ASTM F1884-04(2011)
(Test Method)Standard Test Method for Determining Residual Solvents in Packaging Materials
Standard Test Method for Determining Residual Solvents in Packaging Materials
SIGNIFICANCE AND USE
This test method is intended to measure volatile organic compounds that are emitted from packaging materials under high-temperature conditions.
This test method may be useful in assisting in the development and manufacture of packaging materials having minimal retained packaging ink/adhesive solvents.
Modification of this procedure by utilizing appropriate qualitative GC detection devices such as a mass spectrometer in place of the flame ionization detector may provide identification of volatile organics of unknown identity.
SCOPE
1.1 This test method covers determination of the amount of residual solvents released from within a packaging material contained in a sealed vial under a given set of time and temperature conditions and is a recommended alternative for Test Method F151.
1.2 This test method covers a procedure for quantitating volatile compounds whose identity has been established and which are retained in packaging materials.
1.3 The analyst should determine the sensitivity and reproducibility of the method by carrying out appropriate studies on the solvents of interest. The analyst is referred to Practice E260 for guidance.
1.4 For purposes of verifying the identity of or identifying unknown volatile compounds the analyst is encouraged to incorporate techniques such as gas chromatography/mass spectroscopy, gas chromatography/infrared spectroscopy or other suitable techniques in conjunction with this test method.
1.5 Sensitivity of this test method in the determination of the concentration of a given retained solvent must be determined on a case by case basis due to the variation in the substrate/solvent interaction between different types of samples.
1.6 This test method does not address the determination of total retained solvents in a packaging material. Techniques such as multiple headspace extraction can be employed to this end. The analyst is referred to the manual supplied with the GC-Autosampling system for guidance.
1.7 The values stated in SI units are to be regarded as the standard.
1.8 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: F1884 − 04 (Reapproved 2011)
Standard Test Methods for
Determining Residual Solvents in Packaging Materials
This standard is issued under the fixed designation F1884; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope 2. Referenced Documents
1.1 This test method covers determination of the amount of 2.1 ASTM Standards:
residual solvents released from within a packaging material E177Practice for Use of the Terms Precision and Bias in
contained in a sealed vial under a given set of time and ASTM Test Methods
temperature conditions and is a recommended alternative for E260Practice for Packed Column Gas Chromatography
Test Method F151. E691Practice for Conducting an Interlaboratory Study to
Determine the Precision of a Test Method
1.2 This test method covers a procedure for quantitating
F151Test Method for Residual Solvents in Flexible Barrier
volatile compounds whose identity has been established and
Materials (Withdrawn 2004)
which are retained in packaging materials.
1.3 The analyst should determine the sensitivity and repro-
3. Terminology
ducibility of the method by carrying out appropriate studies on
3.1 Definitions:
thesolventsofinterest.TheanalystisreferredtoPracticeE260
2 2 6 2
3.1.1 ream—3000 ft = 278.7 m = 27.87×10 cm .
for guidance.
3.1.2 retained solvents—those chemical species, which are
1.4 For purposes of verifying the identity of or identifying
retained by packaging material and can be detected in the
unknown volatile compounds the analyst is encouraged to
headspace of sealed sample vials under conditions of elevated
incorporate techniques such as gas chromatography/mass
temperature.
spectroscopy, gas chromatography/infrared spectroscopy or
other suitable techniques in conjunction with this test method.
4. Summary of Test Method
1.5 Sensitivity of this test method in the determination of
4.1 Retained volatile organic solvents are determined by
the concentration of a given retained solvent must be deter-
subjectingthepackagingmaterialtoelevatedtemperaturesina
mined on a case by case basis due to the variation in the
headspace sampling system with subsequent gas chromatogra-
substrate/solvent interaction between different types of
phy of the headspace and detection using a suitable detection
samples.
device such as a flame ionization detector (FID).
1.6 This test method does not address the determination of
4.2 Volatile components can then be quantified by compari-
total retained solvents in a packaging material. Techniques
son with standards of known concentration.
such as multiple headspace extraction can be employed to this
4.3 Qualitative analysis may be carried out on a gas chro-
end. The analyst is referred to the manual supplied with the
matograph (GC) coupled to an appropriate detector capable of
GC-Autosampling system for guidance.
compound detection / identification, such as a mass spectrom-
1.7 The values stated in SI units are to be regarded as the
eter or infrared detector.
standard.
1.8 This standard does not purport to address all of the
5. Significance and Use
safety concerns, if any, associated with its use. It is the
5.1 This test method is intended to measure volatile organic
responsibility of the user of this standard to establish appro-
compounds that are emitted from packaging materials under
priate safety and health practices and determine the applica-
high-temperature conditions.
bility of regulatory limitations prior to use.
1 2
ThistestmethodisunderthejurisdictionofASTMCommitteeF02onFlexible For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Barrier Packagingand is the direct responsibility of Subcommittee F02.15 on contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Chemical/Safety Properties. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved April 1, 2011. Published April 2011. Originally the ASTM website.
approved in 1998. Last previous edition approved in 2004 as F1884–04. DOI: The last approved version of this historical standard is referenced on
10.1520/F1884-04R11. www.astm.org.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
F1884 − 04 (2011)
5.2 This test method may be useful in assisting in the 7.2.2 If desired, water may be used as the diluent for the
development and manufacture of packaging materials having standard. The solvents are diluted in 1 L of water, typically 2
minimal retained packaging ink/adhesive solvents. mLoftheresultingsolutionisaddedpergramofsampleinthe
headspace vial for calibration. 2 mLof 20 µl/Lof 4-heptanone
5.3 Modification of this procedure by utilizing appropriate
containing solution in water can be used as an internal
qualitative GC detection devices such as a mass spectrometer
standard.
in place of the flame ionization detector may provide identifi-
cation of volatile organics of unknown identity.
NOTE1—Waterwillchangethepartitioncoefficientbetweenthesample
and retained solvents.
6. Interferences
Solvent µL/L µg/mL
6.1 Gas Chromatography—Because of the potentially large
Methanol 120 94.96
number of chemical species that can be analyzed using this
Ethanol 80 63.14
2-Propanol 60 47.13
methodology,notallspecieswillberesolvedfromoneanother
n-Propanol 60 48.21
on a particular GC column under a given set of conditions.
Methylethyl ketone 40 32.20
Techniques available to the analyst to verify the identity of
Ethylacetate 40 36.08
2-Propylacetate 20 17.08
chemical species being quantitated include retention time
Benzene 10 8.76
comparisons using alternate GC conditions or using an alter-
Methylisobutylketone 20 16.02
nate GC column. Good judgment in the interpretation of Toluene 10 8.70
Heptanone 20 16.42
chromatographic results is always important. Refer to Practice
E260 for guidance. 7.3 Vials, 20 mL. To ensure against extraneous peaks in the
gas chromatographic traces, wash vials thoroughly and dry in
6.2 Apparatus—Because this method is designed for detect-
a 125°C air oven for a minimum of 4 h before using.
ing trace quantities of organic compounds, contaminants can
lead to misinterpretation of results. Preparing apparatus prop- 7.4 Vial Crimp Caps.
erly and carrying out blank determinations is essential to
7.5 Septa, Teflon/Silicone. To ensure that the septa are free
minimize this possibility.
of volatiles, condition the septa in a vacuum oven at 130°C for
16 h.
TEST METHOD A
4,5
7.6 Crimping Tool for Vials.
7. Apparatus and Reagents
4,6
7.7 Syringe—2 mL gas tight with valve. Store syringe in
7.1 Gas chromatograph equipped as follows:
90°C oven between uses.
7.1.1 FID Detector, compatible with capillary columns.
4,7
7.8 4-Heptanone.
7.1.2 Injector, split/split-less compatible with capillary col-
umns. 7.9 For Manual Injection Only—Hot air oven and heat
7.1.3 Column, DB-5, 30m, 0.25 mm ID, 1 µm film thick- resistant gloves.
ness, Cat. No. 122–5033, or 0.32 mm, Cat. No. 123–5033. A
short piece of deactivated fused silica column may be placed
8. Instrument Setup
between the injector and the column to serve as a guard
8.1 Set up the gas chromatographic system per the manu-
column.
facturer’s recommendations and as follows:
7.1.4 Peak Area Integration System, compatible with GC
8.1.1 Injector Temperature—250°C.
system in use. Alternately, a chart recorder and hand integra-
8.1.2 Detector Temperature—250°C.
tion can be used.
8.1.3 Column Temperature:
7.1.5 Auto sampler is recommended.
8.1.3.1 Initial 40°C for 4 min.
7.2 Standard Solutions, consisting of the organic solvent
8.1.3.2 Program—Adjust temperature program to give a
mixtureofinterest,atconcentrationsthatsimulatetheexpected
retention window of at least 15 min to ensure optimum
retentionlevels.4-Heptanonemaybeaddedtothesolutionsfor
separation of solvents.
use as an internal standard as described in Practice E260.
8.1.4 Attenuation or sensitivity, or both, set to give a
7.2.1 Anexampleofaworkingstandardislistedbelow.The
detector response of 40% or more of full scale on the recorder
standard used will vary based on the solvents present in the
or integrator of the expected internal standard and standard
sample to be tested. The quantities shown in the table will
sample response. See Practice E260 for guidance.
result in roughly equivalent size peaks due to differences in
8.2 Set up autosampler, if used, to heat vials for 20 min at
detector response. If the solvents are mixed neat, adding 1 µL
90°C before autoinjection.
per gram of material in the headspace vial provides a good
starting point for calibration.
The sole source of supply of the apparatus known to the committee at this time
The sole source of supply of the apparatus known to the committee at this time is Cat. No. 33280, Supelco Inc., Bellefonte, PA 16823.
is J. and W. Scientific, Cat. No. 122-5033 and Cat. No. 123-5033. If you are aware The sole source of supply of the apparatus known to the committee at this time
of alternative suppliers, please provide this information to ASTM Headquarters. is Cat. No. 050034, Alltech, 2051 Waukegan Rd., Deerfield, IL 60015.
Your comments will receive careful consideration at a meeting of the responsible The sole source of supply of the apparatus known to the committee at this time
technical committee, which you may attend. is Cat. No. 10, 174-5, Aldrich, 940 W. St. Paul Ave., Milwaukee, WI 53233.
F1884 − 04 (2011)
9. Calibration Procedure (samplescanalsobewrappedtightlyinfoil)fortransporttothe
lab for cutting and loading into vials.
9.1 Standard Curve:
10.3 When taking samples from roll stock, discard the first
9.1.1 Prepare blanks by heating a sample of the packaging
8 to 10 layers before taking samples from the next 30 to 40
materialofinterest(enoughsamplecanbepreparedatonetime
layerstoensurethatthesamplesarerepresentativeoftheentire
for several analysis runs) in a vacuum oven at 90°C for 24 h.
roll.
Remove the blanks and store in a closed container. Blanks
should be cut to the same relative size as the sample prior to
10.4 When possible, samples should have 100% ink cov-
heating in the vacuum oven.
erage in the area selected for testing. Selecting an area with
9.1.2 To prepare a calibration standard place a blank (cut to
100%inkcoveragewillensurethatthetestingwillelucidatea
appropriate size) in the 20 mL headspace vial and add the
worst case. Using a sample area with representative ink
appropriate amount of standard solvent mix to the vial.
coverage may also be considered.
Immediately cap and crimp the vial with the Teflon side of the
10.5 The sample size is dictated by the thickness of the
septum toward the vial. It is suggested that blanks be fortified
sample and the ease of filling the vial. The sample size will
at five different concentrations along with an unfortified blank
varyfrom5to50in. Typically,thevialwillbelessthan20%
be prepared for calibration. See Practice E260 for guidance.
full by volume. Alternately the ratio of the weight of the
9.2 Manual Injection:
sample in grams to the volume of the vial in millilitres should
9.2.1 If using a syringe and hot air oven, heat each vial for
not exceed 1 to 10. In the case of a 20-mL sample vial, the
20 min at 90°C. Ensure that the syringe is heated to at least weight of the sample should not exceed 2 g.
90°C before taking headspace samples from the vials for
10.6 The preferred method of cutting samples is the use of
injection into the chromatograph.
a punch press or die.
NOTE 2—When handling the hot syringe be sure that hands are
10.7 Add the appropriate amount of internal standard (if
adequately protected. Fill the gas tight syringe with 1 mL of air, close
used) to the vial.
valve and insert the needle through the septum into the preheated vial.
Open valve, inject the air into vial. Draw ⁄2 mL of gas from vial into
10.8 Immediately cap and crimp the vial with the Teflon
syringe, inject back into vial. Repeat 2 times. Draw exactly 1 mL of gas
side of the septa toward the vial.
into syringe and close valve. Insert needle into injector of GC and inject.
NOTE 3—Consistent technique from injection to injection of standards
11. Procedure
and sample is required. This step should take no more than 30 s.
11.1 Manual Injection:
9.3 Automated Injection—The recommended method of in-
11.1.1 Forthoseusingthesyringe,placethesample(vial)in
jecting the headspace gas into the GC is use of an automated
headspace sampling system where the vials are heated to 90°C a forced air oven at 90°C for 20 min.
for20minandthentheheadspaceofeachvialisautomatically
NOTE6—Longerheatingtimesmaybeusedifitisdeemednecessaryto
injected onto the GC column.
ensurethatthesolventintheheadspaceofthevialhastotallyequilibrated
with the sample.
9.4 Repeat the procedure for all five calibration standards
NOTE 7—When handling the hot syringe be sure that hands are
and the blank.
adequatelyprotected.Fillthepreheatedgas-tightsyringewith1mLofair,
close valve and insert the needle through the septum into the above
9.5 Construct a standard calibration curve from the data
conditioned vial. Open valve, inject the air into vial. Draw ⁄2 mL of gas
obtainedusingstandardtechniquesasdefinedinPracticeE260.
from vial into syringe, inject back into vial. Repeat 2 times. Draw exactly
1mLofgasintosyringeandclosevalve.InsertneedleintoinjectorofGC
NOTE4—Longerheatingtimesmaybeusedifitisdeemednecessaryto
and inject.
ensurethatthesolventintheheadspaceofthevialhastotallyequilibrated
NOTE 8—Consistent technique from injection to injection of standards
with the sample.
and sample is required. This step should take no more than 30 s.
11.2 Automated Injection:
10. Sampling
11.2.1 Therecommendedmethodofinjectingtheheadspace
10.1 Samples should be taken in such a manner as to
gas into the GC is use of an automated headspace sampling
represent the entire web. The analyst should cut several layers
system where the vials are heated to 90°C for 20 min and then
deep into a roll of packaging material, discarding the outer
the headspace of the vial is automatically injected onto the GC
layers, to ensure the sampling is representative of the entire
column.
roll. Samples should be taken from the left, center and right
NOTE9—Longerheatingtimesmaybeusedifitisdeemednecessaryto
side of the web.
ensurethatthesolventintheheadspaceofthevialhastotallyequilibrated
NOTE 5—Consideration should also be given when sampling rolls
with the sample.
within a production lot to ensure uniformity within the production run.
11.3 Chro
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