1、Designation: E2999 17Standard Test Method forAnalysis of Organic Compounds in Smokeless Powder byGas Chromatography-Mass Spectrometry and FourierTransform Infrared Spectroscopy1This standard is issued under the fixed designation E2999; the number immediately following the designation indicates the y
2、ear oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method describes the analysis of organiccom
3、ponents in smokeless powders by gas chromatography-mass spectrometry (1-6)2and Fourier transform infrared spec-troscopy.1.2 This test method is suited for analyzing samples com-prised of visible grains (whole or partial) of smokeless powder.1.3 Analysis of post-blast debris and items containing gun-
4、shot residue when visible grains of smokeless powder are notpresent is beyond the scope of this test method.1.4 The values stated in SI units are to be regarded asstandard. The values given in parentheses are mathematicalconversions to inch-pound units that are provided for informa-tion only and are
5、 not considered standard.1.5 This test method involves handling of low explosivesand potentially other energetic materials. It is strongly sug-gested that an analyst be trained in the storage and safehandling of energetic materials and be familiar with theproperties and hazards of explosives.1.6 Thi
6、s test method cannot replace knowledge, skill, orability acquired through appropriate education, training, andexperience and should be used in conjunction with soundprofessional judgment.1.7 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is t
7、heresponsibility of the user of this standard to establish appro-priate safety, health and environmental practices and deter-mine the applicability of regulatory limitations prior to use.1.8 This international standard was developed in accor-dance with internationally recognized principles on standa
8、rd-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:3E620 Practice for Reporting Opinions of Scienti
9、fic or Tech-nical ExpertsE1492 Practice for Receiving, Documenting, Storing, andRetrieving Evidence in a Forensic Science LaboratoryE2998 Practice for Characterization and Classification ofSmokeless Powder3. Terminology3.1 Definitions of Terms Specific to This Standard:3.1.1 double-base, npropellant
10、 containing nitrocelluloseand nitroglycerin.3.1.2 grain, nan individual particle of smokeless powder.3.1.3 single-base, npropellant containing nitrocellulose asthe major energetic material.3.1.4 smokeless powder, na propellant and low explosivecomposed of nitrocellulose and other organic and inorgan
11、iccompounds.3.1.5 triple-base, npropellant containing nitrocellulose,nitroglycerin, and nitroguanidine.4. Summary of Test Method4.1 An extracted specimen of smokeless powder is analyzedby gas chromatography-mass spectrometry (GC-MS) and Fou-rier transform infrared (FTIR) spectroscopy to identify org
12、aniccomponents.4.2 Post GC-MS data analysis generates extracted ion pro-files (mass chromatograms) characteristic of the organic com-ponents in smokeless powders. Specific chemical components(target compounds) can be identified by their mass spectra andretention times.1This test method is under the
13、jurisdiction ofASTM Committee E30 on ForensicSciences and is the direct responsibility of Subcommittee E30.01 on Criminalistics.Current edition approved Sept. 15, 2017. Published September 2017. DOI:10.1520/E2999-17.2The boldface numbers in parentheses refer to a list of references at the end ofthis
14、 standard.3For 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.Copyright ASTM International, 100 Barr Harbor Drive
15、, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issu
16、ed by the World Trade Organization Technical Barriers to Trade (TBT) Committee.14.3 FTIR analysis is used in the identification of nitrocellu-lose and nitroguanidine. An FTIR generates a spectrum con-sisting of IR absorption bands that can be searched through areference spectral library for a librar
17、y match to nitrocelluloseor nitroguanidine or compared to known reference materials.5. Significance and Use5.1 This test method establishes a procedure for the analysisand identification of organic components of smokeless powderby GC-MS and FTIR.5.2 FTIR is used in the analysis of nitrocellulose, wh
18、ich isa major component of all smokeless powders, and nitroguani-dine in triple-base powders.5.3 GC-MS is used in the analysis of other organic com-pounds in smokeless powders, such as energetics, stabilizers,plasticizers, and deterrents.5.4 This test method is used concurrently with E2998 for thean
19、alysis of smokeless powders when whole or partial grains arepresent.5.5 GC-MS and FTIR are two techniques used in theanalysis of smokeless powders. Additional techniques areavailable that are acceptable for use in the analysis andidentification of organic components of smokeless powders,such as liqu
20、id chromatography-mass spectrometry, capillaryelectrophoresis, and gas chromatography with flame ionizationdetection.6. Apparatus6.1 Stereo Light Microscope, with an appropriate lightsource.6.2 Gas Chromatograph-Mass SpectrometerA gas chro-matograph (GC) capable of using capillary columns and beingi
21、nterfaced to a mass spectrometer (MS) operating in electronionization (EI) mode.6.2.1 Sample Inlet SystemA sample inlet system that canbe operated in either split or splitless mode with capillarycolumns; the inlet system may use on-column technology.6.2.2 ColumnAcapillary, bonded phase, methylsilico
22、ne orphenylmethylsilicone column or equivalent. Any columnlength or temperature program conditions may be used pro-vided that each component of the test mixture (see 7.3)isadequately separated.6.2.3 GC OvenA column oven capable of reproducibletemperature program operation in the range from 40 to 300
23、C.6.2.4 Mass SpectrometerCapable of acquiring mass spec-tra from m/z 40 to m/z 400 with unit resolution or better, withcontinuous data output.6.2.4.1 SensitivityThe system must be capable of detect-ing each component of the test mixture (see 7.3) and providingsufficient ion intensity data to identif
24、y each component, eitherby computer library search or by comparison with referencespectra.6.2.5 Fourier Transform Infrared SpectrometerAn FTIRcapable of acquiring spectra in the mid-infrared region (wave-number range of 4000 to 650 cm-1).7. Chemicals, Reagents, and Materials7.1 Purity of ReagentsRea
25、gent grade chemicals or bettershould be used in all tests. Unless otherwise indicated, it isintended that all reagents conform to the specifications of theCommittee on Analytical Reagents of the American ChemicalSociety where such specifications are available.4Other gradesmay be used, provided it is
26、 first ascertained that the reagent isof sufficiently high purity to permit its use without lesseningthe accuracy of the determination.7.2 SolventsMethylene chloride and acetone (ACS re-agent grade or better).7.3 GC-MS Test MixtureThe test mixture should consistof nitroglycerin, diphenylamine, ethyl
27、 centralite, and 2,6-dinitrotoluene. The final test solution is prepared by dilutingthe above mixture such that the concentration of each compo-nent is no greater than 0.005 % weight/volume (0.05 mg/mL)in the chosen solvent (see 7.2). Additional compounds com-monly found in smokeless powders may als
28、o be included in thetest mixture, such as methyl centralite, 2,4-dinitrotoluene,2-nitrodiphenylamine, 4-nitrodiphenylamine, diethylphthalate,and dibutylphthalate.7.3.1 Appropriate concentrations of individual referencematerials or standards of these compounds may be used inaddition to or instead of
29、a test mixture.7.4 Internal StandardAn appropriate internal standard(for example, undecane, decane) may be used in the extractionsolvent for GC-MS analysis.7.5 Reference Smokeless PowdersReference smokelesspowders can be obtained as bulk reloading powders fromcommercial and retail sources or directl
30、y from the distributoror manufacturer.7.6 Polystyrene Film Standard.7.7 FTIR SuppliesSalt plates, mortar and pestle, pelletpress.7.8 GC Carrier GasHelium or hydrogen of purity 99.995% or higher.7.9 Glassware and Other SuppliesDisposable test tubes,pipettes, beakers, autosampler vials, weigh boats, w
31、eigh paper,watch glasses.8. Equipment Calibration and Maintenance8.1 GC-MS Calibration and Maintenance:8.1.1 Verify the consistent performance of the chromato-graphic instrument by using blanks and known concentrationsof either a prepared test mixture, reference materials, orstandards (see 7.3). Opt
32、imize gas flows periodically.8.1.2 Tune and check calibration of the mass spectrometer.8.1.2.1 Tune the mass spectrometer using perfluorotribu-tylamine (PFTBA), or another appropriate calibration standard,4Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washing
33、ton, DC. For suggestions on the testing of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,MD.E2999 172ac
34、cording to the instrument manufacturers specifications,prior to use. This should be done at least every day that theinstrument is used or in accordance with the manufacturersrecommendations.8.1.2.2 Maintain tuning documentation as a portion of thequality control documentation.8.1.3 Equipment Mainten
35、ance:8.1.3.1 Change septa and clean or replace injector liners ona periodic basis to avoid sample contamination by carryover ofresidual material from previous sample injections.8.2 FTIR Calibration Check and Maintenance:8.2.1 Verify the consistent performance of the instrument byanalyzing a polystyr
36、ene film standard or equivalent (standardor reference material per manufacturers recommendation)prior to use. This should be done at least every day that theinstrument is used. Compare the obtained spectrum to thatfrom a previously verified polystyrene film standard (orequivalent) to verify acceptab
37、le performance.8.2.2 Maintain calibration documentation as a portion of thequality control documentation.9. Sample Handling9.1 Observe the appropriate procedures for handling anddocumentation of all submitted samples as described in Prac-tice E1492.9.2 For specific sample handling of bulk smokeless
38、powdersamples and post-blast debris or items containing gunshotresidue where intact grains of powder are visible, refer to theSample Handling section in Practice E2998.9.3 This test method is not applicable to items containingtrace gunshot residue or post-blast debris when visible grainsof smokeless
39、 powder are not present.10. Analysis Methods10.1 GC-MS analysis of an extracted specimen will identifythe major organic components of smokeless powder with theexception of nitrocellulose and nitroguanidine.10.2 FTIR analysis is used in the identification of nitrocel-lulose and nitroguanidine on part
40、ial or whole grains of smoke-less powder when sufficient sample is available. This mayinclude collection by attenuated total reflectance, transmission,or use of micro-FTIR.10.2.1 Refer to theAnalysis Plan for the Characterization ofSmokeless Powders section in E2998 for specific extractiontechniques
41、 used to isolate the organic components of smoke-less powder for GC-MS and FTIR analysis.10.3 GC-MS Conditions:10.3.1 Only samples of appropriate dilution should beanalyzed on a GC-MS system.10.3.2 Table 1 describes basic GC-MS parameters that canbe used for the analysis of smokeless powder.10.3.3 A
42、ny column length or temperature program condi-tions may be used provided that each components peak of atest mixture, reference materials, or appropriate standards (see7.3) is adequately resolved.10.3.4 The injector temperature should not exceed 220 C.This is to prevent thermal degradation of several
43、 compoundsused in smokeless powder formulations. The injector can beoperated in either split or splitless mode.10.4 FTIR Conditions:10.4.1 Table 2 describes basic FTIR parameters that can beused for the analysis of nitrocellulose and nitroguanidine.10.4.2 For double and triple-base powder specimens,
44、 thenitroglycerin should be extracted from the specimen grainsprior to FTIR analysis using an appropriate extraction tech-nique as described in E2998.NOTE 1Nitroglycerin and nitrocellulose have similar FTIR spectralfeatures.10.4.3 An FTIR analysis should include an analysis of abackground scan prior
45、 to a specimen analysis.10.4.4 The ATR stage or window should be cleaned with anappropriate solvent between specimen scans.10.5 Quality Control:10.5.1 AGC-MS analysis sequence may consist of a smoke-less powder test mixture, individual standards, a negativecontrol or system blank, a positive control
46、 or reference sample,solvent blanks, and questioned samples.10.5.1.1 Analyzing a solvent blank between samples isrecommended but is not necessary if studies demonstrate thatthe cleaning procedure is adequate to prevent carryover.10.5.2 The instrument detection limit for nitroglycerinshould be evalua
47、ted as a quality control check prior to sampleanalysis if the desired result of the analysis is to identify aquestioned material as a specific class of smokeless powder.11. Data Analysis11.1 General Data Analysis Scheme:11.1.1 Extracted ion profiling and target compound analysisis used to identify t
48、he major peaks in the total ion chromato-gram (TIC) and mass chromatograms of a GC-MS analysis ofa smokeless powder specimen.11.1.2 FTIR analysis is used in the identification of nitro-cellulose and nitroguanidine.11.2 GC-MS Data Analysis:11.2.1 GC-MS data analysis consists of using extracted ionpro
49、filing (EIP) to generate mass chromatograms of targetcompounds found in smokeless powders.TABLE 1 Suggested GC-MS ConditionsGC column: 30 metre, DB-5 capillary columnInitial temp: 45CInitial hold time: 3 minutesRamp 1: 15C/minute to 150CRamp 2: 40C/minute to 265CFinal hold time: 7 minutesInjector temperature: 190 to 220CMode: Electron Ionization (EI)MS scan range: 41 to 400 m/zSolvent delay: 3 minutesTABLE 2 Suggested FTIR ParametersWavenumber range: 4000 to 650 cm-1Background scans: 32Sample scans: 32Resolution: 4 cm-1E2999 17311.2.1.1 The major tar
