Eur. Polym. J. Vol. 32, No. 1, pp.

35-41, 1996
Pergamon Copyright 0 1995Elsevier Science Ltd
Printed in Great Britain. All rights reserved
0014-3057196 fl5.00 + 0.00

EFFECTS OF A MULTIFUNCTIONAL ADDITIVE ON

BOUND RUBBER IN CARBON BLACK AND SILICA
FILLED NATURAL RUBBERS

E. SHENG,‘.2,3* I. SUTHERLAND,* R. H. BRADLEY,3 and P. K. FREAKLEY’

‘Rubber Processing and Engineering Centre, Institute of Polymer Technology and Materials Engineering,
2Department of Chemistry, ‘Institute of Surface Science and Technology, Loughborough University of
Technology, Loughborough, Leicestershire, LEI 1 3TU, U.K.

(Received 2 November 1994; accepted in final form 6 December 1994)

Abatraet-The effects of a multifunctional additive (MFA), i.e. a diamine salt of a carboxylic acid, on
the bound rubber in carbon black and silica filled natural rubber compounds in o-xylene, have been
studied. For the carbon black filled compound, the bound rubber initially decreases with the MFA
concentration and then does not change significantly above an MFA concentration which approximately
corresponds to the monolayer surface coverage of the carbon black. This phenomenon has been explained
in terms of the release of immobilised rubber within the carbon black agglomerates. Bound rubber
measured at high temperatures indicated that the MFA did not improve the chemical interaction between
the carbon black and the rubber in an unvulcanised rubber mix. The MFA has no pronounced effects
on the bound rubber for silica. This may be caused by the combined effects of improved filler dispersion
and silica-rubber interfacial interaction. The ozone oxidation of the carbon black significantly increases
its surface oxygen concentration but has little effect on its specific surface area. The oxidation has been
found to decrease the bound rubber.

1. INTRODUCTION a surface area of 78 m*/g and the silica (Degussa VN3)

When a rubber and a filler are mixed, they interact in
such a way that even a good solvent can only partially
dissolve the rubber which originally is completely
soluble in the solvent. The insoluble rubber is often
referred to as the bound rubber and has been re-
viewed by several authors [l-4]. Bound rubber is
primarily affected by the nature of the filler (e.g.
surface area, structure, surface chemistry) and the
nature of the rubber (e.g. unsaturation, molecular
weight). Mixing and testing conditions, and additives
in the rubber may also effect the bound rubber.
A diamine salt of a carboxylic acid having a general
structure of
RNH;(CH,),NH: (R’COO-)2
which is referred to as a multifunctional additive
(MFA), has been found to act as a rubber processing
aid, a filler dispersant, a cure accelerator, and also a
mould release agent [5-81. In this study, we examined
the effects of an MFA on the bound rubber of a carbon
black and a silica when compounded with a natural
rubber. The effects of ozone oxidation of the carbon
black on the bound rubber were also investigated.
2. EXPERIMENTAL
Table I lists the materials
and the formulation used in
rubber mixing. The carbon black (Cabot N330) used has
*Present address for correspondence: ICI Polyurethanes
Regional Development Center, 8 Lorong Tukang Lima,
Singapore 2261.
has a surface area of 169m2/g as measured by nitrogen
adsorption.
The mixing was performed on a Francis Shaw Kl Inter-
mix. Table 2 gives the mixing cycle used. A smaller mixer,
a Haake Rheocord 90, was used for the ozone oxidised
carbon black, since only limited amounts of carbon black
can be practically oxidised with the ozonator used. The
mixing cycle with the Haake Rheocord 90 (Table 3) was
slightly different. Under the conditions used, no significant
difference in the properties of the resulting rubber com-
pounds or vulcanisates between the two mixers was found.
The bound rubber at room temperature was measured by
immersing ca. 0.25 g of an unvulcanised rubber mix, diced
into about 10 pieces, into 50 ml of o-xylene (AR grade, ex.
Aldrich) in a wide-mouthed glass bottle. The bottle was then
sealed and left standing at room temperature. Following the
extraction, the swollen rubber pieces were taken out and
thoroughly dried in a vacuum oven at WC and thermo-
gravimetrically analysed using a Stanton Redcroft TG-750
analyser. For these measurements, a 10mg sample was
purged in nitrogen and then heated at a rate of SO”C/min
and the weight loss monitored with a chart recorder. Each
sample was first heated in nitrogen and then air. The weight
loss in nitrogen corresponds to rubber and some additives
(if any left after the extraction), whilst the weight loss in air
corresponds to the carbon black (Fig. 1). The ratio between
the two weight loss values (i.e. grams of rubber per gram of
carbon black) was taken as the bound rubber in this study.
For measurements of bound rubber at elevated tempera-
tures (100 and 144°C). about 1 g of a rubber mix was diced
into ca. 40 pieces which were then put into 100 ml o-xylene
in a flask which was kept at 100 f 3°C or refluxed at 144°C
(o-xylene’s boiling temperature). After the extraction, the
carbon black (with bound rubber) was separated from the
solution by ultra-centrifugalisation for 2 hr at 13,000 rpm.
Bound rubber was then determined thermogravimetrically
after the residue was thoroughly dried.

35
36 E. Sheng et ul.

Table I. Materials used and the rubber mixmg formulation

Material Manufacturer Formulatmn (phr)

Natural rubber (SMRZO) MRPRA 100.0

Carbon black (N330) or Cabot 50.0
Silica (Ultrasll VN3) Degussa 30.0
Zinc oxide Union Mmere Oxide (Belgium) 5.0
Stearic acid Caldic UK Ltd. 3.0
Sulphur Schill & Seilacher 2.5
CBS (accelerator) Monsanto Chemuls 0.5
Flectol H (antioxidant) Monsanto Chemicals I .o
Multifunctional additive (EN444) Akzo Chemicals o.o-10.0*

*MFA concentrations of up to 5 phr were used with the untreated carbon black, and concentrations of
up to IO phr were used with the oxldised carbon black and the silica.

In order to establish a suitable o-xylene extraction time is notable that the bound rubber on the carbon black
at room temperature, a carbon black rubber mix with decreases with increasing MFA concentration. This
2.0phr MFA was extracted for a series of durations to initial decrease has been attributed to the release of
examine the dependence of bound rubber on extraction immobilised rubber within the carbon black agglom-
time. Figure 2 shows the relationship between the bound
rubber and extraction time. It can be seen that the bound
erates [9]. In other words, the carbon black dispersion
rubber initially decreased with extraction time and then was improved by increasing the MFA concentration,
attained its limiting value after around four days. To ensure resulting in the reduction of immobilised rubber
a maximum extraction, a period of 10 days was used as the within the voids of the carbon black agglomerates. As
extraction time for all bound rubber measurements at room the MFA level is above 2 phr (the level for a mono-
temperature. Similarly, a period of 24 hr was found suffi- layer coverage of the carbon black, which is to be
cient to dissolve all extractable rubber from the rubber mix discussed later on), limiting carbon black dispersion
at 100 and 144°C and therefore it was used as the extraction is achieved. This results in the levelling off of the
time for bound rubber measurements at 100 and 144°C.
bound rubber as observed in Fig. 3.
o-Xylene extracts were analysed using both X-ray photo-
Figure 3 also shows that the MFA has no pro-
electron spectroscopy (XPS) and FTIR. An extract was first
condensed by a factor of IO by evaporating o-xylene at nounced effects on the bound rubber of silica. It has
room temperature. Three drops of this concentrated extract been demonstrated that the addition of the MFA
were then thoroughly dried on an aluminium stub coated improves the dispersion of the silica in the rubber
with gold and XPS spectrum was taken on a VG ESCALAB [l 11. It is possible that the effects of the MFA on silica
MKI spectrometer. The quantification of the results was filled rubbers are a combination of the dispersion
detailed in a previous paper 191. For FTIR analysis, three improvement and the interaction enhancement at the
drops of the concentrated extract were dried on a KBr disk silica-rubber interface. While the improved dis-
and its infrared spectrum recorded on a Nicolet DXC20
persion decreases the bound rubber, the enhancement
infrared spectrometer.
The adsorption of the MFA onto carbon blacks and silica
of the silica-rubber interfacial interaction increases
in dichloromethane (HPLC grade, ex Fisons) was carried the bound rubber, resulting in no notable net change
out as follows. Solutions with various concentrations were in overall bound rubber result. It should be noted
prepared by dissolving the MFA in dichloromethane. The that the silica is a very polar material while the
filler (with an equivalent total surface area of ca. 3OOm’) natural rubber is a non-polar material. The MFA
was dried at 120°C for 2 hr and cooled to room temperature, molecules can interact strongly with silica surface
and then put into each of the solutions. The amount of the with their polar sites, while their non-polar alkyl
MFA adsorbed was calculated from the reduction in the chains (R and R’) can interact well with the rubber
MFA concentration determined by Fourier transform infra-
molecules. This implies that MFA can act as a
red spectroscopy (FTIR).
The oxidation of the carbon black was carried out by
coupling agent for silica filled natural rubber and
flowing the ozone/oxygen mixture (ozone concentration at therefore improve the interfacial interaction. The
cu. 1% by volume) from an ozonator (BA023, Wallace & strong silica-MFA interaction has been demon-
Tiernan Ltd.) through a fluidised bed-type reactor contain- strated later in the solution adsorption studies.
ing ca. 20 g of the carbon black [IO]. The ozonisation voltage For both the carbon black and silica filled com-
was 2OOV, the flow rate of oxygen was lOOl/hr, and the pounds, tensile strength and 300% modulus were
treatment duration was 1 hr. found to rise to maxima as the MFA level is in-
creased, and then slightly decrease with subsequent
increase in MFA level (see Figs 4 and 5). The initial
3. RESULTS AND DISCUSSION
increase in mechanical properties can be attributed to
3.1. Eflects of MFA on bound rubber the surfactant effect of the MFA on the filler incor-
Figure 3 shows the effects of the MFA concen- poration during mixing, giving improved carbon
tration on the bound rubber of the carbon black black or silica dispersion, whilst the deterioration of
(N330) and the silica (VN3) at room temperature. It the rubber properties at high MFA concentrations is

Table 2. Rubber mixing cycle with Francis Shaw Kl Intermix Table 3. Rubber mixing cycle with Hake Rheocord 90
Time (set) Operation Time (set) Operation
0 NR, ZnO, stearic acid, Flectol H 0 NR, ZnO, stearic acid, Flectol H
120 Carbon black/silica, MFA if any 120 Carbon black/silica, MFA if any
180 CBS 240 CBS
240 Sulphur 300 Sulphur
320 Dump 420 Dump
 Effects of an MFA on bound rubber 31

0.8 -E

‘+
G 06.

#J
g 0.4
(3arbon black

0.2

_
0.0
0

Temperature ( “C)

Fig. 1. A typical thermogravimetric curve.

thought to be caused by the formation of a second
MFA layer which acts as a weak interfacial layer. In
both carbon black and silica filled rubber compounds
studied, no correlation was found between measured
bound rubber levels and the mechanical properties of
the vulcanised compounds. Bound rubber has been
frequently assumed to be a measure of reinforcing
properties of a carbon black. However, as pointed
out by Donnet and Voet [ 121,in view of the complex-
ity of the phenomenon which involves chemical,
physical, and mechanical interactions of the carbon
black and the rubber, this assumption is rather
doubtful.
The o-xylene extracts were analysed with XPS and
FTIR. XPS showed that a dried extract contained
carbon, oxygen, sulphur and zinc. With the increase
in MFA concentration in the rubber mix, the N 1 s
peak started to appear in an XPS spectrum at around
2 phr, indicating that some MFA was extracted from
the rubber mix. Zinc was also found in the extract,
most probably present as zinc stearate.
FTIR spectra of the dried o-xylene extracts of
N330 and VN3 filled natural rubber mixes are shown
in Figs 6 and 7, respectively. They have shown that
no peaks due to the MFA were observed at low
MFA concentrations. However, as the MFA concen-
tration was above a certain level, i.e. ca 2.0 phr for the
carbon black and cu 7.5 phr for the silica, the MFA
peaks (1500 and 1600 cm-‘) started to appear.
This critical MFA concentration may be related to
the monolayer surface coverage of the filler surface
with the MFA. The monolayer surface coverage of
the filler with the MFA can be theoretically calcu-
lated. The total number of carbon atoms in an MFA
molecule was found to be 60 from either XPS analysis
or chemical analysis. The area occupied by one flat
MFA molecule was therefore estimated to be 326 A2
according to the radii of the atoms. As 50 phr carbon

_ 1.6 ,
a
s Silica filled NR
l
z 1.4- 0 .
g ” l
l

2 12-
M .
5
i? l.O-
c
,M
5 0.8 _
S
?1 Carbon black filled NR
z 0.6-
n
8 .
ELI
J
0.4 I I 1 I I
1 I 1 1 0 2 4 6 8
4 8 12 16
MFA concentration (phr)
Extraction time (days)
Fig. 3. Effects of the MFA concentration on bound rubber
Fig. 2. Dependence of bound rubber on o-xylene extraction of the carbon black (N330) and the silica (VN3) at room
time at room temperature. temperature.
38 E. Sheng et al.

30 Table 4. Effects of ozone oxidation on surface oxygen concentration

and specific surface area of the carbon black (N330)
Carbon black filled NR
Surface oxygen Specific
concentration surface area
Carbon black (at.%) (m’ia)
N330: untreated 0.9 78
N330: ozone oxidised 6.1 79

cal interactionbetween the carbon black and the

rubber in an unvulcanised rubber mix.

3.2. Effects of ozone oxidation of the carbon black on

bound rubber
It has been found that the oxidation of the carbon
black with ozone has a significant effect on its surface
lO/ oxygen concentration as detected by XPS while hav-
0 2 4 6 8 10
ing little effect on its specific surface area as measured
MFA concentration (phr) by nitrogen adsorption (Table 4).
Transmission infrared spectrum of the carbon
Fig. 4. Effects of the MFA concentration on tensile strength
black (0.05% dispersion in KBr) showed a prominent
of the carbon black and the silica filled natural rubbers. For
each point, at least six measurements were made.
peak at 1710 cm-’ which can be attributed to CL0
and/or associated COOH groups on the carbon black
surface induced by the ozone treatment. pH measure-
black is used, the amount of MFA needed to cover ment of the carbon black slurry (conforming to
its surface with a flat monolayer is ASTM 01512-84) showed that the pH was lowered
from 8.1 before the treatment to 2.2 after the treat-
50 x 78 x 10’”
326 x 6.02 x 102’ x 936 = 1.9 (phr) ment, indicating that the carbon black surface acidity
was increased significantly.
Effects of ozone oxidation of the carbon black on
where 78 x 10:” (A’jg) is the specific area of the
bound rubber are shown in Fig. 9. It shows that the
carbon black used. 6.02 x 102” is Avogadro’s con-
trends of the bound rubber-MFA concentration
stant, and 936 is the molecular weight of the MFA.
curves are the same for the untreated and treated
The critical MFA level is higher for the silica than
carbon blacks. However, the bound rubber of the
for the carbon black, which can be attributed to the
oxidised carbon black is always lower than that of
way the MFA molecules are adsorbed on the filler
the untreated carbon black. This may be due to the
surface. Carbon black is a non-polar filler, and MFA
reduction by the oxidation in dispersion surface free
molecules are very likely to adsorb flatly on its
energy of the carbon black (vi), resulting in the
surface. However, silica is a very polar material, and
decrease in carbon black-rubber interfacial inter-
the MFA molecules are believed to adsorb with their
action. By using heat of immersion calorimetry, r:’
polar sites firmly attached to the silica surface. In
was found to decrease from 91.5 mJ/m2 before the
other words, the MFA molecules are adsorbed in
treatment to 81.6mJ/m2 after the treatment with
such a way that they are somewhat perpendicular to
ozone. It seems that the critical MFA concentration
the silica surface. Therefore. a monolayer surface
coverage of the silica with the MFA would be
expected to be significantly higher than that for the 17 -
carbon black. Calculations similar to those for car-
bon black have shown that to cover 30phr silica
surface, approximately 10 phr MFA is needed. Carbon black filled N
The bound rubber was also measured at elevated
temperatures (100 and 144’ C) for carbon black filled
natural rubber with various MFA concentrations.
Results are shown in Fig. 8. Bound rubber results for
the carbon black at room temperature in Fig. 3 are
also included in the figure.
As the extraction temperature increases, physically
bound rubber diminishes. Therefore, bound rubber at Silica filled NR
a high temperature has been previously considered
mainly due to the rubber which is chemically bound
to the filler surface [13]. Figure 8 shows that the
bound rubber decreases with increasing extraction -I
temperature, but there is no virtual difference in the 0 2 4 6 8 10
bound rubber except for the control mix (0 phr MFA) MFA concentration (phr)
as the temperature is increased from 100 to 144°C.
Therefore, the bound rubber measured at 144°C may Fig. 5. Effects of the MFA concentration on 300% modulus
be regarded as mainly chemically bound and the of the carbon black and the silica filled natural rubbers. For
.
concentration of the MFA does not affect the chemi- each point, at least six measurements were made.
 Effects of an MFA on bound rubber 39

1
1810 1760 1710 1660 1610 1560 1510

Wavenumber (cm-l)

Fig. 6. IR spectra of dried o-xylene extracts of the carbon black (N330) filled natural rubber with various
MFA concentrations: (a) 0 phr; (b) 0.3 phr; (c) 1.Ophr; (d) 2.0 phr; (e) 3.0 phr; and (f) 5.0 phr.

has shifted from cu 2.0 phr to ca 4.0 phr after the
oxidation of the carbon black. This can be attributed
to the increased monolayer coverage of the oxidised
carbon black surface with MFA since the oxidised
carbon black has a more polar surface than the
untreated carbon black. FTIR spectra of dried o-
xylene extracts also showed that the MFA peaks
started to appear at a MFA concentration of around
4.0phr which was higher than the critical MFA
concentration of 2.0phr for the untreated carbon
black.
3.3. Adsorption of the iUFA onto filler surfaces in
dichloromethane
Adsorption isotherms of the MFA onto surfaces
of carbon blacks (untreated and ozone oxidised)
and silica in dichloromethane are shown in Fig. 10.
On an area basis, the fillers adsorb the MFA differ-
ently. The adsorption increases in the foilowing
order
N330 untreated < N330 oxidised < silica
which is the same order of increasing surface polarity.
The mom polar the filler surface, the more it adsorbs
the MFA. The order of increasing adsorptivity of the
MFA in dichloromethane agrees well with the order
of critical MFA concentration found in the bound
rubber measurement and the FTIR measurements of
the o-xylene extracts.
40 E. Sheng et al.

1810 1710 1610 1510

Fig. 7. IR spectra of dried o-xylene extracts of the silica (VN3) filled natural rubber with various MFA
concentrations: (a) 0 phr; (b) 0.3 phr; (c) 1.0 phr; (d) 2.0 phr; (e) 3.0 phr; (f) 5.0 phr; (g) 7.5 phr; and (h)
10.0 phr.

4. CONCLUSIONS black dispersion. The critical MFA concentration

The effects of a multifunctional additive, i.e. a
diamine salt of a carboxylic acid, on the bound
rubber in o-xylene of a carbon black (78 m2/g, 50 phr)
and a silica (169 mz/g, 30 phr) filled natural rubber
have been studied. For the untreated carbon black,
the bound rubber at room temperature initially de-
creases with the MFA concentration and then levels
off after an MFA concentration of ca 2.0phr. The
initial decrease was suggested to be due to the release
of the immobilised rubber within the carbon black
agglomerates caused by the improvement in carbon
after which the bound rubber levels off was found to
approximately correspond to the monolayer coverage
of the carbon black surface with the MFA.
FTIR studies of the o-xylene extracts from carbon
black filled rubbers showed that IR peaks due to the
MFA started to appear as the MFA concentration
was above ca 2.0 phr, corresponding to the mono-
layer coverage of the carbon black surface.. The
increase of extraction temperature decreased the
bound rubber. The concentration of the MFA had
little effect on the chemical interaction between the
carbon black and the rubber in an unvulcanised mix.
 Effects of an MFA on bound rubber 41

m Room temperature
A 100 oc
0 144 “C

Carbon black N330: ozone oxidised

I I I I

1 2 3 4 5 0 0.01 0.02 0.03

MFA concentration (phr) MFA equilibrium weight fraction

Fig. 8. Effects of the MFA concentration on bound rubber Fig. 10. Adsorption isotherms of the MFA on several filler
of carbon black at various temperatures. surfaces in dichloromethane at room temperature.

For the silica, the MFA concentration has iittle the rubber. The critical MFA concentration, above
effect on the bound rubber at room temperature, which the bound rubber started to level off and the
which might result from the combined effects of the IR peaks due to the MFA began to appear in the IR
release of immobilised rubber due to dispersion im- spectrum of o-xylene extracts, was found approxi-
provement and the enhancement in interaction be- mately doubled by the oxidation. This was believed
tween the silica and the rubber. FTIR studies of the to be caused by the improved MFA adsorptivity on
extracts showed that the MFA peaks started to the carbon black surface by the oxidation.
appear at a much higher MFA concentration (cu
7.5 phr) than for the carbon black (cu 2.0 phr). This Acknowledgements-The authors would like to thank EP-
was clearly caused by the higher MFA adsorptivity of SRC for funding this work and Akzo, Cabot, Pirelli and
the silica surface, as supported by the results of Schill & Seilacher for their support (ES). We would also like
adsorption in dichloromethane. to thank Mr H Ismail for preparing part of the rubber
The ozone oxidation of the carbon black increased mixes.
the surface oxygen concentration and surface acidity
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