From 1936 on the Rubber-Stichting promotes the use of natural rubber

ISSN 1384-9352
The market for natural rubber has undergone
profound changes over the past decade.
Chinas spectacular growth has greatly in-
creased demand for the commodity; the
Asian currency crises of 1997/98 left its
marks on the prices in all major countries
ever since and has only recently seemed to
have been overcome.
To highlight these changes we compare projec-
tion made by the models of Hidde Smit and
Kees Burger in the past and present. The models
consists of
- an analysis of natural rubber production
capacity and supply;
- an analysis of total rubber demand;
- a model describing reactions of demand,
supply and prices to each other.
The futures past
Projections for the natural rubber volumes are
based on two driving forces. On the supply side
actual production is influenced by the produc-
tion capacity; on de demand side it is the
overall demand for rubber in the two main end-
uses (tyre and non-tyre). Production capacity in
the major producing countries is derived in
three steps
acreage of rubber by age of trees;
the standard yield profile that provides the link
between age of the tree and standard yield;
the level of technical progress that charac-
terises a certain year of planting (vintage).
The estimate for this capacity, calibrated over
the past 20 years, is called normal production.
Actual production deviates from this norm
under influence of prices.
Table 1 presents the recent developments, where
we inserted recent estimates for 2005. Both
production and consumption have risen sharply
in this ten-year period. Around 2.7 million tons
has been added to the 1995 levels. Whereas pro-
duction and consumption of NR have risen by
about 45% over the decade, normal production
rose by a mere 30%, and total rubber consump-
tion by 38%. The implication therefore is that
more NR has been produced than could be ex-
pected on the basis of normal capacity utilisa-
tion. And, on the demand side, more NR has
been consumed than could be expected on the
basis of developments in total rubber consump-
tion. While higher NR consumption could be
due to consumer prices of NR being lower,
more NR production would require producer
prices to be higher. We shall see below that
though world market prices in US dollars have
fallen over the period, real prices in producing
countries ended the decade at a higher level than
in 1995. But other factors such as a regional
shift of NR consumption also contributed to
higher shares of NR.
In these conditions of drastic changes in volu-
mes and prices, projections into the future could
not remain unaffected. Figure 1 shows the data
and projections of production volumes until 2010
that were generated in 1995, 2000 and at present.
Two questions arise: what explains the chan-
ging projections of the prices? And how can
recent developments in production volumes,
that go well beyond projected levels be ex-
plained? Furthermore, one may wonder why
volumes could be accurately predicted and
prices wrongly, and vice versa. We start with
the higher-than-expected levels of production,
and focus on the major country, Thailand.
The higher production in Thailand
Since 1990, Thailand is the worlds major pro-
ducer of natural rubber. Malaysia, that held this
first place until then, fell back to the third
position, while Indonesia kept its second place.
Each of the countries produced around 1.2
million tons in 1990. For 2005, projections are
for Thailand to produce nearly 3 million tons,
Indonesia 2.2 and Malaysia 1.1 million tons.
Together the countries produce 71% of world
production, and this share has not changed
much since 1990.
In generating the projections for Thailand, the
steps as outlined above were taken. We distin-
guish acreage by age of the trees, yield per rai
(1ha equals 6rai) by age and employ an estimate
of technical change in the planting material. In
addition, prices have an effect on the utilisation
of the capacity. The underestimation of the pro-
duction in Thailand, shown in Table 2, may
therefore be due to the estimates of each of these
four elements: acreage by age, yield profile,
technical change and prices.
Of the potential causes of underestimation of
Newsletter of the Rubber Foundation Information Center for Natural Rubber
40
4
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5
Gold Medal for Noordermeer
Jacques Noordermeer, professor at the Rub-
ber Technology Department of the Univer-
sity of Twente in the Netherlands, has been
awarded for his contribution to the field of
rubber technology. Noordermeer and his
people work on tire materials for finding
the optimum for rolling resistance, slipping
resistance and wear resistance. He will
accept the award at the IRCO conference in
Lyon, France on May 17, 2006.
The changing outlook for Natural Rubber
Table 1. Major developments 1995-2005
in 1000 tons 1995 2000 2005*
Normal Production NR 5999 6761 7827
Production NR 6070 6730 8791
Consumption NR 5950 7320 8692
Total Rubber Consumption 15160 18040 20935
Price (RSS1 in US$/ton) 1601 668 1403
* Estimate
Table 2. Actual and projected production of NR in Thailand
in 1000 tons 1995 2000 2005 2010
Actual production 1805 2346 2990
Projected in 1995 2208 2135 1928
Projected in 2000 2269 2169
Projected in 2005 3148
Figure 1. Actual and projected production of
Natural Rubber.
12,500
10,000
tons
7,500
5,000
2,500
0
1980 1990 2000 2010 2020
2000
2005
Projections
Actual production
1995
Thai production, it is the yield per rai that we
found to be most guilty. This is not so much
due to its overall level, but to the relative per-
formance of the older age groups. The group of
the ages 21-27, which formed 15% of total
acreage in 2000, constitutes no less than 25%
in the year 2005. The standard yields in this
age group have therefore become more
important too. The higher levels of production
could be ascribed to higher yield levels in this
group, compared to what was assumed before.
When we introduced higher yields in this age
group, this did hardly affect the projections for
earlier years, because the older age group was
not important then. The estimates for the yields
of the group between 21 and 30 years old are
nearly double those employed earlier. Projec-
tions for normal production in Thailand based
on the new approach lead to estimates for 2005
that are much higher than what was projected
in 2000 (2742 compared to 2117 thousand tons)
and forecasts for the future are similarly
higher. But the actual levels not only depend
on normal production levels, but also on prices.
The higher prices for producers
On 1st July 1997, Thai authorities announced
they would no longer support the exchange rate
of the Thai baht. The currency soon lost more
than 30% of its value, and the crisis spread to
other countries in the region, including Indo-
nesia (in 1998 mostly), Malaysia, Singapore,
Vietnam, and also South Korea. As the region
produced more than 70% of the worlds NR,
the devaluation meant that the same quantity of
rubber could be obtained at lower US dollar
prices. The reduction in demand in this period
contributed to dollar prices falling so drasti-
cally, that the real prices in most producing
countries fell despite the devaluation. World
market prices dropped to as low as 42% of the
1996 levels but prices in local currencies did
not fall that much. In real terms, Indonesian
prices even rose to very high levels after the
unprecedented devaluation in 1998. The impli-
cation was that producer prices of NR have im-
proved relative to consumer prices. Essentially
both groups benefited from the devaluation.
The demand side
Consumers face a price for NR that is lower
than it would have been without the devalua-
tion in Southeast Asia. But this is but a small
element in explaining the enormous changes
that have occurred in the demand for natural
rubber. As Table 1 above showed, consumption
of NR rose by over 45% in the period 1995-
2005, which is the highest growth over a ten-
year period since 1974. This cannot be merely
due to price influences, but is more connected
with a redistribution of NR consumption over
the globe. China contributed enormously to this
development. Whereas her consumption in 1995
was 780 thousand tons, this rose to 1038 in 2000
and 1737 (expected) in 2005. Of the total world
consumption increase of 2.7 million tons, China
accounted for 35%, though her share in world
Natuurrubber 40 - 4th quarter 2005
Profile
Rubber Technology part 5, Vulcanisation
consumption is only 20%. China also accounts
for nearly 50% of the growth in consumption of
rubber in general, including synthetic rubber.
The share of NR in total rubber consumption in
China fell from 49% to 39%, which is slightly
below the world-wide share of NR.
Comparing projections for 2010, made in 1995
and 2005, world consumption of rubber was
projected to reach nearly the same levels of
22.1 million tons. But it is now consist for 26%
of Chinas consumption, compared with 12%
expected ten years ago. For NR, however, pro-
jected levels for 2010 are somewhat higher in
2005 than in 1995 (plus 0.62 million tons), but
for Europe, North America and Japan projec-
tions have hardly changed. The higher expected
consumption in China (plus 0.66 million tons)
greatly contributes to the expected global in-
crease. Chinas share was expected to be 19%
and is now expected to be 25%.
Conclusions
Present forecasts for production and consump-
tion of NR in 2010 now reach 9.7 million tons,
compared to 8.8 million projected for 2010 in
1995. Yet, price forecasts have remained fairly
steady at between $2.1 and $2.5 per kg. Under-
lying these changes in projection are dramatic
changes in the distribution of consumption over
the globe, with strong increases in consump-
tion in China. The higher levels of production
required an adjustment of the model notably for
Thailand. This explanation is found in higher
levels of yields of older trees. Another element
in the explanation is that devaluation of their
currencies made real producer prices in most
producing countries higher compared to the
world market price in US dollar, than assumed
earlier. Both consumers and producers bene-
fited from this change in exchange rates.
Kees Burger, Dept. of Economics, Free
University Amsterdam
Email: kburger@feweb.vu.nl
Home page: www.econ.vu.nl/esi
The author is most grateful to the secretariat of
the International Rubber Study Group for pro-
viding the vast majority of all data used in the
analysis.
2
This part of our series on rubber technology
focuses on vulcanisation. This is a chemical
process to give elasticity to shaped products.
The most used and simple shaping method
during vulcanisation is moulding.
Vulcanisation
When rubber molecules are not connected to
each other, they can move more or less freely.
At this stage the material is plastic, which means
that after stretching a strip of unvulcanised
rubber the strip does not return in its original
shape. Vulcanisation is a process during which a
number of bonds so-called crosslinks
between rubber molecules are made. As a result,
after stretching a strip of vulcanised rubber will
almost completely return into its original shape
when released. The number of crosslinks for-
med depends on the amount of vulcanisation
agents, their activity and the reaction time and
temperature. Crosslinking converts a plastic
rubber mass into an elastic product.
Sulphur is the most important crosslinking agent
for natural rubber and certainly the best agent for
most general purpose applications. Another type
of vulcanisation is peroxide crosslinking.
Properties of a vulcanised rubber depend on the
number and type of crosslinks. There are va-
rious types of crosslinks to distinguish. For sul-
phur the crosslinks can be polysulfidic (more
than two sulphur atoms are forming one bound),
disulphidic (two atoms form a bound) or mono-
sulphidic (one sulphur atom). With peroxide
direct carbon to carbon connections are formed
(figure 1). Other additives such as activators
and accelerators are required to speed up the
vulcanisation process. However, the reaction
mechanisms that take place during crosslinking
i.e. curing, resulting in increasing strength,
elasticity and temperature stability are still not
fully understood.
In figure 2 the vulcanisation time is schemati-
cally given as a function of the vulcanisation
temperature. The temperature dependence of
the vulcanisation process is doubled when the
vulcanisation temperature is raised by 8 to 10C.
The vulcanisation process can be described with
an Arrhenius equation:
log k = (-E / 2.0303 RT) + C
k = reaction rate constant
E = activation energy (J. mol
1
)
R = gas constant (R = 8.31441 J mol
1
. K
1
T = absolute temperature (K)
C = constant
In practice curing temperatures from about
140C up to 210 C are used. It is not possible
to raise vulcanisation temperatures higher than
this to achieve shorter vulcanisation times,
because of the risk of processing problems,
particularly in batch vulcanisation systems
such as vulcanisation in moulds.
The curing behaviour of rubber compounds can
be followed with special test equipment.
For measuring the cure behaviour of the com-
pound a rheometer is used. Two different types
of rheometers are available, the oscillating disk
rheometer (ODR) and the moving die rheo-
meter (MDR). The difference in measuring the
torque is that in the ODR the disk is oscillating
and in the MDR the die is oscillating. The
absolute values may differ, but the process pa-
rameters calculated such as scorch (t
s
) and
optimum cure (t
90
) are comparable. In a rheo-
meter a sample of the rubber is heated in a
closed chamber and the oscillating torque is
measured. In figure 3 a vulcanisation curve at a
fixed temperature is shown. At the start the
rubber is heated to the vulcanisation tempe-
rature, where it starts flowing and the torque
decreases to a minimum level (S
min
). At that
point, the scorch time (t
s
), the vulcanisation
starts and crosslinks are formed, giving an
increase of the torque until a maximum value
(S
max
) is reached. For conventional sulphur
based vulcanisation sytems (CV) the torque
starts to decrease after reaching a maximum.
This is called reversion. When using an
efficient vulcanisation system (EV) a plateau in
the torque is reached. The time at which the
torque is 90% of S(S
max
S
min
) is called t
90
.
In most cases the time t
90
is considered to be an
optimal vulcanisation time. For a really good
compression set two times t
90
is often used. At
S
max
different slopes of the torque/temperature
curve are possible depending on the vulcanisa-
tion system.
As mentioned earlier the vulcanisation system
consists of a vulcanising agent (sulphur), activa-
tors and accelerators (and/or sulphur donors).
By choosing a suitable combination of these in-
gredients, it is possible to obtain the preferred
mechanical properties by adjusting the scorch
and vulcanisation time at the applied tempera-
ture.
The rheometer curve is a standard test curve
and the data from the rheometer can be used to
optimise the vulcanisation time of thin-walled
products with a thickness up to 6 mm. For thick
articles an additional vulcanisation time is nee-
ded to raise the temperature in the middle of the
product. For a homogeneous vulcanisation in
thicker products the vulcanisation system has
to be adjusted from a CV- (conventional) to a
SEV- (semi-efficient) or EV- (efficient) system.
As a rule of the thumb, at a given temperature
the curing of a product of e.g. 400 mm thickness
takes a vulcanisation time of about t
90
(min) +
400/ 2 mm x 1 min/ mm = t
90
+200 minutes.
Vulcanisation methodes
There are two main vulcanisation methods, also
known as batch vulcanisation and free vulcani-
sation. The first includes compression moul-
ding, transfer moulding and injection moulding
and is for natural rubber the most commonly
used method. Free vulcanisation comprises auto-
clave vulcanisation and continuous vulcanisa-
tion and is used for endless products.
In most cases the cured products have a so-
called flash, a thin film of excess material
between the mould parts. This flash has to be
removed in a process called finishing. The
method for finishing depends on the shape of
the product. It can be done by trimming products
with of a pair of scissors or using deflashing
methods like freezing and tumbling for more
complex product shapes
Batch vulcanisation
Press curing. Press equipment for the produc-
tion of rubber articles consists of a stiff frame-
work with two or more parallel electrical or
steam heated plates. The mould is situated be-
tween these plates (figure 4). A hydraulic unit
supplies the pressure for a cylinder to close the
mould.
Compression moulding is the oldest shaping
(and vulcanisation) method and for many pro-
ducts the most economic process for producing
small products like dampers in short runs or
large products like tyres in more longer runs.
In a compression mould (figure 5) the uncured
rubber compound is placed directly into the
cavity of a hot mould. After closing the hy-
draulic press the compound is pressed into the
desired shape of the product. After the vulca-
nisation time the press is opened and the vul-
canised product is released from the mould.
Transfer moulding. A transfer mould con-
sists of three parts (figure 6). The rubber com-
pound is placed in a separate (large) cavity.
When closing the press the preheated rubber is
injected into a closed mould cavity or a few small
cavities. An advantage of transfer moulding is
Natuurrubber 40 - 4th quarter 2005
rheometer torque (dNm)
vulcanisation time (minutes)
m
arching m
odulus
plateau-effect
reversion
S
min
S
min
+ 2 dNm
optimum vulcanisation time t
90
scorch time t
s
0.9 S S S
max
Figure 3. Rheometercurve at fixed temperature.
log t
temperature
10
2
150C 175C 200C
10
1
10
0
Figure 2. Arrhenius equation
(time versus temperature).
3
CV SEV EV Perox
CC-
bonds
poly- di- mono-
sulphidic vulcanisation
S
x
S
2
S
Figure 1. Different crosslink structures
Figure 4. Hydraulic press.
Figure 5. Compression mould.
mould
plunger
oil
flash groove
flash
compound mould cavity
rubber
...
mould
closed mould
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the possibility to produce flash-free products.
Besides cure times tend to be shortened, how-
ever the moulds are more expensive. Transfer
moulding is particularly useful for the produc-
tion of larger articles or rubber with metal
bonded components. Vulcanisation temperatures
for compression- and transfer moulding are
150 C up to 175 C.
Injection moulding. The injection moulding
technique is a combination of an extruder with
a plasticising zone and a reciprocating screw
(figure 7). This technique is used to produce
large series of small products with short cycle
times. Curing times are possible within 1 minute.
In this process the mould is closed before
injection. The preheated rubber is pushed
under pressure from an injection head into the
hot mould. Vulcanisation temperatures for
injection moulds are 175 C up to 210 C.
Free vulcanisation
Autoclave vulcanisation is used to vulcanise
products like thick profiles, large buffers and
off-shore hoses and hoses with wrapped re-
inforcement layers. The wrapped layers could be
either metal braid or textile fabric. Large extru-
ded products, rubberised roll covers and con-
fectioned hoses are also cured in autoclaves.
Lengths of autoclaves are up to 20 meters and
can have diameters up to 6 meters. For the vul-
canisation the autoclaves are filled with steam
under pressures up to about 6 bars, correspon-
ding with a temperature of about 160C.
Continuous vulcanisation (LCM) Liquid
bath vulcanisation is a method for curing
rubber profiles in a hot liquid medium. This
method is called the Liquid Curing Method
(LCM). After leaving the extruder the continu-
ous product is submerged in a liquid eutectic
salt mixture at very high temperatures (up to
260C). At the end of the salt bath the vulcani-
sation is completed, the salt is rinsed off and
the product is cooled down. The LCM method
is used for thin-walled products such as strips,
hoses and profiles.
Continuous vulcanisation (Hot Air) Another
method is hot air vulcanisation. In this way a
(polar) extruded compound is preheated by using
an infrared (IR) heating device or an ultra high
frequency (UHF) oven. By using UHF natural
rubber must have a polar behaviour and this
can only be achieved with carbon black filled
compounds. After preheating the extrudate is
vulcanised in a hot air tunnel, followed by
cooling down in water.
Ben van Baarle
Accelerators
Quick-Vulkanisation; Die Formel 1 der
Herstellung von Kautschukformteilen
(Quick vulcanisation; The formula 1 in the
production of rubber molded parts)
U. Masberg, A. Potthoff, GAK 8/2005, p. 499-504
Simulations show the economical benefit of a
new concept for the production of rubber mol-
ded parts at reduced heating time.
Natural Rubber-g-Glycidyl Methacrylate/
Styrene as a compatibilizer in Natural
Rubber/PMMA blends
P. Suriyachi, S. Kiatkamjornwong, P. Prasas-
sarakich, Rubber Chem. & Techn., Vol. 77, No.
5, p. 914-930
Graft copolymerization of styrene and glycidyl
methacrylate onto NR latex. Evaluation of (a)
the effects of several parameters on monomer
conversion and grafting efficiency, (b) mechani-
cal properties as function of grafted NR content
and (c) compatibility of NR/PMMA blends as
function of grafted NR content.
Effect of compound ingredients on adhesion
between rubber and brass-plated steel cord
T. Hotaka, Y. Ishikawa, K. Mori, Rubber Chem.
& Techn., Vol. 78, No. 2, p. 175-187
Hexamethoxymethylmelamine was used to trap
amines generated by N,N-dicyclohexylbenzo-
thiazole-sulphenamide-accelerated sulfur vulcani-
sation that promote stress-induced corrosion
crack in the brass layer. Also the influence of
carbon black on residual amine content was
studied.
New technique for measurement of
rubber-to-metal bond failure
C. C. Lawrence, G. J. Lake, A. G. Thomas,
Rubber Chem. & Techn., Vol. 78, No. 2, p.
271-285
Describes a new test that may give a more
realistic estimate of the true bond strength.
Effect of zinc complexes as activator for
sulfur vulcanisation in various rubbers
G. Heideman, J. W. M. Noordermeer, R. N.
Datta, B. van Baarle, Rubber Chem. & Techn.,
Vol. 78, No. 2, p. 245-257
Comprehensive study on the substitution of
ZnO by zinc complexes in order to reduce zinc
content in rubber compounds.
Mechanical properties of sisal/coir hybrid
fibre reinforced Natural Rubber
A. P. Haseena, K. Priya Dasan, G. Unnikrish-
nan, S. Thomas, Progress in Rubber, Plastics
and Recycling Techn., Vol. 21, No. 3, p. 155-182
The addition of sisal and coir fibres improves the
mechanical properties of NR. This was strengthe-
ned by hexamethylene tetramine and resorcinol
as a rubber-fibre interfacial bonding system.
Mechanochemical devulcanisation of
vulcanised gum Natural Rubber
G. K. Jana, C. K. Das, Progress in Rubber,
Plastics and Recycling Techn., Vol. 21, No. 3,
p. 183-199
Devulcanisation by thio-acid was carried out at
90C on an open two roll-cracker-cum-mixing
mill. More than 80% of original gum rubber
properties were recovered.
Epoxidized Natural Rubber / Silica nano-
scale organic-inorganic hybrid composites
prepared by sol-gel technique
A. Bandyopadhyay, M. D. Sarkar, A. K. Bhow-
mick, Rubber Chem. & Techn., Vol. 77, No. 5,
p. 830-846
Prepared composites exhibit improved mechani-
cal properties with increased loading of Tetra-
ethoxysilane within the Epoxidized NR matrix.
Natural Rubber latex-based nano-
composites with layered silicates
S. Mathew, S. Varghese, Journal of Rubber
Research, Vol. 8(1), 2005, p. 1-15
Nanocomposites based on sulphur prevulca-
nised NR-latex and layered silicates exhibit
improved properties.
Natuurrubber 40 - 4th quarter 2005
4
The R-S Information Center for Natural Rubber
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
E-mail info@rubber-stichting.nl
Internet www.rubber-stichting.info
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 Centers
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.
Figure 7. Injection mould.
Figure 6. Transfer mould.
mould
cavity
channel
mould
closed mould
ram
compound
rubber
mould hopper
nozzle screw
injection chamber
waste
rubber