SIST EN ISO 16014-5:2019

SLOVENSKI STANDARD
SIST EN ISO 16014-5:2019
01-september-2019
Nadomešča:
SIST EN ISO 16014-5:2012
Polimerni materiali - Določevanje povprečne molekulske mase in porazdelitve
molekulske mase polimerov z gelsko izključitveno kromatografijo (SEC) - 5. del:
Metoda s sipanjem svetlobe (ISO 16014-5:2019)
Plastics - Determination of average molecular weight and molecular weight distribution of
polymers using size-exclusion chromatography - Part 5: Light-scattering method (ISO
16014-5:2019)
Kunststoffe - Bestimmung der durchschnittlichen Molmasse und der
Molmassenverteilung von Polymeren mittels Gelpermeationschromatographie - Teil 5:
Lichtstreudetektionsverfahren (ISO 16014-5:2019)
Plastiques - Détermination de la masse moléculaire moyenne et de la distribution des
masses moléculaires de polymères par chromatographie d'exclusion stérique - Partie 5:
Méthode par diffusion lumineuse (ISO 16014-5:2019)
Ta slovenski standard je istoveten z: EN ISO 16014-5:2019
ICS:
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
83.080.01 Polimerni materiali na Plastics in general
splošno
SIST EN ISO 16014-5:2019 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

---------------------- Page: 1 ----------------------

SIST EN ISO 16014-5:2019

---------------------- Page: 2 ----------------------

SIST EN ISO 16014-5:2019


EN ISO 16014-5
EUROPEAN STANDARD

NORME EUROPÉENNE

June 2019
EUROPÄISCHE NORM
ICS 83.080.01 Supersedes EN ISO 16014-5:2012
English Version

Plastics - Determination of average molecular weight and
molecular weight distribution of polymers using size-
exclusion chromatography - Part 5: Light-scattering
method (ISO 16014-5:2019)
Plastiques - Détermination de la masse moléculaire Kunststoffe - Bestimmung der durchschnittlichen
moyenne et de la distribution des masses moléculaires Molmasse und der Molmassenverteilung von
de polymères par chromatographie d'exclusion Polymeren mittels Gelpermeationschromatographie -
stérique - Partie 5: Méthode par diffusion lumineuse Teil 5: Lichtstreudetektionsverfahren (ISO 16014-
(ISO 16014-5:2019) 5:2019)
This European Standard was approved by CEN on 26 May 2019.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this
European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references
concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CEN
member.

This European Standard exists in three official versions (English, French, German). A version in any other language made by
translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management
Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and United Kingdom.





EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2019 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 16014-5:2019 E
worldwide for CEN national Members.

---------------------- Page: 3 ----------------------

SIST EN ISO 16014-5:2019
EN ISO 16014-5:2019 (E)
Contents Page
European foreword . 3

2

---------------------- Page: 4 ----------------------

SIST EN ISO 16014-5:2019
EN ISO 16014-5:2019 (E)
European foreword
This document (EN ISO 16014-5:2019) has been prepared by Technical Committee ISO/TC 61 "Plastics"
in collaboration with Technical Committee CEN/TC 139 “Paints and varnishes” the secretariat of which
is held by DIN.
This European Standard shall be given the status of a national standard, either by publication of an
identical text or by endorsement, at the latest by December 2019, and conflicting national standards
shall be withdrawn at the latest by December 2019.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
This document supersedes EN ISO 16014-5:2012.
According to the CEN-CENELEC Internal Regulations, the national standards organizations of the
following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria,
Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta,
Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and the United Kingdom.
Endorsement notice
The text of ISO 16014-5:2019 has been approved by CEN as EN ISO 16014-5:2019 without any
modification.

3

---------------------- Page: 5 ----------------------

SIST EN ISO 16014-5:2019

---------------------- Page: 6 ----------------------

SIST EN ISO 16014-5:2019
INTERNATIONAL ISO
STANDARD 16014-5
Second edition
2019-05
Plastics — Determination of average
molecular weight and molecular
weight distribution of polymers using
size-exclusion chromatography —
Part 5:
Light-scattering method
Plastiques — Détermination de la masse moléculaire moyenne
et de la distribution des masses moléculaires de polymères par
chromatographie d'exclusion stérique —
Partie 5: Méthode par diffusion lumineuse
Reference number
ISO 16014-5:2019(E)
©
ISO 2019

---------------------- Page: 7 ----------------------

SIST EN ISO 16014-5:2019
ISO 16014-5:2019(E)

COPYRIGHT PROTECTED DOCUMENT
© ISO 2019
All rights reserved. Unless otherwise specified, or required in the context of its implementation, no part of this publication may
be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting
on the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address
below or ISO’s member body in the country of the requester.
ISO copyright office
CP 401 • Ch. de Blandonnet 8
CH-1214 Vernier, Geneva
Phone: +41 22 749 01 11
Fax: +41 22 749 09 47
Email: copyright@iso.org
Website: www.iso.org
Published in Switzerland
ii © ISO 2019 – All rights reserved

---------------------- Page: 8 ----------------------

SIST EN ISO 16014-5:2019
ISO 16014-5:2019(E)

Contents Page
Foreword .v
1 Scope . 1
2 Normative references . 1
3 Terms and definitions . 1
4 Symbols . 2
5 Principle . 2
5.1 SEC . 2
5.2 Light-scattering SEC . 2
6 Reagents . 3
7 Apparatus . 3
8 Procedure. 5
8.1 Preparation of calibration solutions . 5
8.2 Preparation of a solution for determining the L-point . 5
8.3 Preparation of sample solutions . 5
8.4 Preparation of solutions for column performance evaluation . 5
8.5 Setting up the apparatus. 5
8.6 Operating parameters . 5
8.6.1 Flow rate . 5
8.6.2 Injection masses and injection volumes . 5
8.6.3 Column temperature . 6
8.6.4 Detector sensitivity . 6
8.7 Number of determinations . 6
9 Calibration . 6
9.1 Calibration of concentration-sensitive detector and light-scattering detector . 6
9.1.1 General. 6
9.1.2 Calibration method A . 6
9.1.3 Calibration method B . 7
9.1.4 Calibration method C . 7
9.2 Determination of delay volume . 8
9.3 Normalization of detector sensitivity . 8
9.4 Determination of refractive index increment . 8
10 Data acquisition and processing . 8
10.1 Data acquisition . 8
10.2 Evaluation of data and correction of chromatograms . 8
10.3 Data processing . 8
10.3.1 Baseline determination . 8
10.3.2 Determination of calculation range . 9
10.3.3 Calculation of signal intensity . 9
10.3.4 Calculation of molecular weight . 9
10.3.5 Second virial coefficient, A . 9
2
11 Expression of results .10
11.1 Calibration curve .10
11.1.1 General.10
11.1.2 Method A .10
11.1.3 Method B .10
11.2 Calculation of average molecular weight .12
11.3 Differential molecular weight distribution curve .12
11.4 Cumulative molecular weight distribution curve .12
12 Precision .13
© ISO 2019 – All rights reserved iii

---------------------- Page: 9 ----------------------

SIST EN ISO 16014-5:2019
ISO 16014-5:2019(E)

13 Test report .13
13.1 General .13
13.2 Apparatus and measurement parameters .13
13.3 Calibration of the system .13
13.4 Calibration curve .14
13.5 Results .14
Annex A (informative) Interlaboratory test .15
Annex B (informative) Information on light scattering .17
Annex C (informative) Calibration curve in low molecular weight range .21
Bibliography .23
iv © ISO 2019 – All rights reserved

---------------------- Page: 10 ----------------------

SIST EN ISO 16014-5:2019
ISO 16014-5:2019(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
World Trade Organization (WTO) principles in the Technical Barriers to Trade (TBT) see www .iso
.org/iso/foreword .html.
This document was prepared by Technical Committee ISO/TC 61, Plastics, Subcommittee SC 5, Physical-
chemical properties.
This second edition cancels and replaces the first edition (ISO 16014-5:2012), which has been technically
revised. The main changes compared to the previous edition are as follows:
— publication dates of references have been removed;
— molecular mass has been changed to molecular weight according to IUPAC rule.
A list of all parts in the ISO 16014 series can be found on the ISO website.
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.
© ISO 2019 – All rights reserved v

---------------------- Page: 11 ----------------------

SIST EN ISO 16014-5:2019

---------------------- Page: 12 ----------------------

SIST EN ISO 16014-5:2019
INTERNATIONAL STANDARD ISO 16014-5:2019(E)
Plastics — Determination of average molecular weight
and molecular weight distribution of polymers using size-
exclusion chromatography —
Part 5:
Light-scattering method
1 Scope
This document specifies a general method for determining the average molecular weight and the
molecular weight distribution of polymers using SEC-LS, i.e. size-exclusion chromatography coupled
with light-scattering detection. The average molecular weight and the molecular weight distribution
are calculated from molecular weight data and weight concentrations determined continuously with
elution time. The molecular weight at each elution time is determined absolutely by combining a
light-scattering detector with a concentration-sensitive detector. Therefore, SEC-LS is classified as an
absolute method.
This method is applicable to linear homopolymers and to nonlinear homopolymers such as branched,
star-shaped, comb-like, stereo-regular and stereo-irregular polymers. It can also be applied to
heterophasic copolymers whose molecular composition cannot vary. However, SEC-LS is not applicable
to block, graft or heterophasic copolymers whose molecular composition can vary. And the methods are
applicable to molecular weights ranging from that of the monomer to 3 000 000, but are not intended
for samples that contain > 30 % of components having a molecular weight < 1 000.
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 472, Plastics — Vocabulary
ISO 16014-1, Plastics — Determination of average molecular weight and molecular weight distribution of
polymers using size-exclusion chromatography — Part 1: General principles
ISO 16014-2, Plastics — Determination of average molecular weight and molecular weight distribution of
polymers using size-exclusion chromatography — Part 2: Universal calibration method
ISO 16014-3, Plastics — Determination of average molecular weight and molecular weight distribution of
polymers using size-exclusion chromatography — Part 3: Low-temperature method
ISO 16014-4, Plastics — Determination of average molecular weight and molecular weight distribution of
polymers using size-exclusion chromatography — Part 4: High-temperature method
3 Terms and definitions
For the purposes of this document, the terms and definitions given in ISO 472, ISO 16014-1 and the
following apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— ISO Online browsing platform: available at https: //www .iso .org/obp
© ISO 2019 – All rights reserved 1

---------------------- Page: 13 ----------------------

SIST EN ISO 16014-5:2019
ISO 16014-5:2019(E)

— IEC Electropedia: available at http: //www .electropedia .org/
3.1
light-scattering detection
LS detection
technique for determining the mass or size of polymer molecules in solution by measuring the light
scattered by the polymer molecules
3.2
refractive index increment
d /d
n c
rate of change of the refractive index n of a polymer solution as a function of the mass concentration c
Note 1 to entry: It is also called the “specific refractive index increment” in the literature.
Note 2 to entry: The limiting value of d /d at zero concentration is commonly used in light scattering.
n c
4 Symbols
R radius of gyration of a polymer molecule in solution nm
g
3 −2
A second virial coefficient for a polymer molecule in solution cm ⋅mol⋅g
2
−3
c mass concentration of polymer in solution g⋅cm
d /d refractive index increment ml/g
n c
H excess signal intensity of a concentration detector at the ith elution time
i
I excess signal intensity of scattered light at the ith elution time
LS,i
3
V volume eluted during data acquisition time (interval) cm
e
5 Principle
5.1 SEC
For a discussion of size-exclusion chromatography in general, see ISO 16014-1.
5.2 Light-scattering SEC
In SEC-LS, polymer molecules eluted from the SEC columns are irradiated by a beam of monochromatic
visible light. The light scattered by the molecules is continuously detected by a light-scattering detector.
Since the eluate is a dilute polymer solution, the intensity of the scattered light is approximately
proportional to the product of the molecular weight and the mass concentration of the polymer
molecules. The scattered-light intensity divided by the concentration therefore gives the molecular
weight at a particular elution time. The values of the molecular weight and the mass concentration
or mass fraction at each elution time are used to calculate the molecular weight distribution and the
average molecular weight of the polymer.
There are several low molecular weight compounds that can be used, for example ethylbenzene when
tetrahydrofuran is used as eluent or diethylene glycol when N,N-dimethylformamide is used as eluent
(see Annex B).
2 © ISO 2019 – All rights reserved

---------------------- Page: 14 ----------------------

SIST EN ISO 16014-5:2019
ISO 16014-5:2019(E)

6 Reagents
6.1 Eluent.
For a general discussion of eluents, see ISO 16014-1.
For examples of eluents used for SEC measurements at temperatures below and above 60 °C, see
ISO 16014-3:2019, Annex B and ISO 16014-4, respectively.
6.2 Reagent for column evaluation
For examples of low molecular weight compounds used for column evaluation, see ISO 16014-3, for
measurements at temperatures below 60 °C and ISO 16014-4, for those above 60 °C.
6.3 Calibration standards
Since the Rayleigh ratios of toluene and benzene are well-known, these solvents are recommended for
determining the calibration constant of the light-scattering detector (see B.2).
Aqueous solutions of potassium chloride (KCl) or sodium chloride (NaCl) are used for determining the
calibration constant of a refractive index detector. The concentration dependence of the differential
refractive index of the solutions is used to calculate the constant.
A low molecular weight, monodisperse polymer is used to determine the delay volume between the
light-scattering and concentration-sensitive detectors. This polymer may also be used to calibrate the
angular dependence of the detector sensitivity of a multiple-angle light-scattering detector. The radius
of gyration, R , of the polymer molecule used to calibrate the detector sensitivity, should preferably be
g
less than 10 nm. A radius of gyration less than 5 nm is desirable. Other compounds with a well-known
R value may also be used.
g
Polymer reference materials are used for molecular weight calibration ranges from 20 000 to 50 000.
Low molecular weight organic compounds or oligomers of the polymer in the sample under investigation
are used for determining the “L-point”.
6.4 Reagent for flow rate marker, according to ISO 16014-1.
For examples of compounds suitable for use as a flow rate marker, see ISO 16014-3, for measurements
at temperatures below 60 °C and ISO 16014-4, for those above 60 °C.
6.5 Additives, according to ISO 16014-1.
Some examples of additives are given in ISO 16014-3, for measurements below 60 °C and ISO 16014-4,
for those above 60 °C.
7 Apparatus
7.1 General
A typical schematic diagram of an SEC-LS system is shown in Figure 1, which is similar to that shown
in ISO 16014-1. The main difference is that a light-scattering detector is connected in series with the
concentration-sensitive detector. The light-scattering detector and concentration-sensitive detector
may also be connected in parallel. Any component that meets the performance requirements specified
for this method may be used.
Either commercially available SEC-LS systems or SEC-LS systems assembled in the laboratory may be
used for this method, provided they meet the levels of performance required.
© ISO 2019 – All rights reserved 3

---------------------- Page: 15 ----------------------

SIST EN ISO 16014-5:2019
ISO 16014-5:2019(E)

Key
1 eluent reservoir 7 concentration-sensitive detector
2 pump 8 display
3 in-line filter 9 computer
4 injector 10 printer
5 columns 11 to waste
6 light-scattering detector
Figure 1 — Schematic diagram of a typical SEC LS system
7.2 Eluent reservoir, according to ISO 16014-1, and ISO 16014-3.
7.3 Pumping system, according to ISO 16014-1, and ISO 16014-3.
7.4 Injector, according to ISO 16014-1 and ISO 16014-3.
7.5 Columns.
7.5.1 General
According to ISO 16014-1, ISO 16014-3 and ISO
...