products but also profiles, tubing, catheters

and baby teats. One can imagine that all of these
products require rubber with very specific pro-
Compounding ingredients
Natural rubber
The molecular structure of NR exists of very
long hydrocarbon chains of over 1.000.000 mo-
lecules each. A mass of these long molecules do
not readily accept compounding ingredients,
therefore the raw material first of all has to be
masticated to shorten the chain length (and
afterwards vulcanized to maintain its origin
properties). Mastication is carried out mechani-
cally, mostly with the aid of chemical or phy-
sical peptizers (chain modifiers). Compared with
most synthetic rubbers, NR needs only a (very)
small amount of such chain modifiers. After this,
NR is ready to accept compounding ingredients.
Under normal service conditions NR is an ex-
cellent material for general purpose products.
NR crystallizes under strain due to the regular
molecular structure, therefore the mechanical
properties (unfilled) are very high. The high
strength properties combined with low hystere-
sis make NR very suitable as an engineering
material for dynamic applications.
Vulcanization system
Almost all vulcanization systems for natural
rubber are based on sulphur and consist of a
vulcanizing agent (sulphur), activators and acce-
lerators (and/or sulphur donors). Due to the
double bond in the unsaturated hydrocarbon
chain, sulphur is the most interesting cross-
linking (vulcanization) agent. To activate the
sulphur, activators such as metal oxides (zinc
oxide) and fatty acids (stearic acid) are com-
monly used. The vulcanization time depends
on and can be adjusted by the type and quantity
of accelerators used and the vulcanization
temperature. Accelerators are divided in groups
ranking from slow to ultra fast. Examples are
guanidines, sulphenamides, thiazoles, thiurams,
carbamates and xantates. For NR sulphur vul-
canization sulphenimides are commonly used,
sometimes boosted by secondary accelerators
such as thiurams or guanidines to speed up even
Vulcanization systems can be divided in three
classes: high sulphur (conventional), medium
sulphur (semi-efficient) and low sulphur (effi-
cient). Conventional sulphur vulcanizing sys-
tems for soft rubber products consist of relati-
vely high amounts of elemental sulphur (about
1–3 phr) combined with a low concentration of
accelerator(s). If the amount of sulphur is in-
creased to 25-45 phr, a hard rubber, or ebonite,
is formed. Other vulcanization (crosslinking)
systems are based on peroxides or urethanes.
Fillers are used to increase the stiffness (hard-
ness) of the rubber. In principle, in NR a re-
inforcing filler is not needed to improve the
tensile properties but it is used to adjust certain
mechanical properties such as hardness, abrasion
and fatigue. Depending on particle size the fillers
can be divided in reinforcing (< 0,03 micron),
semi-reinforcing (0,03 to 1 micron) and non-
reinforcing fillers (>1 micron). Properties such
as tensile and tear strength, fatigue life and abra-
sion resistance are influenced by the type of filler
used. By increasing the amount of fillers the
rubber becomes harder. The nature of fillers can
be either carbon black or white filler. Carbon
blacks are prepared from crude oil. Most white
mineral fillers are clays, whiting, silicates, etc.
Reinforcing types of (white) fillers are silicas
prepared by precipitation. Organic fillers are
based on high styrene polymeric materials.
These resins do not necessarily increase tensile
strength, but they greatly harden, or stiffen and
improve wearing properties of products.
Softeners, diluents and extenders are applied to
reduce hardness and often also costs of the end
products. Small amounts of softeners, called
plasticizers, are used as processing oils. Large
amounts of softeners are used to soften the rub-
ber and to reduce costs. For NR small amounts
of aromatic oils are commonly used, such mineral
oils are most compatible with NR. However the
use of aromatic oil is suspected to cause health
problems because of the polycyclic aromatic
components it contains. Other with NR compa-
tible mineral oils are naphtenic and paraffinic
oils. For low temperature applications synthe-
tic esther-type oils are used.
From 1936 on the Rubber-Stichting promotes the use of natural rubber
ISSN 1384-9352
Newsletter of the Rubber Foundation Information Center for Natural Rubber


Rubber technology part 3, Compounding
This part of our series on rubber technology
is focussed on compounding and more spe-
cifically, on basic compounding ingredients.
Many people see compounding formulae as
being more or less similar to cookery book
recipes, and think that compounds are opti-
mized by trial-and-error (which was indeed
often the case in the early days). In well-
designed rubber compounds every ingredient
is chosen to get a certain desired effect on
processing properties and/or product pro-
perties. This implies that the intended way of
processing also is an integral part of the total
design of a compound, because many of those
ingredients have effects on the processing
behaviour of a compound.
As already said in part 1, raw NR is hardly
useable as such. It has to be mixed with other
ingredients (“compounded”) to get the required
specific properties. A typical compound contains
specific ingredients that in combination with
proper processing conditions lead to a product
that meets the requirements set beforehand and
that preferably against acceptable costs.
Basically a rubber compound contains various
groups of compounding-ingredients:
1) NR or a blend of NR with one or more poly-
meric materials;
2) a vulcanizing system (including activators
and accelerators);
3) fillers (inorganic and/or organic);
4) softeners (organic and/or synthetic);
5) a protective system (heat stabilizers and anti-
6) processing aids (peptizers, homogenizers and
7) special purpose ingredients such as blowing
agents, flame-retardants, abrasives, anti-sta-
tics, colorants, odorants, fibres, etc.
For each group, the (rubber)technologist has to
choose from numerous possibilities. A total of at
least 10.000 ingredients of different sources and
trade names is available. Besides knowledge of
compounding ingredients the technologist also
has to have sufficient knowledge of processing.
Examples of products based on NR are tyres,
bridge bearings, conveyor belts, engineering
See www. rubber- st i cht i ng. i nf o for
regular updates of the Events list
Protective systems
Most rubber products, particularly those based
on unsaturated rubber like natural rubber, are
rather susceptible to oxidation during their ser-
vice life. To improve the resistance against oxi-
dation antioxidants are used in the case of static
and dynamic applications. Especially rubbers
that will be stretched in service and then expo-
sed to outdoor conditions may be susceptible to
attack by ozone in the air. To prevent cracking
by ozone, antiozonants are used. For black
rubbers, most commonly used are antioxidants
of the phenylenic types, for non-black rubbers
phenolic types. Whenever products are likely
to be exposed to sunlight, a mixture of anti-
oxidants and wax is employed.
Processing aids
Processing aids are specific ingredients inten-
ded to ease or improve the processing of the
rubber in the mastication, mixing and vulcani-
zation phase. Peptizers shorten the chain length
during mastication. Homogenizers are used in
case of blending of two or more polymers.
Tackyfiers make compounds tacky to aid in
confectioning. Other processing aids act both as
internal plasticizer and external release agent.
Special ingredients
Blowing agents are used to manufacture sponge
or cell rubbers. Flame retardants protect pro-
ducts up to a certain degree when exposed to
fire; they may be powders or liquids. Many of
those contain halogens producing toxic fumes
when the rubber is exposed to fire. Nowadays
halogen free ingredients are preferred to protect
humans against inhaling those toxic gases.
Pigments are used in white masterbatches to pro-
duce coloured products and odorants to remove
the characteristic odour of natural rubber.
Compounding recipes
As mentioned before, a compounding recipe
contains almost always some ingredients from
each group. The compounding ingredients are
mentioned either by their chemical names or by
trade names, each followed by their quantity,
usually expressed in parts of the ingredient per
hundred parts of rubber (phr). In case of natural
rubber usually the type is given, such as RSS1
or CV60. Since the rubber manufacturer buys
rubber and ingredients by weight and sells the
finished products by volume; volume costs are
most important. That means that especially the
specific gravity of cheapening fillers is of inte-
rest. As an example, in table 1 three simple re-
cipes are shown, no. 1 without fillers at all, no.
2 with a carbon black filler and no. 3 with a
white filler. In these recipes no explicit specifi-
cation is given for each of the ingredients. Only
the quantities of the filler and the mineral oil are
varied. Optimum mechanical properties for car-
bon black mostly are reached at a volume per-
centage of about 25%. In case of white fillers,
the mechanical properties are mostly below those
of black fillers at the same level, especially the
abrasion resistance.
A typical vulcanizing system contains zinc
oxide, stearic acid, sulphur or a sulphur donor
and an accelerator. The accelerator increases the
rate of vulcanization but influences also the effi-
ciency of the vulcanization system. A low ratio
accelerator to sulphur (A/S) of 0.2 is called
a conventional system (CV), producing mostly
polysulphidic crosslinks. Is that ratio about 1 (0.5
to 1.5) the system is called semi-efficient (SEV)
and when the ratio is 5 to 15 the system is called
efficient (EV). In that case the end product will
contain most mono-sulphidic crosslinks. Com-
pounds with more poly-sulphidic crosslinks have
higher mechanical properties at the cost of the
resistance against heat, compounds with more
mono-sulphidic crosslinks show the opposite
behaviour. Peroxide crosslinks also have worse
mechanical properties but do have a good ther-
mal behavior. The crosslinks of polyurethane
(NOVOR) for natural rubber combine thermal
stability with high mechanical properties, but
those systems are not always safe to process.
All parts of the vulcanizing system should be
well dispersed in the rubber.
Compounding for tyre applications
In case of tyres each part - tread, sidewall, etc. -
needs its own specific rubber compound that
especially is formulated to obtain a specific set
of properties. For instance, a formulae for a
rubber tread with high wearing qualities has to
be set up with the following properties in mind:
– good abrasion resistance;
– good cut resistance;
– good tear resistance;
– good flex cracking resistance;
– high resilience;
– sufficiently high tensile strength;
– adequate hardness.
In table 2 some typical NR-based formulae are
given. The fine-tuning on the desired perfor-
mance of the end product is shown by the use
of different types of carbon black. For truck
treads N110 and a combination of N121/silica
are chosen to obtain high mechanical properties
and for the side wall N375 combined with BR
garantuees a good abrasion resistance and first-
rate dynamic properties. Some mechanical pro-
perties that were determined after vulcaniza-
tion are given in table 3.
As can be seen the NR/silica compound has a
lower hardness (softer compound) for a better
grip on the road. The sidewall NR/BR has been
compounded for a better dynamic behavior (low
Natuurrubber 38 - 2nd quarter 2005
Compounding Name of No. 1 No. 2 No. 3
ingredient group (phr) (phr) (phr)
Natural rubber Polymer 100 100 100
Zinc oxide Activator 3 3 3
Stearic acid Activator 1 1 1
Carbon black Filler - 45 -
Whiting Filler - - 65
Mineral oil Plasticizer - 5 10
Antioxidant Antidegradant 1 1 1
Sulphenamide Accelerator 0.6 0.6 0.6
Sulphur Crosslinker 2.5 2.5 2.5
Total amount 108.1 158.1 183.1
Table 1 Natural rubber start recipes.
Table 2 NR-based recipes.
Truck Truck Side-
tread tread wall
Compounding (phr) silica (phr)
ingredient (phr)
NR (natural rubber) 75 100 50
BR (butadiene rubber) 25 - 50
Zinc oxide 3.5 4 4
Stearic acid 2 2 1
Peptizer 2 - -
Resin 3 4 8
Carbon black (N110) 55 - -
Carbon black (N121) - 40 -
Carbon black (N375) - - 50
Silica (VN3) - 15 -
Silane - 2 -
Mineral oil (HA) 7 - 6
Antioxidant (6PPD) 1 2 2.5
Antioxidant (TMQ) 1 2 1.5
Wax - - 2
Accelerator (CBS) 1 0.75 1
Accelerator (DPG) 0.5 - -
Sulphur 1.8 1.5 1.2
Total amount 177.5 173.25 177.2
Bridge Low Engine
bearing creep mount
Compounding (SEV) (SEV) (EV)
ingredient (phr) (phr) (phr)
SMR CV 60 100 - -
SMR L - 100 -
SMR 10 - - 100
Zinc oxide 5 5 10
Stearic acid 2 - 2
ZEH - 1 -
Carbon black N 550 40 - 50
Carbon black N 762 - 70 -
Oil (naphtenic) 4 - 10
Antioxidant TMQ - 2 2
Antiozonant DPPD 3 4 2
Sulphur 1.5 0.5 0.25
Accelerator CBS 1.5 1.7 -
Accelerator TBBS - - 2.1
Accelerator TMTD - - 1.0
Accelerator TBzTD - 0.7 -
Total amount 157 185.9 178.35
Truck Truck Side-
tread tread wall
Properties silica
Hardness (Shore A) 68 61 52
Modulus 300% (MPa) 9.7 12.8 5.0
Tensile strength (MPa) 22.3 27.4 22.8
Elongation at break (%) 530 510 740
Tear (N/mm) - - 70
Rebound (%) 42 48 -
Abrasion DIN (mm
) 101 100 66
Density (g/cm
) 1.13 1.14 1.10
Table 3 Mechanical properties.
Table 4 Engineering recipes with a hardness
of 60 Shore A.
Natuurrubber 38 - 2nd quarter 2005
Russian take-over
Russian Amtel Holdings Holland NV has bought
Vredestein Banden NV. With this purchase
Amtel gains an import brand with excellent
selling prospects in Russia as well as a sales
and distribution network outside Russia for its
locally made products. The capacity of the ex-
panded Amtel Group increases from 14.4 up to
22 million tyres a year.
QDI antidegradant for cost saving,
productivity in various grades of NR
F. Ignatz-Hoover, B. H. To, Rubber World, Vol.
230, No. 5, p. 22-28
Demonstrates that Quinonediimine antidegradant
(QDI) can reduce mix times up to 25%.
Laboratory simulated aging and the effect
on the oxygen content in rubber
D. L. Schwarz, D. W. Askea, B. D. Lambillotte,
Rubber World, Vol. 230, No. 6, p. 26-31+47
It was found that the oxygen concentration in the
aging gas directly impacted the oxygen content in
the samples and lead to accelerated degradation of
the samples.
Processing effects on NR aging
J. Shell, T. Wang, V. Vejins, Y. L. Wong, Rubber
World, Vol. 231, No. 2, p. 21-28
Demonstrates that latex-phase mixing of NR-
compounds results in improvement of ageing resis-
tance and performance properties compared to con-
ventional dry mixed compounds.
Mold fouling during rubber vulcanization
B. van Baarle, Rubber World, Vol. 231, No. 3, p.
To prevent mold fouling the role of ZnO in rubber
compounds has to be diminished through reduc-
tion of its level or its replacement by nano-ZnO.
The approach through modification of the mold
surface shows very promising first results for
magnetite coatings.
Factors that affect the fatigue life of rubber:
a literature survey
W.V. Mars, A. Fatemi, Rubber Chem. & Techn.,
Vol. 77, No. 3, p. 391-412
Describes primary factors of the effects of mecha-
nical loading history, environmental effects, effects
of rubber formulation and effects due to dissipa-
tive aspects of the constitutive response of rubber,
and presents and reviews literature.
Elastomers for shoe applications
K. A. Ames, Rubber Chem. & Techn., Vol. 77, No.
3, p. 413-475
Reviews the improvements made over the last 15
years in the production of outsoles and midsoles
for footwear by using various materials.
Effect analysis of mixing process variables
on viscoelastic properties of NR tread
A. M. Marks, A. Adhikary, R. Mukhopadhyay,
Rubber World, Vol. 231, No. 2, p. 29-32+63
Factorial designs allow for the simultaneous study
of the effects that several factors may have on a
process. This article shows that a two-level fractio-
nal factorial design can be used as an effective
tool in screening rubber compound mixing proces-
sing variables having different degrees of effects
on viscoelastic behaviour.
heat-built-up) and flex cracking resistance (high
amount of antidegradant system containing anti-
oxidant, antiozonant and wax).
Compounding for engineering
Special attention could be made to compoun-
ding for engineering applications. NR types are
mostly based on field latex. Engineering appli-
cations are focussed on long term behaviour or
applications at high temperature. In this case
semi-efficient (SEV) or efficient (EV) vulcani-
zation systems are more common. For enginee-
ring applications carbon blacks, mostly course
blacks N500-N700, are used. Addition of small
amount (5-10 phr) of oil improve processing of
the rubber.
Three recipes with a hardness of about 60 Shore
A are selected (table 4). The first one is a recipe
for a bridge bearing. A medium carbon black is
used to avoid modulus drop during cyclic tem-
perature behavior. The vulcanization system is
a SEV-system and an antiozonant. The second
recipe is a low creep recipe for high temperature
applications. Also in this recipe a low modulus
carbon black (N762) is chosen without oil. The
stearic acid is replaced by ZEH (a special ingre-
dient for low creep applications). For a (long)
service life at high temperature a SEV-system
is used, combined with an antioxidant and an
antiozonant. The third recipe is developed for
high temperature engine mounts. In this recipe
the zinc oxide content is doubled and an EV-
system is used. A high level of antidegradants
(antioxidant and antiozonant) is chosen.
(to be continued)
School of Carriers, British Institute of Enginee-
ring Technology, Compounding & Compoun-
ding Ingredients.
The Fundamentals of Rubber Technology
- The designing of Technical Rubber Compounds
- Fundamentals of Tyre Technology.
MRPRA EDS 3 Compounding for Engineering
The Natural Rubber Formulary and Property
Index (recipes).
How important is flame retardancy for Natural Rubber products?
At first sight, this seems to be a somewhat odd question. What has flame retardancy to do with
(natural) rubber? Considering that raw rubber, and not only natural rubber, chemically looks much the
same as raw oil might make this question more logical. In fact, without flame retardant chemicals
added almost all rubbers will burn like a pretty good fuel, releasing a lot of energy and keeping on
burning for a rather long period of time. For many products there is nothing wrong with the fact that
most rubbers burn easily. Take for instance bridge bearings, such products are unlikely to catch fire
and anyway, if they would, the exposed surface is rather small keeping the fire propagation limited.
For such a product fire retardancy is not really a must. Also, for many other products like gloves and
condoms flame retardancy is not really needed. For a range of other products like many conveyor
belts and mining belts a good resistance to fire can be very important. Fortunately in these cases it is
not very difficult to introduce flame retardancy. Depending on the type of product and the service
conditions even considerable quantities of sufficient flame retardant additives like aluminium tri-
hydroxide may be added to the compound without impairing the rubber-like properties too much.
But there are other natural rubber products like carpet backings and mattresses, typically domestic
applications, for which flame retardancy obviously is a must and where it is much more difficult to
make those products sufficiently flame retardant. There we talk about large surfaces with excellent
air entrance and therefore optimal burning conditions. The importance of flame retardancy for such
products however is only ‘discovered’ during the last years. Until very recently, for mattresses manu-
facturers thought it to be sufficient to make the outer cover flame retardant. Under pressure of Euro-
pean Regulations nowadays the cores themselves are obliged to be sufficiently flame retardant.
Mostly flame retardancy is obtained by adding to the compounds halogen containing chemicals in
combination with antimonytrioxyde. Because of the toxic nature of halogens these additives are
likely to be banned pretty soon, at least within Europe. Therefore it is necessary to develop other flame
retardant systems to get sufficient protection. The use of expandable graphite is only partly a solution
because this will have a negative influence on the mechanical properties of mattresses. For carpet
backing such a system might do but there aluminium trihydroxide also can be used. The development
of other systems is still under way, but it will take time to develop a proper functioning system. It is
a question whether Europe will wait that long before banning the halogens completely.
Jaap Havinga
Natuurrubber 38 - 2nd quarter 2005
Manager Ing. Jaap Havinga
Editor “Natuurrubber” Ben van Baarle LPRI
Consultants Ing. Jaap Havinga
Ben van Baarle LPRI
Advisor Jim van der Heijden
Delegate from the Board Ing. Wil Aben
Postal Address P.O.Box 6235
5600HE Eindhoven
The Netherlands
The aim of the R-S Information Center for Natural
Rubber is to give information to companies and
institutions about properties and processing of natural
rubber and about products manufactured on the basis of
natural rubber. Information is provided by publishing the
free newsletter “Natuurrubber/Natural Rubber”,
by maintaining the Center’s website and by answering
questions asked by e-mail. For questions that need desk
research the first three hours spent are free.
All reasonable care is taken by the Rubber-Stichting to
ensure the reliability of its communications. The Rubber-
Stichting, however, cannot accept any liability with
respect to the content of this publication.
The R-S Information Center for Natural Rubber
Outlook for NR
Who or what to believe on the
price of Natural Rubber in 2005?
2005 so far, has been a bullish reactionary
market, where hype and speculation have been
the ruling factors, with fundamental physical
factors being almost ignored. 2004 ended on a
modestly firm note, but with most participants
agreeing that the levels had been increasing
now for such a long time, that the levels needed
to be redressed, and rubber needed to find a
more stable and reliable background. Even the
producers, who always like to talk a bullish
book, were mostly in agreement that levels
were high and that although a crash was not
likely, slightly lower levels could be expected.
Having said this, none had foreseen the rise in
the price of crude oil, and the possible effect
on synthetic rubber. Although figures vary de-
pending on who you get them from, there is
only an average of around 3 - 4% of natural to
synthetic global usage that is inter-changeable,
and this is mostly on the less technical products,
where the recipes can be changed with little
effect on the final product. Therefore to say that
as synthetic rubber prices were rising, that NR
had to do also, was a big exaggeration, but still
it was swallowed hook line and sinker by the
natural rubber market, and well promoted by
the producers.
The other main contributor to the current high
prices, has been the way in which a shortage
in any grade can be used in a way to influence
the whole market, and this was first seen on the
RSS 3 rubber market (Ribbed Smoked Sheet),
where due to historically high prices being
traded early in 2005, the Thai producers over
sold, and then were faced with an early start to
the wintering period, which then lasted longer
than usual. This meant that many sales were
either delayed, or defaulted on, and the confu-
sion saw RSS 3 rubber prices rise much higher
that the larger TSR 10/20 rubber tyre market
qualities. Thailand had also over sold liquid
latex for March and April, and this too rose,
and took with it the latex grades such as TSR
CV and TSR L, and the higher the levels went,
the more times that some unreliable producers
resold already sold parcels for a higher price
and further added fuel to the NR rubber price.
The TSR 10/20 rubber market was slow to react,
but it was only a matter of time before the
effect eventually trickled through, and now TSR
20 grade is also being pushed up, and the whole
rubber market is in a bull rush, with no signs of
a slowdown in the near future. There will
always be dips, when dealers have to either
change or rotate their positions and take profit,
but these only usually last a day or so, and then
the upward momentum starts up again.
The main question is how long can this over-
reaction last, and will the fundamentals like
supply and demand return, as still the largest
grade TSR 10/20 is in abundance, and any
large spot orders can still easily be filled, but
although there is no way to reliably predict a
market which is being led by outside factors.
Most believe that the bull run will continue at
least for the coming weeks, if not months.
Therefore the outlook for 2005 is for higher
levels, and all consumers are recommended to
pick and choose their most reliable suppliers,
as if you have bought forward, and are now
looking at a market some 30% higher, will your
supplier still supply, or be tempted to sell else-
Alec F.S. McDougall,
Senior Consultant Wurfbain Nordmann bv.
US dollarcents per kilo
2005 2002 2003 2004 2001
Ozone attack and tire sidewall protection
A. Adhikary, R. Mukhopadhyay, Rubber World,
Vol. 230, No. 6, p. 16-20
Reviews the protection of tires against ozone in
relation to higher performance needs and rising
ozone concentrations in the atmosphere.
Activators in accelerated sulfur vulcanization
G. Heideman, R. N. Datta, J.W.M. Noordermeer,
B. van Baarle, Rubber Chem. & Techn., Vol. 77,
No. 3, p. 512-541
In conventional rubber compounding ZnO is difficult
to substitute. Reduction of ZnO levels would only be
possible with different activator/accelerator systems.
Biaxial tensile behavior of rubber
vulcanizates; 1. Silica and gum stocks
K. Kajiwara, Y. Kameda, Y. Ikeda, H. Urakawa,
T. Kawamura, K. Urayama, S. Kohjiya, 611-623
Properties of NR samples filled with silica via both
conventional and in-situ methods were compared.
Indications were found for differences in the me-
chanism of storage of elastic free energy due to
the filling method.
Carbon black dispersion measurement
in rubber vulcanizates via interferometric
A. P. Smith, T. L. Aybar, R. W. Magee, C. R. Herd,
Rubber Chem. & Techn., Vol. 77, No. 4, p. 691-710
Surface roughness of razor cut samples of black-
filled rubber compounds, determined by interfero-
metric microscopy, correlates to the carbon black
dispersion level in the measured compound.
Effect of network-chain length on strain-
induced crystallization of NR and IR
M. Tosaka, S. Kohjiya, S. Murakami, S. Poompra-
dub, Y. Ikeda, S. Toki, I. Sics, B. S. Hsiao, Rubber
Chem. & Techn., Vol. 77, No. 4, p. 711-723
Due to the lower crystallinity in IR the oriented
amorphous component will bear more stress in IR
than in NR.

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