ELASTOMERE UND KUNSTSTOFFE
ELASTOMERS AND PLASTICS
Zinc oxide · Phase transfer catalysts ·
Sulphur vulcanisation
The impact of reducing zinc oxide con-
tent in IR and E-SBR compounds on vul-
canisation kinetics and vulcanisate
properties was investigated by using
active ZnO(100 nm) and standard ZnO
(1Nm) and by considering the activation
of ZnO by the phase transfer catalyst
18-crown-6.
It was found that active ZnO tends to
agglomerate in rubber compounds. The
difference in activity between active
and standard ZnO grades is smaller in IR
compounds than in SBR ones. It was
proven that 18-cown-6 can play an ac-
tive role in catalyzing the cross-linking
reaction, while causing increased rever-
sion in IR compounds. It is shown that
the ZnO content can be reduced in car-
bon black filled IR compounds to 2 phr
and in E-SBR compounds even to 1 phr
without affecting vulcanisation kinet-
ics and vulcanisate properties.
Untersuchungen zur Verminde-
rung von Zinkoxid in Kautschuk-
mischungen, Einfluss der spezi-
fischen Oberfläche des ZnO und
des Phasentransfer - Katalysa-
tors 18-crown-6
Zinkoxid · Phasentransferkatalysator ·
Schwefelvernetzung
Der Einfluss verminderter Zinkoxiddo-
sierungen auf die Vernetzungskinetik
und die Vulkanisateigenschaften von IR
und E-SBR Mischungen wurde unter
Verwendung von aktivem ZnO (100nm)
und Standard ZnO (1µm) und des Kro-
nenäthers „18-crown-6“ untersucht. Es
wurde gefunden, dass aktives ZnO zur
Bildung von Agglomeraten neigt und
die Unterschiede zwischen aktivem und
Standard ZnO in IR geringer ausfallen
als in E-SBR. Es wurde gezeigt dass der
Kronenäther eine aktive Rolle in der Ka-
talyse des Vernetzungsvorgangs über-
nimmt, jedoch bei IR eine verstärkte Re-
versionsneigung hervorruft. Die ZnO
Dosierung kann ohne Einbußen bei Re-
aktionskinetik und Vulkanisateigen-
schaften bei rußgefüllten IR auf 2phr
und bei E-SBR auf 1 phr gesenkt werden.
1
Editorial note:
With deep regret we report that Mr. Leszek
Pysklo of Piastow, Poland died after completion
of this article.
548 KGK · Oktober 2007
Study on Reduction of Zinc
Oxide Level in Rubber
Compounds Part I1
Influence of Zinc Oxide Specific Surface Area and the Interphase
Transfer Catalyst 18-crown-6
Zinc oxide (ZnO) together with stearic acid
is considered as an indispensible activator
for sulphur vulcanisation. It is used tradi-
tionally in concentrations of 3 or 5 phr.
Recently, the reduction of the ZnO level in
rubber compounds has become an impor-
tant issue because of concern over levels of
Zn in Europe’s waterways and harmful ef-
fect of soluble Zn-compounds to aquatic or-
ganisms [1]. Zn can be released into the en-
vironment from rubber during production,
use, and recycling of rubber goods, particu-
larly tyres. The potential sources of Zn in
ground water are rubber dust worn from
tyres [1] and rubber granulates produced
from end-of-life tyres used in the construc-
tion of artificial sports pitches [2]. According
to Council Directive 2004/73/EC ZnO is clas-
sified as N “Dangerous for the Environ-
ment”, with the risk phrase R50/53 “Very
toxic for to aquatic organisms, may cause
long-term adverse effects in the aquatic en-
vironment”.
The EU-aided research project ‘’Reduced
zinc in rubber compounds for an enhanced
environment (ECOZINC) was performed for
4 years (finished in January 2005) to asses
ways of reducing the Zn-content in rubber
compounds. Interesting results of this re-
search were published [3] and presented at
conferences [4, 5]. Studies on reduction and
substitution of zinc oxide in rubber com-
pounds were also carried out [6-8].
There are two main possible ways to reduce
the amount of zinc oxide in rubber com-
pounds:
t application of so called active ZnO having
nano-particles size and high surface area
[6],
t application of additional effective activa-
tors
Noordermeer proposed to apply zinc ions
saturated montmorillonite saturated with
Zn-ions, called ZnClay [7]. This proposal
looks very interesting but only limited
amount of data is available. It seems that
ZnClay can be used efficiently only in some
types of rubber compounds. The aim of our
project was to evaluate possibility to reduce
the amount of ZnO in IR and SBR com-
pounds by means of interphase transfer
catalysts mostly the crown ether
18-crown-6. The first who applied an inter-
phase transfer catalyst to activate sulphur
vulcanisation were Proycheva [9] and Ro-
manova [10]. However, the authors used
dibenzo-18-crown-6. The conformational
change of stable planar conformation of
dibenzo-18-crown-6 is less effective and
probable than the one for 18-crown-6 be-
cause of the rigidity imposed by the benzo-
groups. This is influencing the complexing
ability of Zn ions [11]. The activation effect
of 18-crown-6 on conventional vulcanisa-
tion systems composed of sulphur and MBT
has been recently evaluated by Kleps and
co-workers [12].
Chemistry of sulphur vulcanisation in
presence of zinc oxide
The most popular accelerators of sulphur
vulcanisation are 2-mercaptobenzothiazole
sulfenamides. Recently, the comprehensive
review on sulphur vulcanisation for benzo-
thiazol accelerated formulations has been
Authors
L. Pysklo, P. Pawlowski,
W. Parasiewicz, Piastow (Poland),
L. Slusarski, Lodz (Poland)
Corresponding author:
Wanda Parasiewicz IPG Instytut
Przemyslu Gumowege Stomil
Kl. Haracerska 30
05-820 Piastow, Poland
published by Ghosh and co-workers [13].In
Benzothiazole –zinc-complex
spite of many studies some aspects of the (ZMBT) [13]
mechanism of sulphur vulcanisation are not
clear. It is postulated that in the case of vul-
canisation systems composed of sulfena-
mides, ZnO, stearic acid and sulphur the ac-
celerator and the activators react to form
the active accelerator complex [13-15]
(Scheme 1):
This complex is largely insoluble in hydro-
carbon rubbers and is render soluble and re-
active through coordination with amine lig-
ands derived from sulfenamide, and sec- cursor. The bound intermediate can react
ondary accelerators and carboxylate ligands with another rubber chain or with another
derived from stearic acid or zinc stearate. A bound intermediate to generate a crosslink.
typical structure of the zinc/benzothiazole The former reaction is more probable be-
ligand complex is shown below (Scheme 2). cause reaction between two pendant inter-
Many studies for different accelerators have mediates requires them to diffuse to each
confirmed that ZnO readily form Zn- com- other, which is unlikely because they are
plexes with MBT, that is generated by ther- bulky molecules with limited mobility [13]
Benzothiazole-zinc-amine complex
mal decomposition of sulfenamide acceler- (Scheme 5).
ator [13]. This reaction does not proceed to The post-crosslinking chemistry is also impor-
completion due to the formation of an in- tant because Zn-accelerator-complexes cause
soluble layer of ZMBT on the surface of ZnO. an increase in the rate of decomposition of di-
The bezothiazole–zinc-amine-complex re- and polysulphidic crosslinks. Their effect on
acts with sulphur and forms the active sul- desulphuration is much greater [15].
phurating complex. According to Chapman
and Porter two sulphuration agents are Experimental
formed [15] but which one is the active sul- Standard test formulations of IR and SBR
phuration agents in a Zn-containing vulcan- compounds according to ISO 2303 and 2322
isation system is the major unsolved prob- respectively were used. The composition of
lem of sulphur vulcanisation (Scheme 3). the compounds is given in Table 1 and 2. The
Ignatz-Hoover et al., based on their studies following raw materials were chosen: IR
using semiempirical quantum mechanical (SKI-3 from russian production), E-SBR
calculations and quantitative structure-ac- (Ker 1500, Firma Chemiczna Dwory S.A., Po- Sulphurating agents postulated by
tivity relationships software, have suggest- land), carbon black N-330, sulphur, N-tert- Chapman and Porter [15]
ed different structures of the sulphuration butyl-2-benzothiazolesulphenamide (Rhe-
complex, having sulphur polythiolate coor- nogran TBBS-80, RheinChemie).
dinated to the Zn ion with the coordination Two grades of ZnO were used: standard ZnO Grade 1,Huta Oława, Poland) and active
number of five or six [16] (Scheme 4). produced by the French Process having large ZnO produced in a wet chemical process
The presence of zinc in the sulphurating particle size and correspondingly a small with average particle size of 36 nm and a
complex provides a nucleophilic character specific surface area 4,7 m2/g (Zinc White specific surface area of 44 m2/g (Zinkoxid
to the sulphur atom attached to the zinc.
The amine ligands further increase the nu-
cleophilicity of the sulphur in the polythi-
olate complex [13]. The formation mecha-
nism of crosslink precursors in the Zn- con-
taining vulcanisation systems is considered
to be a polar one. The presence of ionic spe-
cies during sulphur vulcanisation in the
presence of ZnO was confirmed indirectly
by Hummel based on electrical current
measurements in the course of cure [17].
The poly-thiolate species BtS-SxD- reacts at
the allylic hydrogen of the rubber chains via
a SN2 mechanism to form rubber bound in- Sulphurated accelerator complexes proposed by Ignatz-Hoover at al [16]
termediate whereas the species Bt-SyD+ is
terminated with a hydrogen atom forming
Formation of rubber
Bt-SyH, and zinc is liberated as ZnS. This bound intermediate by
mechanism is generally accepted. The rub- a polar mechanism [14]
ber bound intermediate is a crosslink pre-

KGK · Oktober 2007 549

 ELASTOMERE UND KUNSTSTOFFE
ELASTOMERS AND PLASTICS

Aktiv Plus, Bayer Polymers). The SEM pic-

1
tures of the ZnOs are shown in Figure 1.
Besides 18-crown-6 (Merck) also 15-crown-5
(Borreggaard, Norway), 12-crown-4 (Merck)
and poly (ethylene glycol) (Polikol 1500,
Zakłady Chemiczne “Rokita”, Poland) were
investigated as potential activators of sul-
phur vulcanisation.
IR and E-SBR compounds were mixed on a
two-roll laboratory mill. Vulcanisation
characteristics of IR and SBR compounds
were measured at 150
nC and 160
nC re-
1 SEM picture of zinc oxide a) Zinc White Grade 1, b) Zinkoxid Aktiv spectively with a Moving Die Rheometer
(MDR 2000) at the amplitude of oscillation
0.5 n according to ISO 6502. The scorch time
2 2 Influence of reduc- t10, optimal vulcanisation time t90, extent
tion of zinc oxide of cure %M  MH-ML an d vulcanisation
contents in IR com-
reversion of compounds were determined.
pounds on the
scorch time t10 IR and E-SBR compounds were cured in a
laboratory press at 150
nC and 160 nC re-
spectively according to the optimal vulcan-
isation time t90, increased by 3.5 min. Ten-
sile properties were measured with a ten-
sile testing machine Zwick 1450 according
to ISO 37.
SEM pictures of ZnO were taken with a
Zeiss/LEO 1530 equipped with X-ray micro-
analizer EDS Link ISIS and detector Si-Li at
an acceleration voltage 10 kV. The
Zeiss/LEO 1530 was also used to evaluate
dispersion of zinc oxide in rubber matrix.
3 Conversion of zinc oxide to zinc sulphide during vulcanisation of IR compounds containing Samples were frozen in liquid nitrogen and
different amounts of standard and active zinc oxide and a phase transfer catalyst 18-corona-6; broken and next their fracture surface was
stearic acid was use in the amount of 2 phr observed. Dispersion of zinc oxide was eval-
Activator system, Amount of ZnO Degree of conversion uated on fracture surface of vulcanisates
phr converted to ZnS, phr of ZnO to ZnS, %
frozen in liquid nitrogen.
Standard ZnO 5 0.49 9.9
Standard ZnO 5/18-crown-6 0.3 0.54 10.8 Results and discussion
Standard ZnO 2 0.61 30.7 The influence of the activators has to be an-
Standard ZnO 2/18-crown-6 0.3 0.58 28.8 alysed from two points of view: the vulcan-
Active ZnO 5 0.47 9.4 isation characteristics and the vulcanisates
Active ZnO 5/18-crown-6 0.3 0.55 11.1 properties.
Active ZnO 2 0.71 35.7
Active ZnO 2/ 18-corona-6 0.3 0.64 32.4 IR compounds

Influence of ZnO specific surface area

3 3 Influence of reduc-
on vulcanisation characteristics
tion zinc oxide
The active ZnO provides a slightly longer
contents in IR com-
pounds on the scorch time (t10) and a distinctly longer op-
optimal vulcanisa- timal vulcanisation time t90 than the stan-
tion time t90 dard one. The reduction in the quantity of
both ZnO from 5 to 2 phr has a little influ-
ence on t10 (Fig. 2).
In the case of the active ZnO the scorch
time (t10) does not change down to 1 phr
but below this level it is reduced dramati-
cally. The decrease in the amount of ZnO
has a larger influence on the optimal vul-
canisation time. Below 2 phr of both ZnO
the cure time (t90) is significantly reduced
(Fig. 3).

550 KGK · Oktober 2007

1 IR compound formula 4 Vulcanisate properties of IR compounds containing different amounts of standard zinc oxide
Material phr Property Standard ZnO Standard ZnO+0.3 phr 18-C-6
phr phr
IR 100.0
Sulphur 2.25 5 3 2 1 0.5 5 3 2 1
Stearic acid 2.00 Tensile strength, MPa 27.5 29.6 28.7 26.5 25.5 28.3 29.9 28.4 29.5
Carbon blackN-330 35.0 Elongation at break, % 570 591 623 583 616 592 580 559 568
Zinc oxide Variable (0.5-5.0) Modulus at 300% 8.9 9.3 7.2 7.8 7.7 9.2 10.4 9.9 9.2
TBBS 0.7 extension, MPa
18-crown-6 0.3 Hardness, °Sh 54 54 53 51 51 57 58 58 57

2 SBR compound formula 5 Vulcanisate properties of IR compounds containing different amounts of active zinc oxide
Material phr Property Active zinc oxide Active ZnO +0.3 phr 18-C-6
E-SBR 100.0 phr phr
Sulphur 1.75 5 3 2 1.5 1 0.5 5 3 2 1.5 1
Stearic acid 1.0
Tensile strength, MPa 26.9 29.0 29.3 25.3 26.4 21.7 29.2 27.0 29.2 30.0 28.8
Carbon black N-330 50.0
Elongation at break, % 568 588 602 562 612 593 581 539 580 574 620
Zinc oxide Variable (0.5-3.0)
Modulus at 300 % 8.6 9.3 9.0 8.3 7.7 6.5 9.5 10.0 9.6 10.6 8.0
TBBS 1.0
extension, MPa
18-crown-6 0.3
Hardness, °Sh 55 55 54 53 52 50 59 59 59 57 53

The extent of cure %M decreases distinctly

below 3 phr of standard ZnO and 2 phr of 4 4 Influence of reduc-
active ZnO (Fig. 4). tion zinc oxide
It should be stressed that bellow 2 phr of contents in IR com-
pounds on the
both types of ZnO the extent of vulcanisa-
extent of cure %M
tion reversion increases significantly
(Fig. 5).
The small difference between the active
ZnO and standard ZnO despite nine times
higher specific surface area can be ex-
plained by taking into account the poorer
dispersion of the active ZnO. The micro-
graphs (Fig. 1b) show the tendency of the
active ZnO to form large agglomerates. Be-
sides that it was observed during mixing
rubber compounds on a two-roll mill that it
is more difficult to incorporate into rubber
the active ZnO than the standard one. The
5 5 Influence of zinc
SEM examination of vulcanisates also con-
oxide contents in IR
firms that the active ZnO forms larger ag-
compounds on
glomerates than the standard one what is vulcanisation rever-
shown in Figure 6a and 6b (18). sion

Influence of 18-crown-6
The phase-transfer catalyst 18-crown-6 has
been proven to be a very efficient activator
of sulphur vulcanisation in the presence of
TBBS. In the case of compounds with 5 phr
of either standard or active ZnO addition of
0.3 phr of 18-crown-6 without stearic acid
results in considerable decrease in the
scorch time (t10)and the optimum cure time
(t90) and increase in the extent of cure and
vulcanisation reversion in comparison with
the conventional activators system ZnO respectively. Addition of 0.3 phr of the of addition the crown-ether alone. The re-
and stearic acid was observed (Fig. 7). crown ether together with 2 phr of stearic duction of the content of standard and
The extent of cure of both the ZnO grades acid and 5 phr of ZnO has smaller effect active ZnO to 3 phr in the presence of
is similar. %M amounts 14.54 and on the decrease of t10 and t90. The extent stearic acid and the crown-ether has an
14.15 dNm for active and standard ZnO of cure is on the same level as in the case interesting influence on the curve of the

KGK · Oktober 2007 551

 ELASTOMERE UND KUNSTSTOFFE
ELASTOMERS AND PLASTICS

6 Cure characteristics at 160°C of SBR compound containing different amounts of standard zinc oxide extent of ZnO conversion to ZnS is tree
Standard ZnO+0.3 phr 18-C-6
times higher what indicates the more com-
Standard ZnO
phr phr
plicated post-crosslinkig chemistry at low
concentrations of ZnO, probably due to
5 3 2 1 0.5 3 1
higher sulphur rank of crosslinks. At 2 phr
t10, min 4.56 4.55 3.20 2.84 2.70 2.52 2.59 the active ZnO produces more ZnS than the
t90, min 15.60 15.78 12.05 10.93 10.18 8.92 7.99 standard one (Table 3). Application of
MH – ML, dNm 18.24 18.16 18.74 17.49 14.59 19.20.0 18.13 18-crown-6 does allow to reduce the ZnO
content to 2 phr for both grades of ZnO. Fur-
7 Cure characteristics at 160 °C of SBR compounds containing different amounts of active zinc oxide ther reduction of ZnO content also brings
about significant decrease of t10, t90, extent
Active ZnO Active ZnO+0.3 phr 18-C-6
of cure and increase of vulcanisation rever-
phr phr
sion as in the case of the traditional activa-
5 3 2 1 0.5 3 1 tor system ZnO/stearic acid (Fig. 2-5).
t10, min 5.38 5.49 3.90 3.38 2.80 3.47 2.75
t90, min 19.35 18.09 14.33 12.76 10.63 10.71 8.39 Properties of vulcanisates
MH – ML, dNm 16.69 16.23 17.29 16.08 13.79 18.87 17.41 In the case of standard zinc oxide reduction
in its content to 2 phr in IR compounds with
traditional activators system results in sig-
6 nificant decrease in modulus 300 % and de-
crease of hardness (Table 4).
For active ZnO the reduction of modulus
and hardness occurs at 1 phr (Table 5). In the
presence of 18-crown-6 and stearic acid
even 1 phr of standard ZnO gives the same
vulcanisate properties as 5 phr but in the
case of active ZnO modulus and hardness
are reduced below 1.5 phr.

E-SBR compounds
6 SEM pictures of ZnO agglomerate in IR vulcanisates a) standard ZnO, b) active ZnO The difference between standard and ac-
tive ZnO is more visible in E-SBR com-
8 Vulcanisate properties of SBR compounds containing different amount of standard zinc oxide pounds. Active ZnO gives longer times t10
and t 90 and smaller extent of cure (Ta-
Standard ZnO Standard ZnO+0.3phr 18-C-6
ble 6, 7). There is no difference between 5
Property phr phr
and 3 phr of ZnO. Reduction of ZnO content
5 3 2 1 0.5 3 1 to 1 phr results in shortening of t10 and t90
Tensile strength, MPa 27.1 26.5 27.8 27.6 26.7 25.3 23.1 but the extent of cure is on the same level.
Elongation at break, % 419 398 431 419 510 363 401 The crown-ether 18-crown-6 is activating
Modulus at 300% 18.4 19.6 18.0 19.0 14.1 20.0 18.2 the vulcanisation and increases the extent
extension, MPa of cure but does not bring about vulcanisa-
Hardness, °Sh 67 68 67 70 65 71 69 tion reversion. At 1 phr of both ZnO
18-crown-6 does insure better vulcanisate
properties than traditional activator sys-
9 Vulcanisate properties of SBR compound containing different amounts of active zinc oxide
tem (Table 8, 9).
Active ZnO Active ZnO +0.3phr 18-C-6
phr phr
Property Conclusions
5 3 2 1 0.5 3 1 1. The system of activators composed of
Tensile strength, MPa 27.6 27.6 28.1 27.4 26.7 24.5 25.6
zinc oxide and small amount of
Elongation at break, % 439 454 427 450 537 369 408
18-crown-6 activates efficiently, even in
Modulus at 300% 17.7 17.2 18.4 17.1 12.6 18.6 17.3
the absence of stearic acid, sulphur vul-
extension, MPa
canisation of IR compounds but increas-
Hardness, °Sh 65 66 68 66 65 68 68
es vulcanisation reversion. The reversion
of vulcanisation is reduced in the pres-
ence of stearic acid.
loss modulus S’’ shown in MDR graphs. A The maximum appears as well when 1 phr 2. Application of the system of activators
maximum appears which grows and wid- of both ZnO is used in the absence of the composed of zinc oxide, stearic acid and
ens on lower levels of ZnO. This indicates crown-ether (Fig. 9). 0.3 phr of 18-crown-6 enables to cut
that the formed crosslinks undergo rapid It was observed that at 2 phr of both grades down the zinc oxide level in IR compound
desulphuration and decomposition reac- of ZnO the larger amount of ZnS is produced to 2 phr ensuring suitable vulcanisation
tions (Fig. 8). during vulcanisation than at 5 phr and the characteristics and the similar vulcani-

552 KGK · Oktober 2007

 7 7 MDR curves at
150nC of IR com-
pounds contain-
ing: a) 5phr stand-
ard ZnO and b)
5phr active ZnO
and
0.3phr 18-crown-6
(without stearic
acid)

sates properties as in the case of 5 phr of 8 8 MDR curves at 150nC of IR

zinc oxide. Lower levels of zinc oxide
cause appreciable increase in reversion
of vulcanisation. There is no significant
difference between standard zinc oxide
having particle size larger than 1 micron
and active zinc oxide with particle size
around 36 nm.
3. Lower level of zinc oxide can be used in
emulsion SBR compounds. It seems that
1 phr of zinc oxide is enough to vulcanise
satisfactorily E-SBR compounds.
4. Because of specific and very effective in-
fluence of small amounts of 18-crown-6
on vulcanisation kinetics and efficiency,
it seems that this crown ether and prob-
ably other ones could be useful for inves-
tigating mechanism of sulphur vulcani-
sation particularly NR and IR com-
pounds.
Acknowledgements
The research was financed from resources
of the State Committee for Research for as
the research project No. 4T08E 065 25 per-
formed in the years 2003-2006.
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9 9 MDR curves at
150n
C of IR com-
pounds contain-
ing: a) 1phr stand-
ard ZnO, b) active
ZnO and 2phr
stearic acid

KGK · Oktober 2007 553