INTERNATIONAL ISO

STANDARD 6964

Second edition
2019-02

Polyolefin pipes and fittings —

Determination of carbon black
content by calcination and pyrolysis —
Test method
Tubes et raccords en polyoléfines — Détermination de la teneur en
noir de carbone par calcination et pyrolyse — Méthode d'essai
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ISO 6964:2019
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Reference number
ISO 6964:2019(E)

© ISO 2019
ISO 6964:2019(E)


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ISO 6964:2019
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 ISO 6964:2019(E)


Contents Page

Foreword......................................................................................................................................................................................................................................... iv
1 Scope.................................................................................................................................................................................................................................. 1
2 Normative references....................................................................................................................................................................................... 1
3 Principle......................................................................................................................................................................................................................... 1
4 Method A: Electrical tube furnace....................................................................................................................................................... 2
4.1 Reagents........................................................................................................................................................................................................ 2
4.2 Apparatus..................................................................................................................................................................................................... 2
4.3 Procedure..................................................................................................................................................................................................... 2
4.3.1 Test conditions................................................................................................................................................................... 2
4.3.2 Sampling.................................................................................................................................................................................. 2
4.3.3 Conditioning......................................................................................................................................................................... 2
4.3.4 Silica sample boat preparation for the test................................................................................................ 2
4.3.5 Test portion........................................................................................................................................................................... 3
4.3.6 Determination..................................................................................................................................................................... 3
4.4 Calculation and expression of results (Method A).................................................................................................... 3
5 Method B1 or B2: Muffle furnace (conventional B1) or (microwave B2)................................................... 4
5.1 Apparatus..................................................................................................................................................................................................... 4
5.2 Procedure..................................................................................................................................................................................................... 4
5.2.1 Test conditions................................................................................................................................................................... 4
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5.2.2 Conditioning......................................................................................................................................................................... 4
5.2.3 Sampling.................................................................................................................................................................................. 4
(standards.iteh.ai)
5.2.4 Crucible preparation for the test........................................................................................................................ 4
5.2.5 Test portion........................................................................................................................................................................... 5
5.2.6 Determination.....................................................................................................................................................................
ISO 6964:2019 5
5.3 Calculation and expression of results (Method B1 and B2).............................................................................. 6
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6 Method C: Thermogravimetric analyzer (TGA)..................................................................................................................... 6
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6.1 Apparatus..................................................................................................................................................................................................... 6
6.2 Procedure..................................................................................................................................................................................................... 6
6.2.1 Conditioning......................................................................................................................................................................... 6
6.2.2 Sampling.................................................................................................................................................................................. 6
6.2.3 Test portion........................................................................................................................................................................... 6
6.2.4 Temperature scanning program.......................................................................................................................... 7
6.2.5 Gas-flow rate........................................................................................................................................................................ 7
6.2.6 Determination..................................................................................................................................................................... 7
6.3 Calculation and expression of results (Method C).................................................................................................... 7
7 Test report.................................................................................................................................................................................................................... 8

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ISO 6964:2019(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 of 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
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World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT) see www​.iso​
.org/iso/foreword​.html. (standards.iteh.ai)
This document was prepared by Technical Committee ISO/TC  138, Plastics pipes, fittings and valves
for the transport of fluids, Subcommittee SC 5, General properties of pipes, fittings and valves of plastic
ISO 6964:2019
materials and their accessories — Test methods and basic specifications.
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This second edition cancels and replaces the first edition (ISO 6964:1986), which has been technically
revised. The main changes compared with the last edition are the following:
— Conventional and microwave muffle furnace test methods, and a thermogravimetric analyzer (TGA)
test method have been added.
Any feedback or questions on this document should be directed to the user’s national standards body. A
complete listing of these bodies can be found at www​.iso​.org/members​.html.

iv  © ISO 2019 – All rights reserved

INTERNATIONAL STANDARD ISO 6964:2019(E)

Polyolefin pipes and fittings — Determination of carbon

black content by calcination and pyrolysis — Test method

1 Scope
This document specifies test methods for the determination of the carbon black content of polyolefin
compositions used in particular for the manufacture of pipes and fittings, and provides a basic
specification for polyethylene pipes and fittings.
This document applies equally to the material for manufacture and to any material taken from a pipe or
fitting.

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 11358-1, Plastics — Thermogravimetry (TG) of polymers — Part 1: General principles
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3 Principle (standards.iteh.ai)
It is possible to determine the carbon black content of polyolefin compositions by one of the following
three methods: ISO 6964:2019
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a) Pyrolysis of the sample at (550 ± 50) °C in a stream of nitrogen for 45 min followed by calcination at
988262f47e70/iso-6964-2019
(900 ± 25) °C, by using an electrical tube furnace (Method A).
b) Pyrolysis of the sample in a quartz crystal crucible with lid, by using a muffle furnace. According to
the type of muffle furnace used there are two different procedures:
1) Conventional muffle furnace (Method B1): pyrolysis from (325  ±  25)  °C to (550  ±  25)  °C at
15 °C/min and at (550 ± 25) °C for (10 ± 0,5) min followed by calcination at (900 ± 25) °C.
2) Microwave muffle furnace (Method B2): pyrolysis at (520 ± 25) °C for (10 ± 0,5) min followed
by calcination at (900 ± 25) °C.
c) Pyrolysis of the sample at a constant rate in a thermogravimetric analyzer (TGA) under inert
atmosphere at 800 °C followed by calcination under oxidizing atmosphere at 900 °C (Method C).
NOTE 1 Carbon black is decomposed from 500  °C in air or oxygen. Therefore, the loss observed between
500 °C and 700 °C in air or oxygen corresponds to the overall decomposition of the carbon black.

NOTE 2 If the composition contains, in addition to the carbon black, additives likely to decompose at 900 °C,
for example ingredients such as calcium carbonate, the calculation can lead to an over-estimation of the carbon
black content. If the ash yield is more than 1 %, further investigation can be required.

Calculate the carbon black content from the difference in mass before and after calcination and
pyrolysis.

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ISO 6964:2019(E)


4 Method A: Electrical tube furnace

4.1 Reagents

4.1.1 Dry nitrogen, having an oxygen content less than 20  ppm, under pressure in a steel cylinder
provided with a pressure-reducing valve and flow meter.
NOTE If required, the nitrogen can be purified by bubbling the gas through a pyrogallol solution or by
passing it over heated copper tinsel, foil, wire or turnings or by passing it through a gas purifier prior to passing
into the furnace.

4.2 Apparatus

4.2.1 Silica combustion sample boat, with a sleeve of 50 mm to 60 mm long.

4.2.2 Electric tube furnace, fitted with a device to allow the sample boat to be inserted and
withdrawn. The tube is fitted with nozzles to admit the nitrogen and to evacuate the fumes. A diaphragm
closed by means of a glass-wool bung placed behind the entry nozzle ensures that the nitrogen stream is
distributed uniformly.

The minimum length of the electric tube furnace should be ≥ 3 times the length of the sample boat, and
the minimum length of the quartz tube should be ≥ 7 times the length of the sample boat.

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4.2.3 Desiccator, capable of holding the silica sample boat (4.2.1).

4.2.4
(standards.iteh.ai)
Balance, with an accuracy of ± 0,1 mg.
ISO 6964:2019
4.2.5 Timer, with an accuracy of ± 1 s.
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4.3 Procedure

4.3.1 Test conditions

Determination of mass shall be carried out in a room at standard temperature (23 ± 2) °C.

4.3.2 Sampling

Test specimen may be in the form of pellet or finished product. In the last case, the specimen shall be
reduced to small fragments. 

4.3.3 Conditioning

The test sample shall be conditioned for 24 h at (23 ± 2) °C before preparation.

4.3.4 Silica sample boat preparation for the test

Take the silica sample boat which shall be clean and weighed, and proceed as follows:
Place the silica sample boat in the electric tube furnace and adjust the temperature to (900 ± 25) °C.
Once this temperature is reached, leave to calcination for approximately 1 h. Then, dry the silica sample
boat in the desiccator at room temperature and weigh. Place again the silica sample boat into the
desiccator for 30 min and weigh again. This operation shall be repeated until constant mass, i.e. until
two consecutive weighing do not differ by more than 0,5 mg. This weighing is recorded as m.

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 ISO 6964:2019(E)


4.3.5 Test portion

Three test portions shall be prepared as follows:

Tare the silica sample boat. Weigh, to the nearest 0,1 mg, approximately 1 g of material from the test
sample (4.3.2). Record this mass as m1.

4.3.6 Determination

The determination on each test sample shall be carried out as described below.
Place the silica sample boat with the test portion (4.3.4) in the inlet of the combustion tube of the electric
tube furnace (4.2.2) which has been previously heated to (550 ± 50) °C. Fix the nozzle to the tube inlet
and then connect it to the outlet of the nitrogen stream after, if necessary, the nitrogen has passed
through the purification system; circulate the nitrogen in the apparatus at a rate of (200 ± 20) cm3/min
for approximately 5 min.
Move the combustion tube with the silica sample boat towards the centre of the electric tube furnace,
adjust the nitrogen flow rate to (100 ± 10) cm3/min and leave it to pyrolyse for approximately 45 min.
At the end of this period, return the combustion tube with the silica sample boat to the cold section of
the electric tube furnace and leave it there for 10 min while maintaining the flow of nitrogen.
Remove the silica sample boat from the combustion tube of the electric tube furnace, allow it to cool in
the desiccator (4.2.4) and weigh under the same conditions as prior to the pyrolysis (4.3.3). Record the
mass to the nearest 0,1 mg as m2.
iTeh STANDARD PREVIEW
Place the silica sample boat in the furnace at a temperature of (900 ± 25) °C and calcine until all traces
of carbon black have disappeared.(standards.iteh.ai)
Allow it to cool in the desiccator (4.2.4) and weigh under the same
conditions as prior to the pyrolysis (4.3.3). Record the mass to the nearest 0,1 mg as m3.
ISO 6964:2019
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4.4 Calculation and expression of results (Method A)
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Calculate the carbon black content, expressed as a percentage by mass, from Formula (1).
m2 − m3
× 100% (1)
m1
where

  m1 is the mass, in grams, of the test portion;

  m2 is the mass, in grams, of the silica sample boat plus the test portion after pyrolysis at 550 °C;

  m3 is the mass, in grams, of the sample boat plus the test portion after calcination at 900 °C, with
ash where appropriate.
Calculate the arithmetic mean of the carbon black content determined on the three test portions and
report the result rounded mathematically to two significant figures.
NOTE Where appropriate (see NOTE 2 to Clause 3), calculate the ash content, expressed as a percentage of
the original mass, from Formula (2):

m3 − m
× 100% (2)
m1

where

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ISO 6964:2019(E)


  m is the mass, in grams, of the silica sample boat;

m1 is the mass, in grams, of the test portion;

  m3 is the mass, in grams, of the sample boat plus the test portion after calcination at
900 °C, with ash where appropriate.
Calculate the arithmetic mean of the ash content determined on the three test portions and report the
result rounded mathematically to two significant figures.

5 Method B1 or B2: Muffle furnace (conventional B1) or (microwave B2)

5.1 Apparatus

5.1.1 Crucible, recipient of quartz crystal with a lid of the same material which closes the recipient
just by superposition on the recipient, with approximately 10 ml capacity.

The crucible system generates an inert atmosphere by replacing the air in the crucible due to the gases
released by the sample during the pyrolysis. It is important that there is no damage on the crucible edge
or on the lid because it would allow air to enter and the consequent burning of the sample.

5.1.2 Desiccator, capable of holding the crucibles (5.1.1).

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5.1.3 Balance, with an accuracy of ±0,1 mg.

5.1.4
(standards.iteh.ai)
Conventional muffle furnace, for method B1 (5.2.6.1).
NOTE
ISO 6964:2019
For a muffle furnace that does not have a programming system, a scan of (15 ± 1) °C/min is equivalent
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to heating from 300 °C to 500 °C in approximately 15 min and similarly for the cooling scan.
988262f47e70/iso-6964-2019
5.1.5 Microwave muffle furnace, for method B2 (5.2.6.2).

5.1.6 Timer, with an accuracy of (±1) s.

5.2 Procedure

5.2.1 Test conditions

Determination of mass shall be carried out in a room at standard temperature (23 ± 2) °C.

5.2.2 Conditioning

The test sample shall be conditioned for 24 h at (23 ± 2) °C before preparation.

5.2.3 Sampling

The test specimen may be in the form of a pellet or finished product. In the last case, the specimen shall
be reduced to small fragments.

5.2.4 Crucible preparation for the test

Take the crucible which shall be clean and weighed, and proceed as follows:
Place the crucible in the conventional muffle furnace and adjust the temperature to (900 ± 25) °C. Once
this temperature is reached, leave to calcinate for approximately 1  h. Then, dry the crucible in the
desiccator at room temperature and weigh. Place again the crucible into the desiccator for 30 min and

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 ISO 6964:2019(E)


weigh again. This operation shall be repeated until constant mass, i.e. until two consecutive weighing
do not differ by more than 0,5 mg. This weighing is recorded as m.
This procedure could be carried out also in a microwave muffle furnace at the same temperature but
for 15 min.

5.2.5 Test portion

Three test portions shall be prepared as follows with the mass selected in the range dependent on the
equipment used:
Tare the crucible. Weigh, to the nearest 0,1 mg, approximately 1 g to 10 g of the material according to
the type of crucible used.
Record this mass as m1.

5.2.6 Determination

5.2.6.1 Method B1: Conventional muffle furnace

Place the crucible with lid and with the test portion (5.2.4) in the conventional muffle furnace (5.1.4).
The temperature shall be at (325  ±  25)  °C. Program the heating scan to (10  to  15  ±  1)  °C/min until
reaching (550 ± 25) °C. Let it pyrolize at this temperature for (10 ± 5) minutes. Program cooling scan to
(15 ± 1) °C/min until reaching (325 ± 25) °C, initial temperature of the pyrolysis cycle.
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Remove the crucible with lid from the muffle furnace and allow it to cool in the desiccator until room
temperature is reached. Dry the crucible with lid in the desiccator at room temperature and remove the
(standards.iteh.ai)
lid to weigh the crucible. Place the crucible in the desiccator for 30 min and weigh again. This operation
shall be repeated until constant mass, i.e. until two consecutive weighing do not differ by more than
0,5 mg. This weighing is recorded as m2. ISO 6964:2019
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Place the crucible without lid in the 988262f47e70/iso-6964-2019
muffle furnace and adjust the temperature to (900 ± 25) °C. When
this temperature is reached, calcine for (30 ± 5) min.
Turn off the muffle furnace, wait until the temperature has dropped below 500 °C and remove the crucible.
Dry the crucible without the lid in the desiccator at room temperature and weigh. Place the crucible in the
desiccator for 30 min and weigh again. This operation shall be repeated until constant mass, i.e. until two
consecutive weighing do not differ by more than 0,5 mg. This weighing is recorded as m3.

5.2.6.2 Method B2: Microwave muffle furnace

Place the crucible with lid and with the test portion (4.2.4) in the microwave muffle furnace (5.1.5),
which temperature shall be at (520 ± 25) °C. Leave it to pyrolyse for (10 ± 0,5) min.
Remove the crucible with lid from the microwave muffle furnace and allow it to cool in the desiccator
until room temperature is reached. Dry the crucible with lid in the desiccator at room temperature and
weigh the crucible without the lid. Place the crucible in the desiccator for 30 min and weigh again. This
operation shall be repeated until constant mass, i.e. until two consecutive weighing don’t differ by more
than 0,5 mg. This weighing is recorded as m2.
Place the crucible without lid in the microwave muffle furnace and adjust the temperature at
(900 ± 25) °C. When this temperature is reached, calcine for (10 ± 1) min.
Turn off the microwave muffle furnace, wait until the temperature has dropped below 500  °C
and remove the crucible. Cover the crucible with the lid and introduce it in the desiccator at room
temperature and weigh the crucible without the lid. Place the crucible in the desiccator for 30 min and
weigh again. This operation shall be repeated until constant mass, i.e. until two consecutive weighing
do not differ by more than 0,5 mg. This weighing is recorded as m3.

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