Polymer International Polym Int 48:580586 (1999)

Vulcanization of carboxylated nitrile rubber

(XNBR) by zinc peroxide
L Ibarra* and M Alzorriz
Instituto de Ciencia y Tecnologa de Polmeros (CSIC), Juan de la Cierva, 3, 28006 Madrid, Spain

Abstract: The vulcanization of carboxylated nitrile rubber (XNBR) with zinc peroxide, which produces
ionic crosslinks, has been studied in relation to vulcanization time. Vulcanized compounds present two
transitions, corresponding to the glass transition of the polymer at low temperatures and the ionic
transition resulting from the formation of ionic aggregates. Both transitions are displaced to higher
temperatures with increasing crosslink density. The ionic associations which give rise to high values of
mechanical properties disappear on exposure of the vulcanized compounds to saturated ammonia
vapour. This treatment produces a decreased crosslink density resulting in the disappearance of the
ionic transition. When the action of ammonia is terminated by immersion in solvent followed by
drying, the original crosslink density is recovered and the ionic transition reappears, although at
higher temperatures. However, with increasing crosslink density, the difference between the
temperatures at which both transitions take place diminishes. All these factors can be interpreted as
reecting the generation of a new and more compatible arrangement of the newly-appearing ionic
clusters.
# 1999 Society of Chemical Industry

Keywords: carboxylated nitrile rubber; ionic crosslinking; crosslinking density; mechanical and dynamic
properties

INTRODUCTION ionic elastomers or ionomers with greatly improved

Ionomeric modication of elastomers consists of
introducing small amounts (<10%) of ionic function-
alities (eg COO, SO3) attached to the skeleton of the
elastomeric chain. These ionic groups can unite to
form ion-rich aggregates in an elastomeric matrix. The
ionic domains have a marked effect on the physical and
mechanical properties of the elastomers. Elastomeric
ionomers have been reviewed by MacKnight and
Lundberg.1
Crosslinking of carboxylate groups can occur via a
large number of chemical reactions,2 but the most
relevant method is by salt formation, especially using
divalent metal oxides.
Crosslinking in carboxylated nitrile rubbers
(XNBR) can take place via conventional methods
based on sulphur accelerators or by metallic oxides,
preferentially zinc oxide.3 One disadvantage of the
crosslinking of zinc oxides is that the compounds are
produced very early on which makes its practical
application difcult. This drawback is overcome by
using vulcanization agents, such as metal peroxides,
either in masterbatch with the polymer or in special
preparations.4
During the moulding process of carboxylated nitrile
rubber in the presence of metallic oxide, a carboxylic
acid salt is formed that gives rise to the formation of
physical properties.5,6 The crosslinks produced by the
zinc ion from the zinc oxide or peroxide are ionic as
opposed to those produced by conventional vulcaniza-
tion with sulphur-accelerators or organic peroxides
which are covalent.
There is considerable experimental and theoretical
evidence to support the existence of two principal
groups of ionomer salts, multiplets and clusters.7
Multiplets consist of small numbers of dipole ions
(around 68) grouped together to form larger multi-
plets such as quadrupoles, hexapoles, octapoles, etc.
These multiplets are dispersed within the hydrocarbo-
nate matrix and do not form a separate phase.
Therefore, in addition to acting as ionic bonds, these
also affect the properties of the matrix, such as the
temperature of the glass transition and sensitivity to
water. The clusters are considered to be small micro-
phases, of the order of 5 nm or less, in separate regions
rich in ion pairs but also containing a considerable
amount of hydrocarbon. These display some of the
properties of a separate phase, including relaxation
behaviour associated with a glass transition tempera-
ture, and exert a minimum effect on the properties of
the matrix, although they can have a certain reinfor-
cing effect. The proportion of ionic groups present in
either of these two forms in any particular ionomer is

* Correspondence to: Dr L Ibarra, Instituto de Ciencia y Tecnologa de Polmeros (CSIC), Juan de la Cierva, 3, 28006 Madrid, Spain
E-mail: ictir00@fresno.csic.es
Contract/grant sponsor: CICYT; contract/grant number: Project MAT 95/0099
(Received 29 June 1998; revised version received 15 January 1999; accepted 23 February 1999)

# 1999 Society of Chemical Industry. Polym Int 09598103/99/$17.50 580


determined by the nature of the hydrocarbon skeleton,
the concentration of salt groups and their chemical
nature.8
In an attempt to understand the nature of the
ionomer phases, the effects of plasticizers on their
physical properties have been studied.911 Plasticizers
can be grouped into two main types: plasticizers of the
chain skeleton, which mainly act on the non-polar part
of the hydrocarbon chain, and ionic plasticizers which
act on the ionic clusters: an example of the latter is
ammonia.12 In our laboratory changes in mechanical
properties such as stress relaxation and dynamic
properties were studied in relation to the vulcanizing
agent and the plasticization of ionic clusters, and these
changes were interpreted in terms of the kind of
crosslinking.13 This work shows that plasticization of
ionic aggregates with ammonia, which results in the
disappearance of the corresponding ionic transition, is
eliminated by the action of a solvent.
In the present study, vulcanization of carboxylated
nitrile rubber by zinc peroxide has been studied in
relation to the time of vulcanization and the changes in
mechanical properties, crosslink density and dynamic
properties before and after plasticization of ionic
clusters. The recovery of these properties after treat-
ment with solvent and drying is also studied.
EXPERIMENTAL
The carboxylated nitrile rubber used in this study was
XNBR Krynac 7.4 (Barcelona, Spain) which has an
acrylonitrile content of 27%, and 7.4% of carboxyl
groups.
The zinc peroxide used was Struktol ZP1014
(Hamburg, Germany), a preparation based on 50%
active compounds, 30% inorganic dispersants and
20% organic dispersants with a total zinc peroxide
content of 29% and a specic weight of 2.3 g cm3.
The mixture was prepared in a laboratory cylinder
mixer with a friction ratio of 1:1.25, maintained cool
by cold circulating water. The formula used was:
XNBR Krynac 7.4, 100 plus Struktol ZP 1014, 14
(that corresponds to 4 phr of ZnO2). Similarly, a
mixture with the same formula was prepared to which
2 phr of hydroquinone was added as a capturer of free
radicals.
The vulcanization curve was obtained using a
rotorless Monsanto rheometer (Wiltshire, UK), model
MDR 2000E, at a temperature of 150 C, with an
oscillation arch of 1 . The mixture was vulcanized in a
hydraulic press heated by thermouid to the vulcani-
zation temperature for a specic vulcanization time
corresponding to 50, 100, 200 and 300 min.
The volume of rubber swollen at equilibrium was
estimated using benzene as a solvent at room tem-
perature (23 C) and an immersion period of 6 days.
To measure the tensile properties an Instron
Dynamometer, model 4301 (Barcelona, Spain),
equipped with a video system to determine the
deformations produced was used. Dumb-bell test
Polym Int 48:580586 (1999)
Zinc peroxide vulcanization of XNBR
pieces were used and a deformation rate of 500 mm
min1 was applied. The crosslink density was deter-
mined by stressdeformation measurements, T-type
straight test pieces were used and a deformation rate of
0.5 mm min1 was applied.
The dynamic properties were measured using a
Metravib RAC 815 viscoanalyser (Limonest, France),
which operates in a frequency interval of 51000 Hz at
a temperature varying from 120 to 250 C, and a
dynamic deformation of up to 500 mm, with or without
static deformations.
Treatment with ammonia (Treatment A) consisted
of treating the vulcanized samples in ammonia
saturated vapour (30%) in a desiccator at room
temperature for a period of 24 h. Likewise, samples
previously treated with Treatment A were then swollen
in benzene for 6 days at room temperature, after which
they were dried to a constant weight (Treatment B).
RESULTS AND DISCUSSION
Vulcanization: rheometric curves
Figure 1 shows the vulcanization curve of the com-
pound over a 6 h period, separated into two compo-
nents of the pair of forces at 150 C elastic S' and
viscous S@. Firstly, it is noteworthy that the curve of the
elastic component, considered to be the vulcanization
curve, did not reach a plateau over the entire
vulcanization period. Zones of different gradient can
be distinguished along its length corresponding to
other regions of the curve of the viscous component,
which suggest that the process taking place is not
simply vulcanization.
In contrast, the curve corresponding to the viscous
component rose with vulcanization time, which is a
typical characteristic of ionic vulcanization.14 Never-
theless, this rise in the curve is not homogenous but
can be divided into regions of different gradient. In the
Fig 1 the points corresponding to vulcanizations have
been marked, because these are the most representa-
tive points of the vulcanization curve.
In our opinion, vulcanization with zinc peroxide
undoubtedly gave rise to ionic crosslinks although it is
logical to assume that CC links were also produced
because of the presence of peroxide radicals when the
crosslinking agent was decomposed. Vulcanization
was carried out in the presence of hydroquinone, a
capturer of free radicals, in order to observe possible
changes in vulcanization which would conrm the
presence of these kinds of bonds. In Fig 2 the
vulcanization curves corresponding to both vulcaniza-
tions are compared.
The presence of hydroquinone clearly modied the
vulcanization. It delayed the elastic component or the
start of vulcanization and reduced the degree of
vulcanization shown by the lower value of the
maximum pair. Although the vulcanization did not
reach a plateau, eventually there is only a very gradual
increase in the pair of forces with time, which can
almost be considered to be a plateau. With regards to
581
L Ibarra, M Alzorriz

Figure 1. Vulcanization curves of the

compound at 150 C: ( *) elastic
component S'; (&) viscous component S@.

Figure 2. Vulcanization curves of the

compounds at 150 C: ( *) vulcanization
with zinc peroxide; (&) vulcanization with
zinc peroxide in the presence of
hydroquinone.

the viscous component, this underwent a more Table 1. Tensile properties as a function of vulcanization time

signicant rise than that corresponding to the vulca- Vulcanization time (min)
nization in the absence of hydroquinone, with a
steeper gradient that almost reached a plateau, by 50 100 200 300
which stage the changes in this component with time
Stress at 100% strain (MPa) 1.41 1.88 4.90 5.71
were very small. Thus, if the ionic crosslinks bring
Stress at 300% strain (MPa) 2.61 10.06 15.81
about a rise in the viscous component in the presence
Tensile strength (MPa) 8.03 25.4 18.44 16.1
of hydroquinone that impedes the formation of Elongation at break (%) 601 456 325 259
covalent bonds which reduce this component, the
increase is produced without any restriction.

Influence of vulcanization time on properties properties, such as stress at constant deformation,

Table 1 shows the tensile properties of the vulcanized
compounds at different times. Stresses at constant
deformations increased progressively with time,
whereas the tensile strength reached a maximum
followed by a decline after prolonged vulcanization
times. Logically, elongation at break decreases. These
suggest a growing crosslink density. Nevertheless, the
considerable increase in crosslink density brings about
a reduction in the size of the chains of the network, and
under high stress the unequal distribution of the load
on the short chains has negative effects causing a
decrease in the tensile strength.

582 Polym Int 48:580586 (1999)

 Zinc peroxide vulcanization of XNBR

Table 2. Crosslink density by swelling and stressstrain measurements according to the expression
4 1
v  10 (mol ml )  
2 2 RT
=  1=0 1
Vulcanization time (min) vr Swelling Stressstrain  Mc
50 0.208 0.85 0.80
where f is the crosslinking functionality.
100 0.260 1.66 1.78
As expected, the density and crosslinking increase
200 0.327 3.40 3.55
300 0.348 4.14 4.29
with vulcanization time. Likewise, there is a reasonably
good correlation between the calculated swelling
values and stressstrain measurements. Nevertheless,
it is noteworthy that crosslinking of all the carboxyl
With regard to the crosslink density, Table 2 shows groups in the polymer is not produced, and it should
the values calculated from the measurements of be taken into account that the amount of vulcanization
swelling at equilibrium vr, and the stressdeformation agent incorporated into the mixture (4 phr ZnO2) and
values calculated from the MooneyRivlin equation, the concentration of carboxyl groups in the rubber
according to the following equations: corresponds to a 1:1 ratio, with a total theoretical
crosslinking density of 7.9  104 mol ml1. Thus, at
ln1 vr vr v2r very long vulcanization times, assuming that only ionic
vmol ml1 1=3
V0 vr vr =2 crosslinks are formed, approximately 54% crosslinking
is achieved.
where vr is the volume of rubber expanded at Figures 3 and 4 show changes in the storage
equilibrium, m is the parameter corresponding to the modulus E' and the loss factor tand with the
polymersolvent interaction and V0 is the molar temperature at a vibration frequency of 5 Hz. The
volume of the solvent. vulcanized compounds present two transitions: one at
The MooneyRivlin equation that describes the a low temperature corresponding to the glass transi-
general stressdeformation behaviour is given by the tion of the matrix and another at a high temperature,
expression: which is considered to appear as a result of the
ionomers formed during the crosslinking.17,18 These
 2C1  1=2 2C2 1 1=3 result either from the breakage and reformation of the
isolated multiplets or from movements which take
where C1 and C2 are constants, s/(l l2) is the stress place within the clusters.19,20
reduction and l is the extension or deformation ratio. The peak corresponding to Tg decreases in ampli-
In the representation of stress reduction versus 1/l, the tude and is displaced to higher temperatures with
experimental data t a straight line in a wide interval of increased crosslink density. This is logical because at
1/l.15 In accordance with Mark16 the crosslink density higher densities the polymer chains become increas-
determined by r/M0 can be determined from the stress ingly immobile. Likewise, the ionic transition is also
reduction extrapolated to 1/l = 0, where r is the displaced at higher temperatures and decreases in
density of the polymer and M0 the molecular weight amplitude. This is estimated as the surface area under
of the polymer chains between the sites of crosslinking the curves as the density increases. A similar displace-

Figure 3. Loss factor tan d at different

vulcanization times as a function of
temperature: (*) 50min; ( *); 100min;
(&) 200min; (&) 300min. Vibration
frequency 5 Hz.

Polym Int 48:580586 (1999) 583

L Ibarra, M Alzorriz

Figure 4. Storage modulus, E ' at different

vulcanization times as a function of
temperature. Symbols as in Fig 3.

Table 3. Temperatures of the transitions and apparent activation energies as result of the action of ammonia as an ionic plasticizer.
a function of vulcanization time and frequency
This phenomenon can be observed in Fig 5 for a
Apparent sample vulcanized for 200 min.
Frequency (Hz) activation Likewise, and due to the disappearance of the hard
Vulcanization energy microphase, there is a decrease in the storage modulus,
time (min) 5 8 12.5 20 (kJ mol1) especially in the elastic region. There is practically no
displacement of the temperature of the glass transition
At low temperature (Tg)
which also has the same magnitude as the original
50 10.9 10.1 8.9 7.7 250.6
100 8.5 7.7 6.2 5.2 234.6 value.
200 3.9 2.6 1.4 0.08 219.1 If the same sample is swollen in solvent by
300 1.4 0.06 1.6 3.04 194.2 prolonged immersion followed by drying, the changes
in dynamic properties, storage modulus and loss
At high temperature (Ti)
factors, reect the reappearance of the ionic transition,
50 min 74.9 83.7 84.5 89.5 97.6
as can be observed in Fig 6. Moreover, the tempera-
100 min 75 82.9 85.3 92.6 84.9
200 min 83.8 89.9 98 105.3 70.8 ture of the glass transition is displaced to higher values
300 min 85.3 92.7 101.6 108.1 67.5 without suffering any change in amplitude and there is
an increase in the value of the storage modulus in all
regions because of an increased rigidity produced by
the creation of rigid or hard microzones.
ment has been described for polystyrene21 and Table 4 shows the temperatures of the glass and
ethylene ionomers22 when the degree of neutralization ionic transitions after both treatments in all the
of the acid increases or when there is a rise in the total samples in comparison with the original values. The
amount of ionic links. ionic transition reappears, after swelling, at higher
Table 3 shows the temperature of the two transitions temperatures than in the original sample and an
and the activation energies of each relaxation process additional characteristic also becomes evident.
at the different vibration frequencies. As the cross-link Although the distance, in degrees, between the
density (or the cure time) increased, the temperatures temperatures of both transitions only changes slightly
of both transitions were shifted to higher values. The from 83.5 to 87.7 C, this difference increases in the
activation energy of both transitions decreased with samples after swelling, but gradually decreases again
increasing cross-link density and the activation energy with vulcanization time, from 120 C for the less
of the ionic transition was always lower than that for vulcanized mixtures to 89 C in those with a greater
Tg . degree of crosslinking. This can be interpreted as
representing the reappearance of the ionic transition,
Effect of the ammonia treatment and swelling in the or reformation of the clusters with a different arrange-
solvent ment to that observed in the original sample, as
When an XNBR rubber vulcanized with zinc peroxide microphases which gradually become compatible; this
is treated with ammonia-saturated vapour and its would explain the way in which the peaks of both
dynamic properties are determined, the transition phases, the matrix and the ionic clusters, move closer
resulting from the ionic associates disappears as a together.

584 Polym Int 48:580586 (1999)

 Zinc peroxide vulcanization of XNBR

Figure 5. Storage modulus, E ' and loss

factor tand as a function of temperature in
the 200 min vulcanizate; vibration
frequency 5 Hz: ( *) without treatment;
(*) after ammonia treatment.

Figure 6. Dynamic properties (E ' and tand)

after treatments as a function of
temperature: (&) after ammonia treatment;
(&) after swelling treatment.

The disappearance of the clusters or ionic associa- linking density shown by stressdeformation was
tions has been described as bringing about a drastic determined after each of the vulcanizing treatments,
deterioration in mechanical properties because of the and the results are recorded in Table 5.
lack of a reinforcing effect in these microspheres in the As a result of the ammonia treatment and dissolu-
vulcanized compounds.12 In this work, the cross- tion of the clusters, the crosslink density decreased
because these associations act as multifunctional
Table 4. Transition temperatures at 5 Hz after different treatments as a crosslinks. Logically, their reformation as revealed by
function of vulcanization time
Table 5. Crosslink density after different treatments by stressstrain
After
measurements
ammonia
Original treatment After swelling v  104 (mol ml1)
Vulcanization
time (min) Tg Ti Tg Tg Ti Vulcanization time (min) After NH3 treatment After swelling

50 10.9 74.9 10.3 8.2 111.6 50 0.57 0.98

100 8.5 75 9.0 5.9 100 100 1.49 1.78
200 3.9 83.8 4.6 1.7 97 200 2.27 3.24
300 1.4 85.3 1.2 3 92 300 3.76 4.15

Polym Int 48:580586 (1999) 585

L Ibarra, M Alzorriz
the reappearance of the ionic transition produced an
increase in or a recovery of the crosslink density to the
original values (Table 2) which would be expected to
produce a recovery of the mechanical properties of the
vulcanized compounds.
CONCLUSIONS
The following conclusions can be drawn from our
results.
Vulcanization of carboxylated nitrile rubber mainly
gives rise to ionic crosslinks; covalent links are formed
between chains due to the action of peroxide, although
this can be inhibited by the addition of hydroquinone.
The crosslink density of vulcanized compounds
increases with vulcanization time. With regard to the
mechanical properties, there is an optimum crosslink
density. Similarly, there are two transitions, one that
corresponds to the glass transition of the polymer and
the other is an ionic transition resulting from the
formation of ionic associations. Both of these are
displaced to higher temperatures and decrease in
amplitude with increasing crosslink density. However,
the distance between both peaks is maintained almost
constant.
Ionic aggregates are solvated in ammonia that acts
as an ionic plasticizer producing disappearance of the
ionic transition and resulting in a decreased crosslink
density. This is presumably accompanied by a loss of
mechanical properties which produces a decrease in
the storage modulus due to the loss in rigidity of the
vulcanized compound brought about by the dis-
appearance of the clusters.
The action of ammonia is reversible, i.e. its effects
are eliminated by swelling in the solvent followed by
drying. When this takes place the crosslink density of
the original values is recovered, the ionic transition
reappears, and the value of the storage modulus
increases.
The new ionic transition takes place at a higher
temperature than in the original vulcanized compound
and decreases with increased crosslink density. Simi-
larly, the temperature of the glass transition of the
586
matrix is displaced to higher temperatures as the
crosslink density rises, as a consequence of a greater
immobility of the chains. The smaller difference
between the transition temperatures is probably
associated with a new arrangement of the ionic clusters
that gives rise to greater compatibility between the
phases of the matrix and ionic associations.
ACKNOWLEDGEMENTS
The authors thank CICYT for nancial support of this
work through Project MAT 95/0099.
REFERENCES
1 MacKnight WJ and Lundberg RD, Rubber Chem Technol 57:652
(1984).
2 Brown HP, Rubber Chem Technol 30:1347 (1957).
3 Zakharov ND, Rubber Chem Technol 36:569 (1963).
4 Grassman RF and McKane FW, Rubber World 196:36 (1987).
5 Brown HP, Rubber Chem Technol 36:931 (1963).
6 Chakraborty SK and De SK, Polymer 24:1055 (1983).
7 Eisenberg A, Macromolecules 3:147 (1970).
8 MacKnight WJ, in Structure and Properties of Ionomers. NATO
ASI Series C Mathematical and Physical Sciences, Vol 198, Ed
by Pineri M and Eisenberg A (1986) p 1.
9 Navratil M and Eisenberg A, Macromolecules 7:84 (1974).
10 Bazuin CG and Eisenberg A, J Polym Sci Polym Phys Ed 24:113
(1986).
11 Hara M, Jaraud P and Sauer JA, Polymer 32:1380 (1991).
12 Mandal UK, Tripathy DK and De SK, Polymer 37:5739 (1996).
13 Ibarra L, J Appl Polym Sci in press.
14 Mandal UK, Tripathy DK and De SK, Polymer 34:3832 (1993).
15 Mark JE and Erman B, Rubber Elasticity: A Molecular Primer. John
Wiley and Sons, New York. Chapter 8 (1986).
16 Mark JE, Rubber Chem Technol 55:762 (1982).
17 Weiss RA, Fitzgerald JJ and Kim D, Macromolecules 24:1071
(1991).
18 Weiss RA, Fitzgerald JJ and Kim D, Macromolecules 24:1064
(1991).
19 MacKnight WJ and Earnst TR, J Polym Sci Part D 16:41 (1981).
20 Bazuin CG and Eisenberg A, Ind Eng Chem Prod Res Dev 20:271
(1981).
21 Eisenberg A and Navratil M, Macromolecules 7:90 (1974).
22 MacKnight WJ, McKena LW and Read BE, J Appl Phys 38:4208
(1967).
Polym Int 48:580586 (1999)