TECHNICAL ISO/TS

SPECIFICATION 17796

First edition
2013-06-15

Rubber — Trapping and identification

of volatile components of rubber
fumes with active sampling on a
poly(2,6-diphenylphenylene oxide)
type sorbent, using thermodesorption
and gas chromatographic method with
mass spectrometric
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Caoutchouc — Piégeage et identification des composés volatils des
fumées de procédés du caoutchouc, par échantillonnage actif sur un
sorbant de 17796:2013
ISO/TS type poly(oxyde de 2,6-diphénylphénylène), en utilisant
une méthode par thermodésorption et chromatographie en phase
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gazeuse avec détection par spectrométrie de masse
095afc14f172/iso-ts-17796-2013

Reference number
ISO/TS 17796:2013(E)

© ISO 2013
ISO/TS 17796:2013(E)


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ISO/TS 17796:2013
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095afc14f172/iso-ts-17796-2013

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 ISO/TS 17796:2013(E)


Contents Page

Foreword......................................................................................................................................................................................................................................... iv
1 Scope.................................................................................................................................................................................................................................. 1
2 Terms and definitions...................................................................................................................................................................................... 1
3 Principle......................................................................................................................................................................................................................... 2
4 Sampling......................................................................................................................................................................................................................... 2
4.1 Equipment.................................................................................................................................................................................................... 2
4.2 Operating conditions.......................................................................................................................................................................... 2
4.3 Procedure..................................................................................................................................................................................................... 3
5 Thermal desorption, gas chromatography ...............................................................................................
mass spectrometry............................................................................................................................................................................................ 3
5.1 General............................................................................................................................................................................................................ 3
5.2 Reagents........................................................................................................................................................................................................ 3
5.3 Apparatus..................................................................................................................................................................................................... 4
5.4 Procedure..................................................................................................................................................................................................... 4
6 Test report.................................................................................................................................................................................................................... 6
Annex A (informative) Example of application to a laboratory EPDM/peroxide mix........................................ 7
Annex B (informative) Example of application to a laboratory NR mix.........................................................................10
Bibliography.............................................................................................................................................................................................................................. 13
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ISO/TS 17796:2013(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. 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. 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.
The committee responsible for this document is ISO/TC 45, Rubber and rubber products, Subcommittee
SC 2, Testing and analysis. iTeh STANDARD PREVIEW
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TECHNICAL SPECIFICATION ISO/TS 17796:2013(E)

Rubber — Trapping and identification of volatile

components of rubber fumes with active sampling on a
poly(2,6-diphenylphenylene oxide) type sorbent, using
thermodesorption and gas chromatographic method with
mass spectrometric detection

1 Scope
This Technical Specification specifies a qualitative method of thermodesorption – gas chromatography –
mass spectrometry (TD-GC-MS) for the identification of volatile components in rubber fumes, after trapping
on a solid sorbent based on 2,6-diphenylphenylene-oxide polymer resin. It is applicable to a screening of
emissions from the processing of rubber compounds in the ambient workplace and storage environment.
CAUTION — Persons using this Technical Specification should be familiar with the procedures for
gas chromatography – mass spectrometry measurement and analysis. All the operative details
for the application and set-up of the GC-MS are assumed to be in agreement with the operative
instructions provided by the manufacturer. Therefore, the detailed procedure for the operation
is not included in this Technical Specification. This Technical Specification specifies a qualitative
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method which is not aimed at quantitative analyses.

2 Terms and definitions

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ISO/TS 17796:2013
For the purposes of this document, the following terms and definitions apply.
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semi-volatile organic compound
SVOC
organic compound whose boiling point is in the range from (240 to 260) °C to (380 to 400) °C
Note 1 to entry: This classification has been defined by the World Health Organization.[4]

Note 2 to entry: Boiling points of some compounds are difficult or impossible to determine because they decompose
before they boil at atmospheric pressure. Vapour pressure is another criterion for the classification of compound
volatility that may be used for the classification of organic chemicals. SVOCs have vapour pressures of between
10−2 kPa and 10−8 kPa.

2.2
volatile organic compound
VOC
organic compound whose boiling point is in the range from (50 to 100) °C to (240 to 260) °C
Note 1 to entry: This classification has been defined by the World Health Organization.[4]

Note 2 to entry: Boiling points of some compounds are difficult or impossible to determine because they decompose
before they boil at atmospheric pressure. Vapour pressure is another criterion for the classification of compound
volatility that may be used for the classification of organic chemicals. VOCs generally have saturation vapour
pressures at 25 °C greater than 102 kPa.

2.3
very volatile organic compound
VVOC
organic compound whose boiling point is in the range from <0 °C to (50 to 100) °C
Note 1 to entry: This classification has been defined by the World Health Organization.[4]

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Note 2 to entry: Boiling points of some compounds are difficult or impossible to determine because they decompose
before they boil at atmospheric pressure. Vapour pressure is another criterion for the classification of compound
volatility that may be used for the classification of organic chemicals. VVOCs typically have vapour pressures of
greater than 15 kPa.

3 Principle
Rubber fumes are sampled on an adsorbent support using a pump. They are recovered from the trap
by thermal desorption and the substances composing the desorbed fume are identified by the mass
spectrometer. The method identifies the components adsorbed on the trap support used, except benzene.
The actual composition of the emissions depends on the selection of ingredients used for compounding
and on the thermal and mechanical conditions applied to the rubber. Moreover, environmental humidity
might interfere with the sorption capability of the sorbent material.
The sorbent tube is used for the trapping of volatile (VOC) (boiling point >50 °C to 100 °C) and semi-
volatile (SVOC) (boiling point >240 °C) organic compounds in the C6 to C26 range, which are chemically
stable against a desorption temperature of 200 °C. Very volatile compounds (VVOC) (boiling point
approximately 50 °C to 100 °C) are only partially retained by the sorbent. Other sorbents based on
carbon molecular sieve or by multi-sorbent bed tube may be more appropriate in this case.
The upper limit of the useful range is set by the sorptive capacity of the sorbent used and by the linear
dynamic range of the gas chromatograph column and detector or by the sample-splitting capability of
the analytical instrumentation used. The sorptive capacity is measured as a breakthrough volume of air,
which determines the maximum air volume that shall not be exceeded when sampling.
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NOTE Small amounts of benzene could be created by the thermal decomposition of the sorbent.
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4 Sampling ISO/TS 17796:2013
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4.1 Equipment 095afc14f172/iso-ts-17796-2013

4.1.1 Trap support, poly(2,6-diphenylphenylene oxide)1), of quantity 180 mg to 200 mg, of particle
size 0,18 mm to 0,25 mm (60/80 mesh), and of specific surface 20 m2/g to 35 m2/g. Another quantity,
particle size or specific surface may be chosen if the test result is proven to be equivalent.

4.1.2 Adsorbent tubes, stainless steel tube.

4.1.3 Calibrated pump

Calibrate the pump with the sorbent tube assembly inline, using a calibrated external flowmeter.
One end of the calibrated flowmeter shall be kept at atmospheric pressure to ensure proper operation.

4.2 Operating conditions

4.2.1 Trap support

Recondition the trap sorbent material before sampling, heating it at 300 °C under inert gas for 1 h
(minimum) to 8 h (maximum). Check the cleaning of the trap support by GC-MS analysis.
Recondition tubes stored for more than four weeks before sampling.

1) One example of poly(2,6-diphenylphenylene oxide) is Tenax TA®, which is an example of a suitable product
available commercially. This information is given for the convenience of users of this Technical Specification and
does not constitute an endorsement by ISO of this product.

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4.2.2 Sampling flowrate

The sampling flowrate shall be 100 ml/min maximum at room temperature.

4.2.3 Sampling volume

The sampling volume shall be 6 l maximum.

Two sampling tubes should be placed in parallel, in the same location, and operated simultaneously in
case of trap or analysis dysfunction. Only one tube shall be analysed.

4.3 Procedure
When used for fixed-location sampling, a suitable sampling site is to be chosen. The location of sampling
shall be close to the source. Sampling the surrounding atmosphere is also admissible.
Assemble the sampling line. The sampling train includes, in the following order, a sample source, a
sampling tube(s), a flow controller and a pump. Prepare a tube assembly by joining the tubes in series
with a union if more than one tube is used to ensure that the breakthrough volume for the analyte
of interest is not exceeded. Attach the pump to the sorbent tube or tube assembly with plastic (PE or
PTFE) or rubber tubing. Turn on the pump and adjust the flowrate so that the recommended sample
volume is taken within the available time. The recommended air sample volume for the VOCs covered
by this Technical Specification amounts to a total of 6 l maximum. An appropriate sampling flowrate
is in the range of 50 ml/min to 100 ml/min. Note the starting time, temperature and, if necessary for
calculation, also the barometric pressure. At the end of the sampling period, note the flowrate or register
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the readings. Turn off the pump, and note the time, temperature and, if necessary, barometric pressure.
Disconnect the sampling tube from the sampling line and seal both ends using screw-cap fittings with
PTFE ferrules.
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If the sampling flowrate is determinedISO/TS by using an integrated flow-measuring device, e.g. a mass
17796:2013
flowmeter, connect the sampling tube to the sampling line, start the pump, note the time and flowrate
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or register readings. Note temperature and, if necessary, barometric pressure. An appropriate sampling
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flowrate is in the range of 50 ml/min to 100 ml/min. At the end of the sampling period, note the flowrate
or register readings. Turn off the pump, note and register the time the pump was turned off. Disconnect
the sampling tube from the sampling line and seal both ends using screw-cap fittings with PTFE ferrules.
For storage between sampling and analyses, store the closed tubes at room temperature in a container
free of any emission. The storage time shall not exceed four weeks.

5 Thermal desorption, gas chromatography – mass spectrometry

5.1 General
For analysis, volatile compounds are thermally desorbed from the sampling tubes. The individual
substances are separated using a capillary column in a gas chromatograph and detected with a mass
spectrometric detector.

5.2 Reagents

5.2.1 Trap coolant, used for freezing the cool trap in the thermal desorption apparatus (−30 °C or
colder). Liquid nitrogen or other alternatives (e.g. a Peltier device) are required. A secondary sorbent cold
trap may be used to focus the analytes.

5.2.2 Gas chromatograph carrier gas, helium.

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5.3 Apparatus

5.3.1 Thermal desorption apparatus or equivalent, connectable with a gas chromatograph and
capable of heating up to 300 °C.

5.3.2 Gas chromatograph, equipped with the following accessories:

— capillary column;
— stationary phase: 5 % diphenyl, 95 % polydimethylsiloxane;
Experience shows that a column of 60 m, diameter 0,25 μm and 0,20 μm thickness film, with a flowrate
of 1,2 ml/min is usually appropriate.
— injector system: depending on the desorption system;
— split value: properly adapted in accordance with the sampled amount;
— oven temperature program: established to separate compounds.

5.3.3 Mass spectrometer, quadrupole mass spectrometer in electronic impact mode, specified as follows:

— transfer line temperature: 300 °C;

— ion source temperature: 230 °C to 300 °C;
— ionizing voltage: 70 eV;
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— scan range: 25 m/z to 600 m/z;
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— analysis mode: full scan. ISO/TS 17796:2013
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5.4 Procedure

5.4.1 Principle

Heat the support at 200 °C and trap the volatile compounds generated during the heating period at a
temperature of −30 °C or colder. After desorption and cold trapping to preconcentrate the analytes, start
the GC-MS measurement in order to obtain the gas chromatogram and mass spectra.

5.4.2 Thermal desorption

Typical desorption conditions for volatile compounds analysis using a secondary cold trap and sampling
tube containing 180 mg to 200 mg of sorbent are:
— desorption temperature: 200 °C;
— desorption time: 30 min;
— desorption gas flowrate: 50 ml/min;
— cold-trap high temperature: 300 °C;
— cold-trap low temperature: −30 °C or colder;
— transfer-line temperature: 250 °C minimum;
— split ratios: split ratios between the sample tube and secondary trap and between the secondary
trap and analytical column (if applicable) should be selected depending on the expected atmospheric
concentration. (See the handbook of the respective manufacturers of the thermal desorption apparatus.).

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5.4.3 Analysis

For the identification of single, non-target substances, analyse the samples in the scan mode. Identify
substances detected in the sample using the mass spectrometer’s total ion chromatogram and the
retention time of the compounds. The identification of substances is achieved by matching the unknown
mass spectrum with the reference mass spectrum stored in a library of pure substances. This task is
usually performed by specialized algorithms included in the software of the GC-MS equipment. The
quality of the match is indicated with a custom match index. The acceptance of the matching result is
based on the analyst carrying out visual comparison of the mass spectra.
NOTE As a general indication, a quality index greater than 90 % or a reference standard using retention time
and mass spectrum will grant the correct identification of the substance.

Substance identification and acceptance of the proposed mass spectra from library research shall be
validated by the operator.

5.4.4 Verification of the system

5.4.4.1 Analysis of laboratory blank

A sorbent sampling tube, conditioned according to 4.2.1, is analysed under the conditions stated in 5.4.3.
The resulting chromatogram shall be clean of peaks.

5.4.4.2 Analysis of a control standard

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For the qualification of the TD-GC-MS system and its sensitivity, a control standard mix shall be analysed.
The mix consists of model substances solved in an appropriate solvent. A sorbent sampling tube shall be
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spiked with a defined volume by means of a microlitre syringe on the surface of the sorbent material in
the tube. After this, a defined volume of pure air shall be pumped through the sampling tube according
to the sampling procedure as stated above. ISO/TS
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breakthrough volume is to be checked by using a second
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tube connected downstream of the first. Both tubes shall be analysed according to the procedure in 5.4.
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The TD-GC-MS chromatogram has to show all peaks of the control components, and a signal-to-noise
ratio of 3 to 1 shall be reached as a minimum.
Considering the determination of some specially selected components, the control mix shall be adjusted
to the Scope.
NOTE 1 The substances in Table 1, dissolved in an appropriate solvent, have proved suitable for checking the
system.

NOTE 2 The Grob solution is also possible.

Table 1 — Control mixture

Benzene n-Undecane
n-Heptane 2,6-Dimethylphenol
Toluene n-Dodecane
n-Octane n-Tridecane
p-Xylene n-Tetradecane
o-Xylene Dicyclohexylamine
n-Nonane n-Pentadecane
n-Decane n-Hexadecane
2-Ethylhexanol-1 Di-(2-ethylhexyl) adipate

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