ISO 19984-3:2017

Rubber and rubber products — Determination of biobased content — Part 3: Biobased mass content

ISO 19984-3:2017 specifies measuring methods for the determination of the biobased mass contents in rubber and rubber products. The biobased mass content of rubber materials or final products can be determined by separating the sample into the rubber, the inorganic ingredient (including carbon black) and the solvent extract, each of whose 14C content is determined, and then converting the results to the biobased mass content using the procedure described in this document. ISO 19984-3:2017 applies to NR, IR, BR, SBR, IIR, BIIR, CIIR and their modified rubbers, as well as to their mixtures. ISO 19984-3:2017 uses only the accelerator mass spectrometry (AMS) method for the purpose of determination of biobased content.

Élastomères et produits à base d'élastomères — Détermination de la teneur en composés biosourcés — Partie 3: Teneur en masse biosourcée

General Information

• Status: Published
• Publication Date: 13-Aug-2017
• ICS: 83.060 - Rubber
• Technical Committee: ISO/TC 45/SC 2 - Testing and analysis
• Drafting Committee: ISO/TC 45/SC 2 - Testing and analysis
• Current Stage: 9093 - International Standard confirmed
• Completion Date: 21-Feb-2023

Standards Content (Sample)

INTERNATIONAL ISO
STANDARD 19984-3
First edition
2017-08
Rubber and rubber products —
Determination of biobased content —
Part 3:
Biobased mass content
Élastomères et produits à base d’élastomères — Détermination de la
teneur en composés biosourcés —
Partie 3: Teneur en masse biosourcée
Reference number
ISO 19984-3:2017(E)
©
ISO 2017

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ISO 19984-3:2017(E)

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ISO 19984-3:2017(E)

Contents Page
Foreword .iv
Introduction .v
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 2
4 Principle . 2
5 Separation of a vulcanized rubber sample and determination of the biobased
mass content . 2
5.1 General . 2
5.2 Reagents and materials . 3
5.3 Apparatus . 3
5.4 Sampling . 4
5.5 Procedure . 4
5.5.1 Solvent extraction . 4
5.5.2 Separation of the rubber from a vulcanized rubber . 4
5.5.3 Separation of inorganic ingredients (including carbon black) from a
vulcanized rubber . 5
5.5.4 Determination of the biobased carbon content . 7
5.6 Determination of the content of rubber and carbon black . 7
5.7 Calculation . 7
5.7.1 Biobased mass content of each component . 7
5.7.2 Calculation of the biobased mass content of a vulcanized rubber sample . 8
5.8 Examples of determinations . 9
6 Determination of the biobased mass content of raw materials or latices .9
6.1 Determination of the biobased carbon content . 9
6.2 Calculation . 9
7 Precision . 9
8 Test report .10
Annex A (informative) Confirmation of the blend ratio of separated rubber .11
Annex B (informative) Precision results from an interlaboratory test programme .13
Annex C (informative) Examples of determination of biobased mass content of a rubber
model composite .15
Annex D (informative) Examples of the determination of biobased mass content for rubber
and rubber products .17
Annex E (informative) Determination of the biobased mass content of a tyre .18
Bibliography .19
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ISO 19984-3:2017(E)

Foreword
ISO (the International Organization for Standardization) is a worldwide federation of national standards
bodies (ISO member bodies). The work of preparing International Standards is normally carried out
through ISO technical committees. Each member body interested in a subject for which a technical
committee has been established has the right to be represented on that committee. International
organizations, governmental and non-governmental, in liaison with ISO, also take part in the work.
ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of
electrotechnical standardization.
The procedures used to develop this document and those intended for its further maintenance are
described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the
different types of ISO documents should be noted. This document was drafted in accordance with the
editorial rules of the ISO/IEC Directives, Part 2 (see www .iso .org/ directives).
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
any patent rights identified during the development of the document will be in the Introduction and/or
on the ISO list of patent declarations received (see www .iso .org/ patents).
Any trade name used in this document is information given for the convenience of users and does not
constitute an endorsement.
For an explanation on the voluntary nature of standards, the meaning of ISO specific terms and
expressions related to conformity assessment, as well as information about ISO’s adherence to the
World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT) see the following
URL: w w w . i s o .org/ iso/ foreword .html.
This document was prepared by Technical Committee ISO/TC 45, Rubber and rubber products,
Subcommittee SC 2, Testing and analysis.
A list of all parts in the ISO 19984 series can be found on the ISO website.
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ISO 19984-3:2017(E)

Introduction
The use of biomass materials in rubber compounds helps to decrease the rubber industry’s dependence
on fossil resources. It is also expected to lead to a reduction of carbon dioxide emission, reducing global
warming and promoting a sustainable global environment.
In the ISO 19984 series, biomass is the term used for the biological material from living or recently
living organisms such as wood and agricultural waste materials.
Industrial scale biomass is now readily being grown from numerous types of plants sources and a variety
of tree species. Biomass nowadays also includes plant or animal matter used for the production of fibres
or chemicals. It may also include biodegradable wastes. Biomass excludes organic materials which have
been transformed by geological processes into substances, such as petroleum or coal. Although fossil
fuels have their origin in ancient biomass, they are not considered biomass by the generally accepted
definition because they contain carbon that has been “out” of the modern carbon cycle.
The composition of biomass is mainly carbon, hydrogen and oxygen. Nitrogen and small quantities of
other elements can also be found.
The ISO 19984 series specifies methods for the determination of the biobased content of rubber and
rubber products. The results will give manufacturers and users a quantitative indication of their
contribution to the preservation of the environment.
ISO 19984-1 specifies how to categorize constituents of rubber and rubber products and also how to
calculate the biobased content using the compound formulation and the chemical structure of each
constituent.
ISO 19984-2 specifies how to determine the biobased carbon content by radio chemical analyses,
14
i.e. determination of C. It can be obtained from the fraction of carbon atoms derived from biomass
against the whole amount of carbon atoms in the rubber or rubber products. The methods specified in
ISO 19984-2 allow consumers to determine the biobased carbon content even when the formulation of
the rubber is unavailable.
ISO 19984-3 specifies how to separate rubber compounds into constituents, how to obtain each
constituent’s composition ratio and how to determine the biobased carbon content of each constituent
by chemical analyses. Thus, the biobased mass content for each constituent can be derived and the
biobased mass content for the whole rubber can be obtained by summing up all the constituent values.
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INTERNATIONAL STANDARD ISO 19984-3:2017(E)
Rubber and rubber products — Determination of biobased
content —
Part 3:
Biobased mass content
WARNING 1 — Persons using this document should be familiar with normal laboratory practice.
This document does not purport to address all of the safety problems, if any, associated with its
use. It is the responsibility of the user to establish appropriate safety and health practices and to
determine the applicability of any other restrictions.
WARNING 2 — Certain procedures specified in this document might involve the use or generation
of substances, or the generation of waste, that could constitute a local environmental hazard.
Reference should be made to appropriate documentation on safe handling and disposal after use.
1 Scope
This document specifies measuring methods for the determination of the biobased mass contents in
rubber and rubber products.
The biobased mass content of rubber materials or final products can be determined by separating the
sample into the rubber, the inorganic ingredient (including carbon black) and the solvent extract, each
14
of whose C content is determined, and then converting the results to the biobased mass content using
the procedure described in this document.
This document applies to NR, IR, BR, SBR, IIR, BIIR, CIIR and their modified rubbers, as well as to their
mixtures.
This document uses only the accelerator mass spectrometry (AMS) method for the purpose of
determination of biobased content.
2 Normative references
The following documents are referred to in the text in such a way that some or all of their content
constitutes requirements of this document. For dated references, only the edition cited applies. For
undated references, the latest edition of the referenced document (including any amendments) applies.
ISO 1382, Rubber — Vocabulary
ISO 1407:2011, Rubber — Determination of solvent extract
ISO 4650, Rubber — Identification — Infrared spectrometric methods
ISO 4661-2, Rubber, vulcanized — Preparation of samples and test pieces — Part 2: Chemical tests
ISO 9924-3, Rubber and rubber products — Determination of the composition of vulcanizates and uncured
compounds by thermogravimetry — Part 3: Hydrocarbon rubbers, halogenated rubbers and polysiloxane
rubbers after extraction
ISO 17257, Rubber — Identification of polymers — Pyrolytic gas-chromatographic method using mass-
spectrometric detection
ISO 19984-1:2017, Rubber and rubber products — Determination of biobased content — Part 1: General
principles and calculation methods using formulation of the rubber compound
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ISO 19984-3:2017(E)

ISO 19984-2:2017, Rubber and rubber products — Determination of biobased content — Part 2: Biobased
carbon content
3 Terms and definitions
For the purposes of this document, the terms and definitions given in ISO 1382, ISO 19984-1 and
ISO 19984-2 apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— IEC Electropedia: available at http:// www .electropedia .org/
— ISO Online browsing platform: available at http:// www .iso .org/ obp
4 Principle
14
As described in ISO 19984-2, measuring C in a rubber sample only allows to determine its biobased
carbon content. When the sample consists of a single component such as a raw rubber material or a
certain chemical, the biobased carbon content equals to the biobased mass content theoretically.
However, when the sample is a mixture of components each of which has different amount of carbon
included, the two biobased content values will be different because of the varied carbon amount as
well as the varied formulation ratio. Therefore, in order to determine the biobased mass content of
the whole, the information of each component’s biobased carbon content and the formulation ratio is
required. For a vulcanized rubber, each content such as rubber, inorganic ingredients (including carbon
black) and solvent extract, is to be analysed for calculations.
5 Separation of a vulcanized rubber sample and determination of the biobased
mass content
5.1 General
To separate a vulcanized rubber sample, employ a series of thermal decomposition methods. Any
organic ingredients that are free from cross-linking formations are extracted by the solvent. Inorganic
filler ingredients, including carbon black, are to be separated by thermogravimetry. If it is known
that there are carbonate included in the filler, apply hydrochloric acid treatment to remove them. As
a result, the vulcanized rubber is to be separated into rubber, inorganic fillers (including carbon black
and excluding carbonate) and solvent extract. When the rubber sample is unvulcanized, vulcanize it
before the separation procedure.
The flow chart of the separation scheme of a vulcanized rubber is shown in Figure 1.
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ISO 19984-3:2017(E)

14
Figure 1 — Scheme of separating a vulcanized rubber to obtain a test sample for C
measurement
5.2 Reagents and materials
Use only reagents of recognized analytical grade.
5.2.1 Acetone.
5.2.2 1,2-Dichlorobenzene.
5.2.3 Chloroform.
5.2.4 Cyclohexane.
5.2.5 Toluene.
5.2.6 Diluted hydrochloric acid, dilute 1 volume of the concentrated hydrochloric acid with 5 volumes
of water.
5.3 Apparatus
5.3.1 Freezer mill, capable to crush the rubber sample using liquid nitrogen into particles smaller
than 0,15 mm.
5.3.2 Extraction apparatus, as specified in ISO 1407.
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ISO 19984-3:2017(E)

5.3.3 Heater, such as mantle heater or block heater, capable of being maintained at 180 °C ± 5 °C.
5.3.4 Centrifugal separator, capable of operation at the rotation speed of 15 000 rpm.
5.3.5 Thermogravimetric balance, as specified in ISO 9924-3.
5.3.6 Vacuum oven, capable to perform under 0,1 kPa condition.
5.3.7 Balance, accurate to the nearest 0,1 mg.
5.3.8 Rotary evaporator.
5.4 Sampling
Select a laboratory sample in accordance with ISO 4661-2.
5.5 Procedure
5.5.1 Solvent extraction
Crush the laboratory sample into particles around 0,1 mm size with the freeze crusher or freezer mill
(5.3.1).
Perform extraction on 1 g of the crushed sample with acetone (5.2.1) for more than 8 h, in accordance
with ISO 1407:2011, Method A.
14
Residual acetone will affect the result of following C determination, so dry the extract completely
with the vacuum oven (5.3.6) for 2 h at room temperature.
Weigh the extract after it is completely dried and calculate the content of the extract (m ) in accordance
e
with ISO 1407.
The extract obtained here will be applied for the determination of the biobased carbon content (see 5.5.4).
Set aside the residue from this solvent extraction for the separation procedure by thermal decomposition
(see 5.5.2.2 or 5.5.2.3).
5.5.2 Separation of the rubber from a vulcanized rubber
5.5.2.1 Selection of method
When no information is available about the sample’s rubber type(s), examine whether it is single or
blended using procedures specified in ISO 4650 or ISO 17257 (if the type of rubber is already known,
skip this process).
For a single rubber, apply the separation method in 5.5.2.2. For a blended rubber, select the separation
method in 5.5.2.3 instead.
NOTE It is not necessary to degrade 100 % of the compound during this separation procedure.
5.5.2.2 Separation of rubber by heating an empty glass tube
5.5.2.2.1 Place the residue after solvent extraction (see 5.5.1) of test sample of 100 mg in a test tube
capped with glass wool and heat it for about 10 min in a heater (5.3.3) regulated at 180 °C ± 5 °C.
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ISO 19984-3:2017(E)

5.5.2.2.2 Allow the heated residue to cool, transfer to a 100 ml flask fitted with a reflux condenser and
add 50 ml of chloroform (5.2.3) to the flask. Cyclohexane (5.2.4) may be used instead of chloroform.
5.5.2.2.3 Dissolve the degraded rubber in the chloroform for 15 min with the
...