5

Characterisation of Devulcanised
Rubber and Products Containing
Devulcanised Rubber

5.1 Characterisation of Devulcanised Rubber

The large range of processes and technologies that have been
developed for the devulcanisation of waste rubber have been
described in Chapter 4. One thing that all these processes have in
common is the need to characterise and evaluate the product that
has resulted once they have been brought to completion. This is
even truer during the research and development (R&D) stages of
a novel process, where it is essential to monitor the process of the
devulcanisation reaction to ensure that its efficiency is being optimised
and that the occurrence of any undesirable side reactions (e.g., those
involving chain scission or other forms of main-chain modification)
are minimised.

As is usually the case, the need for analysis and characterisation does
not stop once a devulcanisation process has been fully developed
and commercialised, as it is important to carry out quality control
checks at regular intervals as an integral part of any quality assurance
and good manufacturing practice system. Carrying out such tests
provides the purchasers of the devulcanised product with reassurance
that the system is not only inherently capable of producing a
high-quality product, but that it is also able to do this consistently
over an extended period of time.

It is also the case that once devulcanised rubber has been incorporated
into a rubber matrix, or is used on its own, testing is required to
ensure that it has the appropriate processing characteristics, curing
characteristics and, once vulcanisates have been generated, physical

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Recycling and Re-use of Waste Rubber

properties for the intended application. Mention of these types of

evaluations was a common occurrence throughout the sections in
Chapter 4 that reviewed the different devulcanisation processes as
they demonstrate if the ultimate goal has been reached; i.e., does the
devulcanised rubber, high quality though it might be in terms of a
large reduction in crosslink density without loss of molecular weight
(Mw), actually do the job that is needed throughout the various
processing stages and in service?

The types of processing and physical property tests that are required
to assess the important characteristics referred to above are also
continually cited in the later sections of this book dealing with the
use of waste rubber crumb in rubber products, thermoplastics, and
thermosets, for the same reasons (Chapter 7). Many other specific
property tests (e.g., acoustic) are also referred to in this book
but, unfortunately, there is insufficient space here to cover them.
A reasonably detailed section on the characterisation of rubber crumb
is provided in Chapter 6, Section 6.4, because understanding the
nature of this material is as important as understanding the properties
of devulcanised rubber when it comes to its re-use applications.

In order to provide these characterisation data it is possible to employ

both chemical analysis techniques and physical testing methods.
The background to these types of techniques and their application
to rubber materials and products have been the subject of a number
of texts, including those by Forrest [1], Loadman [2] and Brown [3]
and it is not appropriate here to describe the techniques in detail.
Instead, a concise summary is provided in Sections 5.1.1 to 5.1.4 of
the types of tests that workers in this area have found to be the most
useful in their studies.

5.1.1 Chemical Analysis Tests that can be Carried Out on

Waste Rubber Prior to Devulcanisation

It can often be necessary to carry out some initial compositional

characterisation tests on samples of waste rubber prior to carrying

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 Characterisation of Devulcanised Rubber and Products Containing
Devulcanised Rubber

out any devulcanisation work. The reasons for this could vary from
a quality control function, as dictated by a quality system linked to
good manufacturing practice, to the need to obtain fundamental
compositional information (e.g., rubber type(s), proportions of major
constituents, type of filler(s) and so on) in order to carry out some
R&D work on a new devulcanisation process.

The chemical analysis tests that are carried out to obtain this type
of information tend to only use relatively small amounts of samples
(e.g., 10 mg to 1 g) and can be conducted on the rubber whether it
is in the form of complete products (e.g., tyre tread, weather strip
and so on), crumb or powder.

Two of the most common types of tests that are carried out on
rubber samples are those that ascertain the type of polymer that a
rubber has been manufactured from and those that determine its
bulk composition.

To determine the polymer(s) that are present in a rubber it is usual

to use either Fourier-transform infrared spectroscopy or nuclear
magnetic resonance (NMR) spectroscopy. These techniques are
normally applied to a sample that has undergone some preliminary
preparation. For example, a solvent extraction can be carried out to
remove process oils and other low-Mw organic compounds and then
the extracted sample is often pyrolysed to remove any interferences
from the fillers present. As solid-state NMR techniques become more
advanced and sensitive, however, it may become easier to obtain this
information directly on samples in the future.

With regard to the determination of the bulk composition of the

rubber, this is usually achieved by thermogravimetric analysis. This
method only requires a small sample (e.g., 10 mg) and is capable
of providing a quantitative determination of the amount of process
oil, polymer, carbon black and inorganic constituents in the rubber
sample. This type of information can also be obtained on larger
samples (e.g., 5 g) by combining two or more techniques, for example,
by carrying out a quantitative solvent extraction and then heating

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Recycling and Re-use of Waste Rubber

the extracted sample in a tube furnace under first nitrogen and then
an oxygen atmosphere.

If further information is required on a rubber sample (e.g., type of

process oil, inorganic filler or cure system) then additional analysis
work will need to be carried out using either spectroscopic, thermal
or chromatographic techniques, or combinations thereof.

5.1.2 Tests that can be Carried Out to Assess the Quality of

Devulcanised Rubber

To determine the effectiveness of the devulcanisation process in

removing crosslinks, the sol fraction (i.e., fraction that is soluble in
a solvent) can be determined using a solvent extraction test with a
solvent that has a high affinity for the particular rubber that is being
examined, e.g., chloroform or acetone in the case of natural rubber
(NR) vulcanisates. The greater the sol fraction the more crosslinks
the process has removed. An important point to make here is that
if degradation of the rubber, leading to chain scission, has occurred
as a result of the process, this will also increase the sol fraction and
so the result that is obtained could be misleading. In order to ensure
that the increase in sol fraction is due to crosslink destruction alone,
the Mw of the sol fraction can be determined using the technique of
gel permeation chromatography.

It is also possible to determine the relative degree of crosslink removal

by equilibrium swelling using a high-affinity solvent. The greater
the volume swell of a particularly sample, the lower the crosslink
density of the matrix.

Physical tests that directly measure the viscosity of a rubber

compound can also be useful. A good example of such a test is
the one that can be conducted using a rubber process analyser to
determine the modulus of a rubber compound. As the crosslinks are
removed from a rubber the modulus will be reduced accordingly. If
‘standards’ are prepared by vulcanising samples to various degrees

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 Characterisation of Devulcanised Rubber and Products Containing
Devulcanised Rubber

of crosslink density to obtain calibration data of crosslink density

against modulus, the amount of crosslink destruction from a fully
cured rubber can be estimated. Care has to be taken, of course, to
ensure that other factors that affect modulus (e.g., proportions of
the major constituents  –  polymer, filler and process aids) are the
same, and so the calibration approach can only provide accurate
data when the composition of the rubber that is being devulcanised
is understood and does not vary too much. This can be a problem
with large-tonnage waste products, such as tyre tread crumb that has
been generated from a range of different types and brands of tyre.

An instrument that functions in a similar way to a rubber analyser

is the Mooney viscometer, and this can also be used to measure and
assess the extent of devulcanisation.

5.1.3 Tests that can be Carried Out to Determine

Processing Properties of Devulcanised Rubber

Once a rubber has been devulcanised to the desired level, with the
Mw retained at the target level, it has to have cure characteristics
(e.g., scorch time) that ensure it is processible. This is particularly
true if the devulcanised rubber is to be used with little, or no,
modification, but also important if it is to be blended into another
rubber compound, although the amount that is to be incorporated
into the blend obviously has an impact on the significance of this
property.

The scorch time and cure time at a given temperature of the

devulcanised rubber can be determined using a rheometer (e.g., a
Monsanto rheometer).

When it comes to assessing the quality of the product that can be

obtained from the devulcanised rubber during shaping operations
(e.g., extrusion) a laboratory extruder fitted with a die that has been
developed for this purpose (e.g., a Garvy die) can be employed. This
is a small-scale test that prevents large amounts of product being

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Recycling and Re-use of Waste Rubber

consumed by a full-scale trial. If the results from this laboratory

trial look promising, then the full trial can be carried out with much
greater confidence.

Other processing trials can be carried out, preferably under

representative industry conditions, to assess the performance of
the devulcanised rubber during compression moulding, injection
moulding, transfer moulding or any other technique used to produce
the final product.

5.1.4 Tests that can be Carried Out to Obtain Physical

Properties of Vulcanisates Containing Devulcanised
Rubber

Once the vulcanisates have been produced, their performance needs

to be fully evaluated against any in-house, industry or national/
international standards that are applicable. Some of this work will
be carried out on final products (e.g., seals) and examples of these
tests are provided in Table 5.1 in Section 5.2.2.1.

However, many tests, particularly the fundamental property tests

that are used to acquire physical data such as tensile strength, tear
strength, oil and fluid resistance, and ageing performance are usually
carried out on specially prepared test sheets due to the need for
standard test pieces of a particular geometry.

The results obtained by this suite of tests will enable a final decision
to be made, earlier decisions having been made during the progress
that has been made up to this point in the recycling process, as to
whether the devulcanised rubber is capable of being used for the
intended application.

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