1、Designation: F 1884 04Standard Test Methods forDetermining Residual Solvents in Packaging Materials1This standard is issued under the fixed designation F 1884; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revisi
2、on. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers determination of the amount ofresidual solvents released from within a packaging materialcontained in a
3、sealed vial under a given set of time andtemperature conditions and is a recommended alternative forTest Method F 151.1.2 This test method covers a procedure for quantitatingvolatile compounds whose identity has been established andwhich are retained in packaging materials.1.3 The analyst should det
4、ermine the sensitivity and repro-ducibility of the method by carrying out appropriate studies onthe solvents of interest. The analyst is referred to PracticeE 260 for guidance.1.4 For purposes of verifying the identity of or identifyingunknown volatile compounds the analyst is encouraged toincorpora
5、te techniques such as gas chromatography/mass spec-troscopy, gas chromatography/infrared spectroscopy or othersuitable techniques in conjunction with this test method.1.5 Sensitivity of this test method in the determination ofthe concentration of a given retained solvent must be deter-mined on a cas
6、e by case basis due to the variation in thesubstrate/solvent interaction between different types ofsamples.1.6 This test method does not address the determination oftotal retained solvents in a packaging material. Techniquessuch as multiple headspace extraction can be employed to thisend. The analys
7、t is referred to the manual supplied with theGC-Autosampling system for guidance.1.7 The values stated in SI units are to be regarded as thestandard.1.8 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of this s
8、tandard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2E 177 Practice for Use of the Terms Precision and Bias inASTM Test MethodsE 260 Practice for Packed Column Gas Chromatograp
9、hyE 691 Practice for Conducting an Interlaboratory Study toDetermine the Precision of a Test MethodF 151 Test Method for Residual Solvents in Flexible BarrierMaterials33. Terminology3.1 Definitions:3.1.1 ream3000 ft2= 278.7 m2= 27.873106cm2.3.1.2 retained solventsthose chemical species, which areret
10、ained by packaging material and can be detected in theheadspace of sealed sample vials under conditions of elevatedtemperature.4. Summary of Test Method4.1 Retained volatile organic solvents are determined bysubjecting the packaging material to elevated temperatures in aheadspace sampling system wit
11、h subsequent gas chromatogra-phy of the headspace and detection using a suitable detectiondevice such as a flame ionization detector (FID).4.2 Volatile components can then be quantified by compari-son with standards of known concentration.4.3 Qualitative analysis may be carried out on a gas chro-mat
12、ograph (GC) coupled to an appropriate detector capable ofcompound detection / identification, such as a mass spectrom-eter or infrared detector.5. Significance and Use5.1 This test method is intended to measure volatile organiccompounds that are emitted from packaging materials underhigh-temperature
13、 conditions.1This test method is under the jurisdiction of ASTM Committee F02 on FlexibleBarrier Materials and is the direct responsibility of Subcommittee F02.15 onChemical/Safety Properties.Current edition approved Sept. 1, 2004. Published September 2004. Originallyapproved in 1998. Last previous
14、edition approved in 1998 as F 1884 98.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.3Withdrawn.1Copyright A
15、STM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.5.2 This test method may be useful in assisting in thedevelopment and manufacture of packaging materials havingminimal retained packaging ink/adhesive solvents.5.3 Modification of this procedure by
16、 utilizing appropriatequalitative GC detection devices such as a mass spectrometerin place of the flame ionization detector may provide identifi-cation of volatile organics of unknown identity.6. Interferences6.1 Gas ChromatographyBecause of the potentially largenumber of chemical species that can b
17、e analyzed using thismethodology, not all species will be resolved from one anotheron a particular GC column under a given set of conditions.Techniques available to the analyst to verify the identity ofchemical species being quantitated include retention timecomparisons using alternate GC conditions
18、 or using an alter-nate GC column. Good judgment in the interpretation ofchromatographic results is always important. Refer to PracticeE 260 for guidance.6.2 ApparatusBecause this method is designed for detect-ing trace quantities of organic compounds, contaminants canlead to misinterpretation of re
19、sults. Preparing apparatus prop-erly and carrying out blank determinations is essential tominimize this possibility.TEST METHOD A7. Apparatus and Reagents7.1 Gas chromatograph equipped as follows:7.1.1 FID Detector, compatible with capillary columns.7.1.2 Injector, split/split-less compatible with c
20、apillary col-umns.7.1.3 Column, DB-5, 30m, 0.25 mm ID, 1 m film thick-ness, Cat. No. 1225033, or 0.32 mm, Cat. No. 1235033.4Ashort piece of deactivated fused silica column may be placedbetween the injector and the column to serve as a guardcolumn.7.1.4 Peak Area Integration System, compatible with G
21、Csystem in use. Alternately, a chart recorder and hand integra-tion can be used.7.1.5 Auto sampler is recommended.7.2 Standard Solutions, consisting of the organic solventmixture of interest, at concentrations that simulate the expectedretention levels. 4-Heptanone may be added to the solutions foru
22、se as an internal standard as described in Practice E 260.7.2.1 An example of a working standard is listed below. Thestandard used will vary based on the solvents present in thesample to be tested. The quantities shown in the table willresult in roughly equivalent size peaks due to differences indet
23、ector response. If the solvents are mixed neat, adding 1 Lper gram of material in the headspace vial provides a goodstarting point for calibration.7.2.2 If desired, water may be used as the diluent for thestandard. The solvents are diluted in 1 L of water, typically 2mL of the resulting solution is
24、added per gram of sample in theheadspace vial for calibration. 2 mL of 20 l/L of 4-heptanonecontaining solution in water can be used as an internalstandard.NOTE 1Water will change the partition coefficient between the sampleand retained solvents.Solvent L/L g/mLMethanol 120 94.96Ethanol 80 63.142-Pr
25、opanol 60 47.13n-Propanol 60 48.21Methylethyl ketone 40 32.20Ethylacetate 40 36.082-Propylacetate 20 17.08Benzene 10 8.76Methylisobutylketone 20 16.02Toluene 10 8.70Heptanone 20 16.427.3 Vials, 20 mL. To ensure against extraneous peaks in thegas chromatographic traces, wash vials thoroughly and dry
26、ina 125C air oven for a minimum of 4 h before using.7.4 Vial Crimp Caps.7.5 Septa, Teflon/Silicone. To ensure that the septa are freeof volatiles, condition the septa in a vacuum oven at 130C for16 h.7.6 Crimping Tool for Vials.4,57.7 Syringe2 mL gas tight with valve.4,6Store syringe in90C oven betw
27、een uses.7.8 4-Heptanone.4,77.9 For Manual Injection OnlyHot air oven and heatresistant gloves.8. Instrument Setup8.1 Set up the gas chromatographic system per the manu-facturers recommendations and as follows:8.1.1 Injector Temperature250C.8.1.2 Detector Temperature250C.8.1.3 Column Temperature:8.1
28、.3.1 Initial 40C for 4 min.8.1.3.2 ProgramAdjust temperature program to give aretention window of at least 15 min to ensure optimumseparation of solvents.8.1.4 Attenuation or sensitivity, or both, set to give adetector response of 40 % or more of full scale on the recorderor integrator of the expect
29、ed internal standard and standardsample response. See Practice E 260 for guidance.8.2 Set up autosampler, if used, to heat vials for 20 min at90C before autoinjection.9. Calibration Procedure9.1 Standard Curve:4The sole source of supply of the apparatus known to the committee at this timeis J. and W
30、. Scientific, Cat. No. 122-5033 and Cat. No. 123-5033. If you are awareof alternative suppliers, please provide this information to ASTM Headquarters.Your comments will receive careful consideration at a meeting of the responsibletechnical committee, which you may attend.5The sole source of supply o
31、f the apparatus known to the committee at this timeis Cat. No. 33280, Supelco Inc., Bellefonte, PA 16823.6The sole source of supply of the apparatus known to the committee at this timeis Cat. No. 050034, Alltech, 2051 Waukegan Rd., Deerfield, IL 60015.7The sole source of supply of the apparatus know
32、n to the committee at this timeis Cat. No. 10, 174-5, Aldrich, 940 W. St. Paul Ave., Milwaukee, WI 53233.F18840429.1.1 Prepare blanks by heating a sample of the packagingmaterial of interest (enough sample can be prepared at one timefor several analysis runs) in a vacuum oven at 90C for 24 h.Remove
33、the blanks and store in a closed container. Blanksshould be cut to the same relative size as the sample prior toheating in the vacuum oven.9.1.2 To prepare a calibration standard place a blank (cut toappropriate size) in the 20 mL headspace vial and add theappropriate amount of standard solvent mix
34、to the vial.Immediately cap and crimp the vial with the Teflon side of theseptum toward the vial. It is suggested that blanks be fortifiedat five different concentrations along with an unfortified blankbe prepared for calibration. See Practice E 260 for guidance.9.2 Manual Injection:9.2.1 If using a
35、 syringe and hot air oven, heat each vial for20 min at 90C. Ensure that the syringe is heated to at least90C before taking headspace samples from the vials forinjection into the chromatograph.NOTE 2When handling the hot syringe be sure that hands areadequately protected. Fill the gas tight syringe w
36、ith 1 mL of air, closevalve and insert the needle through the septum into the preheated vial.Open valve, inject the air into vial. Draw12 mL of gas from vial intosyringe, inject back into vial. Repeat 2 times. Draw exactly 1 mL of gasinto syringe and close valve. Insert needle into injector of GC an
37、d inject.NOTE 3Consistent technique from injection to injection of standardsand sample is required. This step should take no more than 30 s.9.3 Automated InjectionThe recommended method ofinjecting the headspace gas into the GC is use of an automatedheadspace sampling system where the vials are heat
38、ed to 90Cfor 20 min and then the headspace of each vial is automaticallyinjected onto the GC column.9.4 Repeat the procedure for all five calibration standardsand the blank.9.5 Construct a standard calibration curve from the dataobtained using standard techniques as defined in PracticeE 260.NOTE 4Lo
39、nger heating times may be used if it is deemed necessary toensure that the solvent in the headspace of the vial has totally equilibratedwith the sample.10. Sampling10.1 Samples should be taken in such a manner as torepresent the entire web. The analyst should cut several layersdeep into a roll of pa
40、ckaging material, discarding the outerlayers, to ensure the sampling is representative of the entireroll. Samples should be taken from the left, center and rightside of the web.NOTE 5Consideration should also be given when sampling rollswithin a production lot to ensure uniformity within the product
41、ion run.10.2 Samples should be taken and handled in such a way asto minimize loss of solvent from the sample between the timethe sample is taken, cut and loaded into the sample vial. Takingsamples at press side, cutting and loading into vials immedi-ately is the preferred method.Alternately, full we
42、b samples canbe collected at press side and placed in a sealed container(samples can also be wrapped tightly in foil) for transport to thelab for cutting and loading into vials.10.3 When taking samples from roll stock, discard the first8 to 10 layers before taking samples from the next 30 to 40layer
43、s to ensure that the samples are representative of the entireroll.10.4 When possible, samples should have 100 % ink cov-erage in the area selected for testing. Selecting an area with100 % ink coverage will ensure that the testing will elucidate aworst case. Using a sample area with representative in
44、kcoverage may also be considered.10.5 The sample size is dictated by the thickness of thesample and the ease of filling the vial. The sample size willvary from 5 to 50 in.2Typically, the vial will be less than 20 %full by volume. Alternately the ratio of the weight of thesample in grams to the volum
45、e of the vial in millilitres shouldnot exceed 1 to 10. In the case of a 20-mL sample vial, theweight of the sample should not exceed 2 g.10.6 The preferred method of cutting samples is the use ofa punch press or die.10.7 Add the appropriate amount of internal standard (ifused) to the vial.10.8 Immed
46、iately cap and crimp the vial with the Teflonside of the septa toward the vial.11. Procedure11.1 Manual Injection:11.1.1 For those using the syringe, place the sample (vial) ina forced air oven at 90C for 20 min.NOTE 6Longer heating times may be used if it is deemed necessary toensure that the solve
47、nt in the headspace of the vial has totally equilibratedwith the sample.NOTE 7When handling the hot syringe be sure that hands areadequately protected. Fill the preheated gas-tight syringe with 1 mL of air,close valve and insert the needle through the septum into the aboveconditioned vial. Open valv
48、e, inject the air into vial. Draw12 mL of gasfrom vial into syringe, inject back into vial. Repeat 2 times. Draw exactly1 mL of gas into syringe and close valve. Insert needle into injector of GCand inject.NOTE 8Consistent technique from injection to injection of standardsand sample is required. Thi
49、s step should take no more than 30 s.11.2 Automated Injection:11.2.1 The recommended method of injecting the headspacegas into the GC is use of an automated headspace samplingsystem where the vials are heated to 90C for 20 min and thenthe headspace of the vial is automatically injected onto the GCcolumn.NOTE 9Longer heating times may be used if it is deemed necessary toensure that the solvent in the headspace of the vial has totally equilibratedwith the sample.11.3 Chromatograph the sample under the same conditionsused for establishment of the
