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oSIST prEN 1186-13:2006
01-december-2006
Materiali in predmeti v stiku z živili - Polimerni materiali - 13. del: Preskusna
metoda za celotno migracijo pri visokih temperaturah
Materials and articles in contact with foodstuffs - Plastics - Part 13: Test method for
overall migration at high temperatures
Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln - Kunststoffe - Teil 13:
Prüfverfahren für die Gesamtmigration bei hohen Temperaturen
Matériaux et objets en contact avec les denrées alimentaires - Matiere plastique - Partie
13 : Méthodes d'essai pour la migration globale a températures élevées
Ta slovenski standard je istoveten z: prEN 1186-13
ICS:
67.250 Materiali in predmeti v stiku z Materials and articles in
živili contact with foodstuffs
oSIST prEN 1186-13:2006 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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EUROPEAN STANDARD
DRAFT
prEN 1186-13
NORME EUROPÉENNE
EUROPÄISCHE NORM
October 2006
ICS 67.250 Will supersede EN 1186-13:2002
English Version
Materials and articles in contact with foodstuffs - Plastics - Part
13: Test method for overall migration at high temperatures
Matériaux et objets en contact avec les denrées Werkstoffe und Gegenstände in Kontakt mit Lebensmitteln
alimentaires - Matière plastique - Partie 13 : Méthodes - Kunststoffe - Teil 13: Prüfverfahren für die
d'essai pour la migration globale à hautes températures Gesamtmigration bei hohen Temperaturen
This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee CEN/TC 194.
If this draft becomes a European Standard, 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.
This draft European Standard was established by CEN 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 Management Centre has the same
status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,
Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,
Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are aware and to
provide supporting documentation.
: This document is not a European Standard. It is distributed for review and comments. It is subject to change without notice and
Warning
shall not be referred to as a European Standard.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36 B-1050 Brussels
© 2006 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 1186-13:2006: E
worldwide for CEN national Members.
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prEN 1186-13:2006 (E)
Contents Page
Foreword.3
Introduction .5
1 Scope.6
2 Normative references.6
3 Method A – total immersion in olive oil.6
3.1 Principle.6
3.2 Reagents.7
3.3 Apparatus.7
3.4 Preparation of test specimens .7
3.5 Procedure.7
3.6 Expression of results.9
3.7 Test report.10
4 Method B – adsorption by modified polyphenylene oxide.10
4.1 Principle.10
4.2 Reagents.10
4.3 Apparatus.11
4.4 Sample preparation.11
4.5 Procedure.12
4.6 Expression of results.15
4.7 Test report.15
Annex A (informative) Aluminium block .17
Annex B (informative) Precision data.18
Annex ZA (informative) Relationship of this European Standard with Regulation 1935/2004 and
Commission Directive 2002/75/EC and associated Directives .19
Bibliography .21
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Foreword
This document (prEN 1186-13:2006) has been prepared by Technical Committee CEN/TC 194 “Utensils in
contact with food”, the secretariat of which is held by BSI.
This document is currently submitted to the CEN Enquiry.
This document has been prepared under a mandate given to CEN by the European Commission and the
European Free Trade Association, and supports essential requirements of EU Directive(s).
For relationship with EU Directive(s), see informative Annex ZA, which is an integral part of this document.
This document will supersede EN 1186-13:2002.
This European Standard has been prepared as one of a series of methods of test for plastics materials and
articles in contact with foodstuffs.
At the time of preparation and publication of this standard the European Union legislation relating to plastics
materials and articles intended to come into contact with foodstuffs is incomplete. Further Directives and
amendments to existing Directives are expected which could change the legislative requirements which this
standard supports. It is therefore strongly recommended that users of this standard refer to the latest relevant
published Directive(s) before commencement of any of the test or tests described in this standard.
EN 1186-13 Method A and Method B should be read in conjunction with EN 1186-1. Also, EN 1186-13
Method A should be read in conjunction with EN 1186-2.
Further Parts of this standard have been prepared concerned with the determination of overall migration from
plastics materials into food simulants. Their titles are as follows:
EN 1186 Materials and articles in contact with foodstuffs – Plastics –
Part 1 Guide to the selection of conditions and test methods for overall migration
Part 2 Test methods for overall migration into olive oil by total immersion
Part 3 Test methods for overall migration into aqueous food simulants by total immersion
Part 4 Test methods for overall migration into olive oil by cell
Part 5 Test methods for overall migration into aqueous food simulants by cell
Part 6 Test methods for overall migration into olive oil using a pouch
Part 7 Test methods for overall migration into aqueous food simulants using a pouch
Part 8 Test methods for overall migration into olive oil by article filling
Part 9 Test methods for overall migration into aqueous food simulants by article filling
Part 10 Test methods for overall migration into olive oil (modified method for use in case where
incomplete extraction of olive oil occurs)
Part 11 Test methods for overall migration into mixtures of 14C-labelled synthetic triglyceride
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Part 12 Test methods for overall migration at low temperatures
Part 14 Test methods for 'substitute tests' for overall migration from plastics intended to come into
contact with fatty foodstuffs using test media iso-octane and 95 % ethanol
Part 15 Alternative test methods to migration into fatty food simulants by rapid extraction into iso-octane
and/or 95 % ethanol
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Introduction
Migration testing with olive oil at high temperatures introduces a number of analytical difficulties. Experience
has shown that it is difficult to achieve reproducible results owing to different laboratories having different
equipment which give rise to variations in the time taken to reach the exposure temperature. A method is
described for determining overall migration by total immersion using an aluminium block with a consistent
thermal capacity. Other analytical difficulties with olive oil include possible oxidation of oil at elevated
temperatures and the hazard to personnel working with hot oil. Replacement of olive oil by an appropriate
adsorbent material, in principal, can solve or reduce these problems and offers further experimental
advantages.
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prEN 1186-13:2006 (E)
1 Scope
This European Standard specifies test methods for the determination of the overall migration into fatty food
simulants from plastics materials and articles, by total immersion of test specimens in a fatty food simulant at
temperatures from 100 °C up to and including, 175 °C for selected times. Also described is a procedure with
a substitute test medium. In this substitute procedure the mass of components adsorbed on modified
polyphenylene oxide (MPPO) is taken as a measure for the assessment of the overall migration into olive oil.
NOTE 1 The total immersion test method has been written for use with the fatty food simulant, olive oil. The test
method can also be used with appropriate modifications with 'other fatty food simulants' called simulant D - a synthetic
mixture of triglycerides, sunflower oil and corn oil. These other fatty food simulants will produce different chromatograms
for the simulant methyl esters to those of the methyl esters of olive oil. Select suitable chromatogram peaks of the methyl
esters of the other fatty food simulants for the quantitative determination of the simulant extracted from the test specimens.
NOTE 2 A comparative migration test carried out with polypropylene and polyethylene terephthalate high temperature
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application containers as test samples at conditions 2 h at 100 °C and 2 h at 175 °C, respectively, in contact with C-
labelled synthetic triglyceride and MPPO provided test results comparable within the analytical tolerance of the methods.
NOTE 3 To obtain reproducible and repeatable results using the MPPO method it may be necessary to measure the
temperature of the test specimen before starting the migration period. An appropriate method for measuring the
temperature of the test specimen needs to be established.
The described methods are most suitable for food contact articles in the form of sheets and films, but can also
be applied to a wide range of articles and containers.
2 Normative references
This European Standard incorporates by dated or undated reference, provisions from other publications.
These normative references are cited at the appropriate places in the text and the publications are listed
hereafter. For dated references, subsequent amendments to or revisions of any of these publications apply to
this European Standard only when incorporated in it by amendment or revision. For undated references the
latest edition of the publication referred to applies (including amendments).
EN 1186-1:2002, Materials and articles in contact with foodstuffs – Plastics – Part 1: Guide to the selection of
conditions and test methods for overall migration
EN 1186-2:2002, Materials and articles in contact with foodstuffs – Plastics – Part 2: Test methods for overall
migration into olive oil by total immersion
3 Method A – total immersion in olive oil
3.1 Principle
The overall migration from a sample of the plastics is determined as the loss in mass per unit of surface area
intended to come into contact with foodstuffs.
The selection of the conditions of test will be determined by the conditions of use, see clauses 4, 5 and 6 of
EN 1186-1:2002.
Test specimens of known mass are immersed in olive oil for the exposure time, at temperatures from 100 °C
up to 175 °C, then taken from the olive oil, blotted to remove oil adhering to the surface, and reweighed.
The specimens will usually retain absorbed olive oil which is extracted and determined quantitatively by
means of gas chromatography after conversion to methyl esters. Methylation is carried out by reacting a
boron trifluoride/methanol complex with fatty acids formed by hydrolysing the oil with potassium hydroxide. An
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prEN 1186-13:2006 (E)
internal standard, triheptadecanoin, is added prior to the extraction of the absorbed olive oil from the test
specimens. This ensures that any active or extractable components of the plastics react with the internal
standard, as well as with the extracted olive oil. The internal standard is also subjected to the hydrolysis and
methylation reactions, providing compensation for any inefficiencies in the hydrolysis and methylation
processes.
Migration into the olive oil is calculated by subtracting the mass of olive oil retained by the test specimen from
the mass of the test specimen after removal from the olive oil, then subtracting this mass from the initial mass
of the specimen.
The total loss in mass is expressed in milligrams per square decimetre of surface area of the specimen and
the overall migration is reported as the mean of a minimum of three determinations on separate test
specimens.
To allow for inaccuracies which may arise during the procedure and which may be difficult to detect, due for
example to contamination or loss of oil during the sample handling stages, four determinations are carried out
on the sample allowing for the result from one specimen to be discarded.
This method includes variations which are applicable to certain plastics.
NOTE Before starting a migration exercise, the test sample should be examined for the presence of components
interfering in the determination of the amount of olive oil extracted, see 9.3 of EN 1186-1:2002. If an unacceptable amount
of interference is present then suitability of one of the 'other fatty food simulants' should be examined, see Annex A and
9.3 and 9.5 of EN 1186-1:2002. If an interference is present which would interfere with the triheptadecanoin internal
standard an alternative internal standard should be used, see Annex A, and 9.3 of EN 1186-1:2002.
3.2 Reagents
The reagents shall be as described in clause 4 of EN 1186-2:2002.
3.3 Apparatus
The apparatus shall be as described in clause 5 of EN 1186-2:2002, with the addition of:
Aluminium block or blocks with wells for holding up to ten glass tubes, see 5.11 of EN 1186-2:2002, during the
exposure time period in the oven or incubator.
NOTE A diagram of a suitable block is shown in Figure A.1. The wells in the block should hold the tubes so that
there is close contact between the tubes and the block. The block should be of sufficient depth that when the specimen is
placed in the oil in the tubes, the level of the oil is lower than, or equal to the height of the block.
3.4 Preparation of test specimens
Prepare the test specimens in accordance with EN 1186-2, except that an additional test specimen is
required. This test specimen shall be placed in the tube in which the temperature is monitored.
3.5 Procedure
3.5.1 General
See 7.1 of EN 1186-2:2002.
3.5.2 Initial weighing of test specimens
Perform the initial weighing in accordance with 7.2 of EN 1186-2:2002.
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3.5.3 Exposure to food simulant
Insert a thermocouple in the metal block (3.3). Place the metal block and thermocouple in the thermostatically
controlled oven or incubator, set at the test temperature and leave for 24 h.
Observe the temperature of the metal block. Confirm that the temperature of the metal block reaches the test
temperature, taking into account the tolerances specified in Table B.1 of EN 1186-1:2002.
NOTE 1 If the oven temperature is at the test temperature, but the temperature of the metal block is not, taking into
account the tolerances specified in Table B.1 of EN 1186-1:2002, check the accuracy of the thermocouple and the
temperature control of the oven. If necessary adjust the oven temperature, either by increasing or decreasing the oven set
temperature, until the temperature of the metal block reaches the test temperature.
Take six of the glass tubes, mark them for identification purposes. Measure 100 ml ± 5 ml of olive oil into
each tube by measuring cylinder and stopper the tube.
NOTE 2 If the procedure described in Annex D of EN 1186-2:2002 is used, it may be necessary to dry all of the olive oil
used for the migration test.
Alternatively mark the tubes for a volume of 100 ml and fill with olive oil to the mark. Place into one of the
tubes a thermometer or thermocouple and stopper the tubes. Two extra tubes with a minimum of 50 ml of
olive oil are required as blank simulant, if the procedure described in Annex D of EN 1186-2:2002 is used.
Place the six or eight tubes, and two empty tubes, in the metal block or blocks (3.3) then put the metal block
or blocks in the thermostatically controlled oven or incubator (5.12 of EN 1186-2:2002) set at the test
temperature. Leave until the olive oil has attained the test temperature, using the thermometer or
thermocouple to monitor the temperature.
NOTE 3 More rapid temperature equilibration of the oil can be established by lifting the tubes from the block
periodically and rotating gently before replacing rapidly or by stirring the oil in the tubes with a metal or glass rod, without
removing from the block.
Place into four of the tubes containing olive oil, weighed test specimens prepared as in 3.4 and conditioned if
necessary. Stopper the tubes. Ensure that the test specimens are totally immersed in olive oil; if they are not,
then add either glass beads or glass rods (5.22 of EN 1186-2:2002) to raise the level of the olive oil until total
immersion is achieved.
WARNING 1 Take care when handling the hot metal block or blocks during removal from and
replacement to the oven or incubator, to prevent skin burns. Take particular care when placing the
test specimens in the hot olive oil to prevent splashing or spillage of the olive oil on to the skin. It is
recommended that heat protective gloves and a face shield are worn.
NOTE 4 The olive oil in the fifth tube is used as a reference standard in constructing the calibration graph and if the
procedure described in Annex D of EN 1186-2:2002 is used, as the third blank sample for Karl Fischer titrations. The olive
oil in the sixth tube is used to check the temperature of the oil. If glass beads or glass rods have been used to raise the
level of the olive oil to achieve total immersion, then similar glass beads or glass rods should be added to the sixth tube.
Place one test specimen in the sixth tube where the temperature of the oil is being monitored.
NOTE 5 If a test specimen is not added to the tube the temperature monitored will be high in comparison with
temperature of the oil in the other tubes containing test specimens. For the determination of migration from thin films,
which have little thermal capacity, it is not necessary to include a test specimen in the sixth tube, only the supports and
gauzes as used to mount the test specimens. For thicker materials, which will have some thermal capacity, it should
consist of an extra test specimen.
Place the remaining two test specimens into the empty tubes and stopper.
NOTE 6 These two test specimens are used to check whether the sample loses mass from the evaporation of
volatiles, such as solvents, during the test period.
Replace the block or blocks containing all eight or ten tubes in the thermostatically controlled oven or
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incubator set at the test temperature. This part of the operation should be carried out in the minimum time to
prevent undue heat loss.
NOTE 7 Where the test time for migration test is between 0,5 h and 4 h, it is particularly important that the time period
between placing the test specimens in the olive oil and the olive oil reaching the test temperature, be kept as short as
possible. This time period can be minimized by placing the test specimens in the tubes without removing the tubes from
the block and without removing the block from the oven or incubator. It may be necessary to raise the tubes from the
block to check that the oil is above the level of the sample and that the test pieces remain separated. The tubes should be
raised the minimum amount necessary to carry out these checks and then replaced as quickly as possible. The sixth
tube, i.e. the tube in which the temperature is monitored, should be treated in a similar manner.
Observe the temperature of the thermostatically controlled oven or incubator or the olive oil in the sixth tube
and leave the tubes for the selected test period, taking into account the tolerances specified in Table B.1 of
EN 1186-1:2002, after the olive oil in the sixth tube has reached a temperature within the tolerance specified
in Table B.2 of EN 1186-1:2002. For test temperatures between 100 °C and 150 °C the time between the
immersion of the test specimens and the test temperature being regained shall be 10 min or less. For test
temperatures between 151 °C and 175 °C the time shall be 15 min or less.
NOTE 7 It has been found that these times can be achieved by using silicone oil in the wells to increase thermal
conductivity between the block and the tube.
NOTE 8 Annex B of EN 1186-1:2002 includes tolerances on a wide range of contact times and contact temperatures.
All of these contact times and contact temperatures are not necessarily relevant to this Part of the standard.
Take the metal block or blocks containing the tubes from the oven or incubator and immediately remove the
test specimens from the tubes. Discard the test specimen that was in the sixth tube in which the temperature
had been monitored. For the remaining specimens which have been in olive oil, allow the oil to drain.
WARNING 2 Take care when handling the metal block or blocks and removal of the test specimens
from the olive oil at the end of the exposure period, to prevent skin burns. Use the protective wear
recommended in WARNING 1.
Remove any adhering olive oil by gently pressing between filter papers (5.13 of EN 1186-2:2002). Repeat the
pressing procedure until the filter paper shows no spots of olive oil. For test specimens on supports, remove
the individual test pieces from the supports to carry out this operation. Clean the supports of oil by washing
with the extraction solvent and replace the test pieces on them.
3.5.4 Final weighing of test specimens
Perform the final weighing in accordance with 7.4 of EN 1186-2:2002.
3.5.5 Extraction of absorbed olive oil
Extract the absorbed oil in accordance with 7.5 of EN 1186-2:2002.
3.5.6 Determination of extracted olive oil
Determine the extracted olive oil in accordance with 7.6 of EN 1186-2:2002.
3.6 Expression of results
3.6.1 Method of calculation
Express the results in accordance with 8.1 of EN 1186-2:2002.
3.6.2 Precision
See Annex B.
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3.7 Test report
Prepare the test report in accordance with clause 9 of EN 1186-2:2002.
4 Method B – adsorption by modified polyphenylene oxide
4.1 Principle
The surface of the article to be tested is covered with modified polyphenylene oxide and held at the selected
time-temperature test conditions where the maximum temperature applicable is 175 °C. The heating takes
place in a conventional oven even if the samples are for use in a microwave oven. The exposure is followed
by extraction of the adsorbent using diethyl ether. Finally, the extract is evaporated to dryness using a
nitrogen stream and the residue remaining is determined gravimetrically. Modified polyphenylene oxide is a
porous polymer with a high molecular weight, 500 000 to 1 000 000, a very high temperature stability (T =
max
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350 °C), a high surface area and a low specific mass (0,23 g/cm ).
4.2 Reagents
NOTE All reagents should be of recognized analytical quality, unless otherwise specified.
4.2.1 Diethylether of 99,8 % purity and stabilized with 1,5 % to 2,5 % ethanol.
4.2.2 Modified polyphenylene oxide (MPPO), 60 mesh to 80 mesh
Gas chromatograms obtained from extracts of new commercial MPPO have shown that unacceptably high
levels of impurities may be present. Therefore, prior to its first use in this test procedure, the MPPO shall be
purified by soxhlet extraction, using diethylether. The extraction is carried as follows : place the MPPO in a
soxhlet cartridge and extract for 6 h with diethylether. Spread the MPPO in a Petri dish of a suitable diameter
and place the dish in a fumehood. Allow the ether to evaporate while frequently mixing with a glass rod. Then
place the dish in an oven at 160 °C for 6 h. After heating store the MPPO, if not needed immediately, in a
closed conical flask.
NOTE 1 Heating of MPPO saturated with diethylether may be explosive. Therefore, it should be ensured that
diethylether is completely evaporated before drying at 160 °C.
NOTE 2 MPPO cleaned in this way can be used repeatedly.
NOTE 3 MPPO is powdery and lightweight and is readily blown about by air currents. When drying MPPO or carrying
out the exposure in a forced air oven, the oven should be set to low and cover dishes to prevent the MPPO from blowing
about.
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4.2.3 Nitrogen, purity 99,999 %
4.3 Apparatus
4.3.1 Cutting implement, scalpel, scissors, sharp knife or other suitable device
4.3.2 Rule, graduated in mm, with an accuracy of 0,1 mm
4.3.3 Brush
4.3.4 Analytical balance capable of determining a change in mass of 0,1 mg
4.3.5 Oven or incubator, thermostatically controlled and capable of maintaining the set temperature within
the tolerances specified in Table B.2 of EN 1186-1:2002.
NOTE In case of an oven with a ventilating system the ventilation rate should be switched to low.
4.3.6 Petri dishes, glass with an internal diameter of 140 mm, heat resistant
4.3.7 Rings, glass with an internal diameter of 125 mm and an external diameter of approximately 130 mm
4.3.8 Erlenmeyer flasks, glass-stoppered, capacity of 300 ml
4.3.9 Filter funnels, glass
4.3.10 Filter, folded, with a diameter of 125 mm
4.3.11 Vials, glass with capacities of 10 ml and 100 ml
4.3.12 Dropping pipettes with dropper teats
4.3.13 Lint-free cloth
4.3.14 Plates, glass, to cover the dishes or trays
4.3.15 Erlenmeyer flask, glass-stoppered to wash the MPPO
NOTE The size of the flask depends on the mass of MPPO that is used (see Table 1).
4.3.16 Apparatus to blow off solvent with nitrogen
4.4 Sample preparation
4.4.1 General
It is essential that test specimens are clean and free from surface contamination (many plastics can readily
attract dust due to static charges). Before preparing test specimens, remove any surface contamination from
the sample by gently wiping it with a lint free cloth, or by brushing with a soft brush. Under no circumstances
wash the samp
...