three similar samples per point were processed and the
ples were prepared by purring solutions on aluminum trays average values had the error of ±0.5%.
followed by solvent evaporation producing films at room
temperature. Each dry polymer sample had weight around
3 mg. The CL intensities are expressed in Hz g−1, because Results
the recorded count numbers must be normalized to the sam-
ple mass for the accurate comparison of results obtained on The radiation processing applications for the manufacture
different mass samples. The inertness of aluminum to oxi- of new polymeric products are based on the bond scission,
dation assures the lack of counting background. whose energy values present lower values. According with
FT-IR spectra were recorded on JASCO 4200 A (Japan) the figures listed in Table 2 and the nonspecificity energetic
spectrophotometer at 50 scans and 4 cm−1 resolution. Car- transfer from incidental radiation and polymer macromol-
bonyl and hydroxyl indexes were calculated as the ratios ecules, the highest probability for scission is presented by π
between the absorbances measured at 1718 and 3390 cm−1, bond of C=C, C–Cl and C–Br [36]. They are the sources of
respectively and the absorbance at 2920 cm−1 [33]. The carbon-centered radicals involved in further reactions.
molar extinction coefficients, 310 and 90 l mol−1 cm−1 [34] These places become radical sources by the further
were used for the calculation of carbonyl and hydroxyl con- processes especially oxidation. Under high energy irra-
centrations, respectively. diation the two main initial processes takes place, scis-
The measurements of swelling degrees (Q), free vol- sion and crosslinking. Their radiochemical yields of scis-
umes (Vr) and crosslink densities (ν) were performed by sion and crosslinking characterized by the number of
the immersion of samples (15 × 15 × 1 mm) in toluene (ana- events occurred for 100 eV absorbed energy, G(S) and
lytical grade) at room temperature and weighing after 5
days of stabilization, according to ASTM D-3616-5 stand-
ard. During this operation testing samples were covered Table 2  Bond energies of constituent components in butyl rubbers
avoiding solvent evaporation. For the calculation of swell- Bond Bond energy (kJ mol−1)
ing degree we used the equation:
–C–C– 347
m − m0 –C=C– 614 (347+267)
Q= × 100 (1)
m0 –C–H 413
where Q is swelling degree (%), m and ­m0 are the sample –C–Cl 327
weights after and before swelling. –C–Br 281

13
 J Polym Environ

G(X) respectively, define the radiation strength. Butyl rub-

bers have G(X) less than 0.5 and G(S) 2.9–3.7 [32, 37].
The large difference between the values of G(S)/G(X) for
butyl rubber (~6) and ethylene-propylene-diene terpolymer
(~0.62) [38] emphasizes the role of butyl rubbers as free
radical providers in the mixtures with EPDM.

Solubility Tests

In the solubility tests defining the molecular cohesion the

penetration rate for solvent molecules depends on many
factors, through which the free space between molecules,
the size of molecules and the crosslinking degree are rel-
evant. The γ-exposure of IIRs causes a diminution in the
polymer molecular weight and an increase in the dispersion
indices.
The swelling investigations underline the differences
between butyl rubbers when halogen atoms exist in their
configurations. While the IIR-Br presents slight differ-
ences between the swelling degrees for different doses and
immersion times due to the obvious high degree of scis-
sions still on the early stage of irradiation, neat and chlo-
rinated butyl rubber present significant increasing in the
absorbed amounts of toluene as the dose enhances for all
swelling times (Fig. 2). In Fig. 2a the swelling degrees
corresponding to the immersion times longer than 72 for
irradiated butyl rubber at 200 kGy could not be evaluated
because samples were completely dissolved. This bearing
can be explained by the high degree of fragmentation. In
Fig. 2b the samples of chlorinated butyl rubber shows an
increase in swelling at 5 kGy, then decreases up to 100 kGy
and further increases significantly at 200 kGy, because this
rubber is simultaneously degraded at two positions: dou-
ble bonds (unsaturation degree: 1.26 mol%) and chloride
substitutions. Their contributions determine the changes in
swelling degree as the irradiation dose is augmented.
The radiation stability of these butyl rubbers is tightly
correlated with the diffusion of foreign molecules, because
the energy transfer during irradiation is characterized by
fragmentation and by a positive variation in free volumes
(Fig. 3). The presence of double bond in the backbone of
butyl rubber (unsaturation degree is 1.70 mol%) determines
a continuous reduction in ­ vr figures for low irradiation Fig. 2  Modification in the swelling degrees of γ-processed IIR (a),
doses. After γ-exposure the other two halogenated butyl IIR-Cl (b) and IIR-Br (c). ( ) 0 kGy; ( ) 5 kGy; ( ) 50 kGy; ( )
rubbers (unsaturation degrees are 1.03 and 1.26 for bromi- 100 kGy; ( ) 200 kGy. (Color figure online)
nated and chlorinated rubbers, respectively) the values of
free volume are somewhat constantly maintained (Fig. 3b, raw material. While the swelling degree of this mate-
c). rial is maintained constant (around 142%, Fig. 2a) on
The action of γ-radiation concerns simultaneous scis- the early stage of irradiation, the crosslinking density
sion and crosslinking. Figure 4 illustrates the variation of decreases monotonically (Fig. 4a). Meanwhile the butyl
crosslinking in γ-irradiated butyl rubbers. The strike dim- rubber exhibits a sharp dropping in crosslinking density,
inution of crosslinking density happened in γ-exposed the gelation of the other two halogenated materials pro-
butyl rubber is the effect of high insoluble fraction in gresses unlikely. The increasing dose affects IIR-Cl by

13
J Polym Environ

Fig. 3  Modification in the free volumes of γ -exposed IIR (a), IIR-Cl Fig. 4  Modification in the crosslinking density of γ-irradiated IIR
(b) and IIR-Br (c). The color meanings are similar to Fig. 2. (Color (a), IIR-Cl (b) and IIR-Br (c). The color meanings are similar to
figure online) Fig. 2. (Color figure online)

the slight diminution of intermolecular crossing bridges energies are less than the energy of C–C bonds forming
with an evident effect at the doses exceeding 100 kGy. intermolecular network.
For IIR-Br the deterioration of material integrity could The inclination of γ-irradiated butyl rubbers to the dif-
not be proved. It can be assumed that the deposited fusion of foreign entities, either molecules or free radi-
energy from incidental radiation is preferentially con- cals, is demonstrated by the adequate swelling proper-
sumed by the scission of C–Cl and C–Br bonds, whose ties, which can be considered basic information for their

13
 J Polym Environ

radiation processing. The reclaiming of polymer wastes is

realistically justified by the inherent potential of radiolysis
transformations.

Oxidation Investigation by FT‑IR Spectroscopy

FT-IR spectra reveal the changes in the oxidation states.

The new created free radicals are involved in the com-
petitive recombination and oxidation. Due to IIR compo-
nents the increase in the oxidation level can be noticed
at greater doses correlated with the effects of the chemi-
cal nature and concentration. In Fig. 5 the comparison
Fig. 6  FTIR spectra recorded on EPDM/IIR-Br (10 phr) exposed to
between FT-IR spectra recorded on the irradiated samples various doses. ( ) 0 kGy; ( ) 40 kGy; ( ) 100 kGy; ( ) 180 kGy; ( )
at 220 kGy shows the differences that exist when EPDM 280 kGy; ( ) 300 kGy. (Color figure online)
is compounded with butyl rubbers. As it is known [17] the
ethylene-propylene terpolymer is the most stable compo-
nent. The halogenated IIR plays the opposite role of radical is the representing dose point, when the vibration carbonyl
provider according with the easiness in the bond scission. band centered on the 1715 cm−1 peak becomes meaning-
The most vulnerable units, the isoprene configurations ful. On the lower dose range the intensities on the FT-IR
where halogen atoms are linked, become carbon centered region 1586–1851 cm−1 grow similarly. It means that the
sites where oxygen would be attached to form peroxyl oxidation is not a selective process because of the second-
radicals. The chains of the both components, EPDM and ary reactions of peroxyl radicals and hydroperoxides [40],
IIR, are simultaneously fragmented during γ-irradiation while at doses exceeding 100 kGy up to 300 kGy. The rise
because double bonds exist in ethylidene 2-norbornene and in carbonyl products is fed by the decomposition of high
isoprene moieties, respectively. Due to the molecular scis- concentration of hydroperoxides.
sion the new born radicals initiate further oxidation, if the The faster accumulation of carbonyl compounds in
recombination does not preferentially occur [39]. The oxi- respect with the increasing amounts of hydroxyl structures
dation is propagated by the attack of peroxyl radicals onto (Fig. 7) is happened either by the linking of molecular
the both types of materials or by disproportionation reac- oxygen on main chain and the decay of peroxyl units into
tions (classical Bolland and Gee mechanism) followed by C=O function, or by the decomposition of hydroperoxides.
the oxidation of new formed double bonds decreasing the The loading of 5% of butyl rubber is the most convenient
quality of final product. The oxidation progresses by the concentration in respect with the lowest oxidation state
accumulation of oxidation products, namely carbonyl and in γ-processed EPDM/IIR blends. This assertion can be
hydroxyl containing structures, whose concentrations are extended to the other two studied formulations because the
well characterized by carbonyl and hydroxyl indexes. In number of scissions increases proportionally with received
Fig. 6 the contribution of IIR-Br component to the increas- doses.
ing the oxidation degree is shown. The value of 100 kGy The contributions of aldehydes and ketones to the oxi-
dation state are defined by the competition between chain
scission reactions and decomposition of hydroperoxides in
which water is produced. The formation of water is sug-
gested by the twin peaks at 2331 and 2360 cm−1 recorded
in the spectra of irradiated blends containing IIR. The con-
comitant growth of these bands and the 1715 cm−1 band is
the proof for water springing from the reactions of hydrop-
eroxides. It may be assumed that the accumulated water is
subjected to radiolysis and their degradation intermediates,
protons and hydroxyls participate in some extent to the
radiolytic oxidative degradation of polymers.
The comparison between the radiation resistances of
butyl rubbers is shown in Fig. 8, where the presence of
halogen atoms affects the rate of oxidation. The mate-
Fig. 5  FTIR spectra recorded on γ-exposed EPDM/IIR films. Dose
100 kGy. IIR concentration 10 phr. (1) EPDM/IIR-Br, (2) EPDM/IIR- rial behavior reflects the increasing in the ratios of radi-
Cl, (3) EPDM/IIR-neat, (4) EPDM ochemical scission to crosslinking yields, G(X)/G(S),

13
J Polym Environ

Fig. 8  Carbonyl and hydroxyl indexes evaluated on EPDM/IIR

Fig. 7  Evolution of carbonyl and hydroxyl indexes for EPDM matrix. blends for 100 kGy γ-dose. IIR phase contents: (white) 5 phr, (dark
Butyl rubber load: (filled square) 5 phr, (filled circle) 10 phr, (filled grey) 10 phr, (black) 20 phr
triangle) 20 phr

Table 3  Charlesby–Pinner dependences for γ-processed EPDM/IIR

blends

Blend Relationship Correlation factor

defined by Charlesby-Pinner equation, which become
EPDM/IIR Y=1.66 + 6.57 X 0.98872
more and more far from unit by changes in the molecu-
EPDM/IIR-Cl Y=1.61 + 6.93 X 0.99428
lar structures from pristine IIR onto halogen substituted
EPDM/IIR-Br Y=1.74 + 5.07 X 0.98934
IIR. The expelling halogen atoms from the molecules of
chlorinated and brominated butyl rubbers is demonstrated
by the diminishing of their vibration bands at 615 and
536 cm−1 ascribed to C–Cl and C–Br, respectively [41]. Oxidation Investigation by Chemiluminescence
The decay in the diene could be observed by the
modification in the transmittance intensities at 808 cm−1 The experimental technique of chemiluminescence allows
[42, 43]. The double bonds from butyl rubbers and the the developing oxidation profiles in a good connection with
unsaturation from ethylene propylene terpolymer (trans- the temperature effects on polymeric structures. Chemi-
vinylene at 965 cm−1, vinyl at 909 cm−1 and vinylene at luminescence spectra are recorded by the decay process
889 cm−1 [34]) are also formed during radiolysis, but the of excited-state carbonyl groups formed during the termi-
recorded intensities are the results of their simultaneous nation step in the autocatalytic degradation process [44].
formation and consumption (Table 3 ). The CL emission intensities are considerable different in

13
 J Polym Environ

the function of intermediate populations [45]. In the cases (oxygen and bromine) are electronegative elements. On the
EPDM/IIR blends, the presence of any butyl rubber creates other side, the rate of oxidation is higher when halogenated
oxidation centers from where oxidation is spread [46]. The molecules are present in the degrading samples, because
increase in degradation temperature brings about an aug- their thermal and radiochemical instabilities are deficient.
mentation in the scission probability and the acceleration Even the both pristine polymers show the second peak at
of oxygen diffusion. The oxidation takes place faster in the 210 °C, it does not exist in the cases of halogenated butyl
rubber phase, where weaker bonds are placed and where rubbers, because they are faster oxidized. The greater CL
the penetration of oxygen is more facile. The CL spectra of intensities recorded at higher temperatures on halogenated
studied systems subjected to 100 kGy γ dose are presented IIR samples prove that the rate of excited intermediates as
in Fig. 9. The great difference between them is the pres- carbonyl groups is dominant. The macroradicals that result
ence of the emission peak recorded at 100 °C in ethylene- from the scission of polymeric chains are easily oxidized
propylene terpolymer/pristine butyl rubber. It disappears on at higher temperatures because they can facilely move in
the spectra obtained with halogenated butyl rubbers. The less viscous environment to collide oxygen molecules. The
explanation of this behavior would be the screening action mechanism of oxidative degradation in EPDM and IIR-X
of halogen atoms in respect with double bond of isoprene was previously reported [46, 47]. In fact, the efficient pro-
units against the attack of oxygen, because the both atoms cessing of the studied systems by γ-irradiation must be
accomplished at exposure doses less 100 kGy, because the
oxidation of materials reaches convenient degree. This dose
range is a proper option for the post-processing operations
of EPDM/IIR-X because during rolling, extrusion, com-
pression molding, injection molding or thermoforming
occurred at higher temperatures the degradation is acceler-
ated (Fig. 9).

Crosslinking

The reinforcement of polymer materials is based on radi-

cal recombination, which is in competition with oxidation.
At low dose rate like it was applied in this study the free
radicals react preferentially with diffused oxygen. Con-
sequently, the accumulation of gel fraction is smooth as it
was previously reported [32].
The addition of oxidation protector brought about a
minimization of oxidation in the favor of radical recom-
bination. The successful method for hardening polymer
wastes foreseen in their reclaiming as resistant products is
based on the scavenging capacity of additive. The variation
of gel content (Fig. 10) describes the evolution of gelation
in EPDM/IIR blends principally based on the crosslinking
of EPDM. The correlation between the changes in swell-
ing degrees, free volumes and crosslink densities in irradi-
ated butyl rubbers (Figs. 2, 3, 4) with the increase in the
gel content of γ-exposed EPDM-based blends points out
the specific contributions of the second component to the
homolytic crosslinked fractions. The sharp decrease in the
crosslink density of IIR suggests the formation of network
in EPDM/IIR blend about exclusively due to elastomer
component. The difference between the oxidation propa-
gation in halogenated butyl rubbers explains the competi-
tion effect involving the preferential mechanism of radical
Fig. 9  Nonisothermal CL spectra recorded for all studied composi- decay: recombination and reactions with oxygen. The evi-
tions of a EPDM/neat IIR and b EPDM/IIR-Br irradiated at 100 kGy.
(filled square) EPDM reference, (filled circle) 5 phr (filled up trian- dences of IIR-Br for oxidation are described by two investi-
gle) 10 phr, (filled down triangle) 20 phr gation methods, FTIR (Fig. 5) or gel content measurements

13
J Polym Environ

Conclusion

In this paper the radiation processing of butyl rubbers

demonstrates the availability of radiochemical recycling
of EPDM/IIR blends in respect with landfill, incinera-
tion and pyrolysis procedures based on the molecular
fragmentation without any other negative concern. The
blends consisting of ethylene-propylene terpolymer and
butyl rubbers under different halogen-substitution type
in isoprene moieties show oxidation and crosslinking,
but the recyclability depends on the effects of the com-
petition between recombination and oxidation occurred
to the processing conditions. The oxidative degradation
accomplished under γ-irradiation progresses much faster,
because the concentration of halogenated component
Fig. 10  Accumulation of gel content in radiation treated EPDM/IIR
provides free radicals available for oxidation at low dose
blends. Butyl rubber concentration: 5 phr; IRGANOX 1010 concen- rate.
tration, 0.5 phr (filled square) EPDM/IIR, (filled circle) EPDM/IIR- The use of these blends in the technological applica-
Cl, (filled triangle) EPDM/IIR-Br tions recommends EPDM/neat IIR as the most resistant
material because, at least, the increases in the carbonyl
and hydroxyl indexes are smooth. In economical prac-
tice it is expected that the conversion of elastomer wastes
assisted by γ-irradiation at the doses below 100 kGy
would be efficient. Because the diffusion of oxygen from
working environment depends on the crosslinking degree
the higher dose rates and low rubber loading would be
preferred for the proper management of processing. So
far this kind of investigation can be successfully extended
to any other end-of-life material options. It must not
disregard that new product which has low crosslinking
degree could be further recycled.
The irradiation option for recyclable polymer materials
with different origins like EPDM and IIR is self-recom-
mended accomplishment as a background operation in the
economical loops, because the improved performances in
respect with further employment can be achieved by the
design of proper formulation. The change of virgin mate-
Fig. 11  Charlesby–Pinner representation for radiation treated
EPDM/IIR blends. The composition details and the color meanings
rial into composite systems creates the encouraging input
are similar to Fig. 10. (Color figure online) sources for several technologies essentially defined as
saving procedures. The presumable applications of post-
consumer plastics recovered by γ-irradiation will be the
(Fig. 10). The Charlesby–Pinner representation (Fig. 11) start-points in the reconsideration of polymer wastes.
and the equations followed by the persisting sol amounts The stability analysis by chemiluminescence simulta-
(Table 2) prove that γ-irradiation of EPDM/IIRs mixtures neously done with spectroscopic investigation and swell-
is a praxis solution for the conversion of butyl rubbers into ing evaluation provides a realistic description of techno-
useful products. The slope values in the liner dependencies logical potential of radiation processing for saving natural
of S + S1/2 (where S is soluble fraction) on reciprocal dose resources which generate long life polymers.
indicate the tendency to destroy the new formed networks.
By this processing alternative the product life time and
diversity in material formulation can be optimized.
It must emphasize that the notable effect of this “clean”
recovery of rubbers is the convenient resistance of final
products relative to the diversity of foreseen applications.

13
 J Polym Environ

References 25. Zaharescu T, Jipa S, Giurginca M, Podină C (1998) Polym

Degrad Stab 62:569
26. Chipară MD, Grecu VV, Chipară MI, C. Ponta, J. Reyes Romero
1. Burillo G, Clough RL, Czvikovszky T, Guven O, Le Moel A,
(1999) Nucl Instrum Meth Phys Res B151:444
Liu WW, Singh A, Yang JT, Zaharescu T (2002) Radiat Phys
27. El-Sabbagh SH (2003) J Appl Polym Sci 90:1
Chem 64:41
28. Tostar S, Stenvall E, M. R. S. J. Foreman, Boldizar A (2016)
2. Sinha V, Patel MR, Patel JV (2010) J Polym Environ 18:8
Recycling 1&:p 101t;/bib>
3. Khan WS, Asmatulu R, Davuluri S, Dandin VK (2014) J Mater
29. M. H. Haji-Saeid, M. E. Sampa, N. Ramamoorty, A.
Sci Technol 30:854
Chmielewski, O. Güven (2007) Nucl Instrum Meth Phys Res
4. Enomoto I, Katsumura Y, Kube H, Sekiguchi M (2010) Radiat
B265&:p 51t;/bib>
Phys Chem 7:718
30. Zaharescu T, Cazac C, Jipa S, Setnescu R (2001) Nucl Instrum
5. Johnson J (2014) Post-consumer plastic recycling rates continue
Meth Phys Res 185&:p 360t;/bib>
strong growth. Plastics News Report
31. Manaila E, Stelescu D, Craciun G (2012) In: Boczkowska A (ed)
6. Marsh K, Bugusu B (2007) Food J Food Sci 72:R39
Polymer series—advanced elastomers. Technology, properties
7. EEA—European Environment Agency Report (2016) Most
and applications, ch. 1. INTECH, Rijeka
recent data: Further Eurostat Information. Main tables and
32. Zaharescu T, L. I. P. Kayan, Lungulescu ME, Parra DF, Lugão
database
AB (2016) Iranian Polym J 25:725
8. Pritchard G (1999) Reinforced plastics durability, ch. 2. CRC,
33. Allen NS, Hoang E, Liauw CM, Edge M, Fontan E (2001)
Boca Raton
Polym Degrad Stab 72&:p 367t;/bib>
9. IAEA—International Atomic Energy Agency (2004) Advances
34. Carlsson DJ, Čhmela S, Weiss DM (1989) Makromol Chem
in radiation chemistry of polymers. TECDOC 1420
Macromol Symp 27&:p 139t;/bib>
10. IAEA—International Atomic Energy Agency (2009) Controlling
35. Barton AFM (1991) In: Handbook of solubility parameters and
of degradation effects in radiation processing of polymers. TEC-
other cohesion parameters, 2nd edition. CRC Press, Boca Raton
DOC 1617
36. Luo Y-R (2007) Comprehensive handbook of chemical bond
11. Zaharescu T, Jipa S, Setnescu R, Setnescu T (2000) J Appl
energies. Taylor & Francis, Boca Raton
Polym Sci 77:982
37. Makuuchi K, Cheng S (2012) Radiation processing of polymer
12. A. G. Chmielewski, M. Haji-Saeid and Ahmed S (2005) Nucl.
materials and its industrial applications. (Wiley, New York
Instrum. Meth. Phys. Res. B236 44
38. Wood RJ, Pikaev AK (1993) Applied Radiation Chemistry.
13. Martínez-López M, Martínez-Barrera G, Barrera-Díaz CE,
Wiley, New York
Ureña-Nuñez F, Loredo dos Reis JM (2016) Constr Build Mater
39. Zaharescu T, Jipa S, Giurginca M (1998) J Macromol Sci Pure
121:1
Appl Chem A35:1093
14. Wang BL, Xu ZY, Zeng XM, Ma SM, Zang YX, Sun DM (1993)
40. Šećerov B, Marino-Cincović M, Popović S, Nedić Z, Kačarević-
Radiat Phys Chem 42:215
Popović Z (2008) Polym Bull 60:313
15. Barttacharya A (2000) Prog Polym Sci 25:371
41. Mateescu G (1982) In: FTIR Spectroscopy. Romanian Academy
16. Teinov AV, Zavyalov NV, Khokhlov YA, Sitnikov NP, Smetanin
Printing House, Bucharest, p.<background-color:#96C864;> </
ML, Tarantasov VP, Shadrin DN, Shorikov IV, Liakumovici A.
background-color:#96C864;>235
L., F. K. Miryasova (2002) Radiat Phys Chem 63:245
42. Rivaton A, Cambon S, J–L. Gardette (2006) Polym Degrad Stab
17. Karaağaç B, Şen M, Deniz V, Güven O (2007) Nucl Instrum
91:136
Meth Phys Res B265:290
43. Zaharescu T, Zen HA, Marinescu M, Scagliusi SR, E. C. L. Car-
18. Smith M, Berlioz S, Chailan JF (2013) Polym Degrad Stab
doso, Lugão AB, Chem (2016) Papers 70&:p 459t;/bib>
98:682
44. Fearon PK, Whiteman DJ, Billingham NC, Bigger SW (2001) J
19. Botros SH (1998) Polym Degrad Stab 62:471
Appl Polym Sci 79:1986
20. Singh RP, Chandra R (1982) Polym Photochem 2:257
45. Ahlblad G, Reitberger T, Terselius B, Sternberg B (1999) Polym
21. Davenas J, Stevenson I, Celette N, Vigier N, David L (2003)
Degrad Stab 65:169
Nucl Instrum Meth Phys Res B208:461
46. Zaharescu T, Postolache C, Giurginca M (1996) J Appl Polym
22. Abou Zeid MM, Rabie ST, Nada AA, Khalil AM, Hilal RH
Sci 59:969
(2008) Nucl Instrum Meth Phys Res B266&:p 111t;/bib>
47. Zaharescu T, Giurginca M, Jipa S (2009) Polym Degrad Stab
23. Özdemir T (2008) Radiat Phys Chem 77:787
63:245
24. Hacioğlu F, Özdemir T, Çavdar S, Usanmaz A (2013) Radiat
Phys Chem 83:122

13