TEST REPORT T71-6-1

QUALITATIVE ANALYSIS OF PRIMERS, TRACERS, IGNITERS,INCENDIARIES, BOOSTERS, AND DELAY COMPOSITIONS ON

A MICRO SCALE BY USE OF INFRARED SPECTROSCOPY

by

David E. CheasanGeorge Norwitz

June 1971

D C'

AMC CODE 4931.0M.6350 SEP 13 1971

This document has been approved for public release and sale;its distribution is unlimited,

NATIONAL TECHNICALINFORMATION SERVICE

DEPARTMENT OF THE ARMYFRANKFORD ARSENAL

Philadelphia, Pa. 19137

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DISCIAI41

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Stcu.it y Classiflcation

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a. ORSINATCNG'ACTI VI f (Cw'mte Author) -6.. REPORT SECURITY CLASSIFICATION -

Commanding Officer I UNCLASSIFIEDFrankford Arsenal 2b. GROUP

ATTN: 13100-64-3, Philadelphia, Pa.

3. REPORT TITLEQualitative Analysis of Primers, Tracers, Igniters, Incendiaries, Boosters, andDelay Compositions on a Micro Scale by Use of Infrared Spectroscopy

4. 091CRIPTIVE NOTES (1).pe ofreport sdinelu v date*)

Test Report3S. AUTHORISI (Pirst MAW. middle Initial, last nam)

David E. ChasanGeorge Norwitz

4. RfORT OATE 7a. TCTAI. NO. OF PAGES Tb NO. OF aEFS

June 1971 351a. CONTRACT OR GRANT NO. . ORIGINATOR'S REPORT HUMSERIS)

AMC Code 4931.OM.6350 T71- -1

16 PROJECT No.

-5. OTHER REPORT NOll) (Any OWher mbera that may be aseealdthis tport)

d.

IS. OHIOSTRUTION STATEMENT

-Release to OTS is authorized.-This document has been approved for public release and sale; its distributionis unlimited.

!I- I hLIMUNTARY PICE94 12. SPONSORING MILITARY ACTIVITY

Army Materials Agency

. A5St'RACT '

-

The application of infrared spectroscopy to the detection of the constituents ofprimers) tracers, igniters, incendiaries, boosters, and delay compositions on a microscale was investigated. It is shown that these constituents can be identified quicklyand with certainty, using infrared pellet technique to detect organic and inorganiccompounds and emission spectroscopy to identify the metals. In making the pellet,I to 2 mg of the material is ground with 300 mg of potassium bromide and the pelletformed in the die press. The grinding and pressing operation has been found to becompletely safe even with the most sensitive Lxplosives, once the material has beenmixed with the potassium bromide. The infrared spectra of 43 of the most commoningredients of primers, tracers, igniters, incendiaries, boosters, and delay compositi sare given over the range 2.5 to 50 microns. The qualitativc analysis of seven typicalcompositions is demonstrated.

pow 11111 RPLACES 00 FORM 2478. 1 JAN WHIossCH I*,e.v.1473 ::=::': = TE ARAY U69.5ecuity Clhm(itlof

Scutty Claveification14. - I LINK A LINK M LINK C

KEY WORDS-, ROLE WT ROLE WT ROLE WT

PrimersTracersIgnitersIncendiariesBoostersDelay CompositionsInfrared Spectroscopy

SecuritY Classlfication

T71-6- i

QUALITATIVE ANALYSIS OF PRIMERS, TRACERS, IGNITERS,INCENDIARIES, BOOSTERS, AND DELAY COMPOSITIONS ON

A MICRO SCALE BY USE OF INFRARED'SPECTROSCOPY

by

David E. Chasan

George Norwitz

Project - Materials Testing Technology -

AMS Code 4931.0M.6350PRON Al-O-P6350-Ol-AW-F6

This document has been approved for public release and sale;its distribution is unlimited.

Quality Assurance DirectorateFRANKFORD ARSENAL

Philadelphia, Pa. 19137

June 1971

TABLE OF CONMNTS

P~age

.SU. .RY . . . . . . . . . .

II. RECOMMENDATIONS ......... . .. . * .

1II. INTRODUCTION. . . # - ..v

IV. STUDY

A. Reconwiended Method for Preplration of Spectra . . 2

-+' B. Results and Discussion ........ ....

V. BIBLIOGRAPHY . ..... . .... . . ..

V1. TABLES . . . .. .................... . . . . 6

''1

f.--4, 4

I. SUMARY

The application of infrared spectroscopy to the detection of theconstituents of primers, tracers, igniters, incendiaries, boosters,and delay compositions on a micro scale was investigated. It is shownthat these constituents can be identified quickly and with certainty,using infrared pellet technique to detect organic and inorganiccompounds and emission spectroscopy to identify the metals. In makingthe pellet, I to 2 ing of the material is ground with 300 mg of potassiumbromide and the pellet formed in the die press. The grinding andpressing operation has been found to be completely safe even with themost sensitive explosives, once the material has been mixed with thepotassium bromide. The infrared spectra of 43 of the most commoningredients of primers, tracers, igniters, incendiaries, boosters, anddelay compositions are given over the range 2.5 to 50 microns. Thequalitative analysis of seven typical compositions is demonstrated.

I1. RECOMMENDATIONS

It is recommended that the methods and spectra described in thisreport be included in MIL-STD-650 (Military Standard, Explosive:Sampling, Inspection and Testing).

511. INTRODUCTION

The constituents of primers, tracers, igniters, incendiaries,boosters, and delay compositions are ordinarily identified by wetchemical tests for the organic compounds, anions, and metals (frequentlyemission spectrography is used for the metals). These wet tests areoften untrustworthy, especially if applied on a micro scale.

' 1

This laboratory undertook an investigation on the application ofinfrared spectroscopy to the detection of the organic compounds andinorganic compounds present in primers, tracers, igniters, incendiaries,boosters, and delay compositions. It was believed that such an infraredtechnique together with emission spectroscopy (for inorganic materialsthat do not give infrared spectra) would provide an excellent meansfor the qualitative analysis of the constituents in question.

Pristera and Fredericks (3) have compiled spectra of most consti-tuents of propellants and explosives. However, their compendium doesnot include many of the very s(!nsitive explosive compounds found inprimers, tracers, igniters, incendiaries, boosters, and delay com-positions and it does not include the far infrared. Miller et al(1, 2) have compiled spectra of inorganic compounds but their collectiondoes not include many of the inorganic compounds found in primers,tracers, igniters, incendiaries, boosters, and delay compositions.Pristera and Fredericks (3) and Miller et al (1, 2) used a prism typeinfrared spectrophotometer; the present authors used a grating type.

IV. STUDY

A. RECOMMENDED METHOD FOR PREPARATION OF SPECTRA

1. Apparatus and Reagents

Perkin-Elmer Model 621 Infrared Spectrophotometer.

Evacuable potassium bromide die (Model 186-0025, Perkin-Elmer

Corp., Norwalk, Conn).

Adapters for mounting KBr discs on spectrophotometer.

Twenty-ton hydraulic press.

Vacuum pump.

Mortars (o.d. 50 mm) with pestles.

Plastic microspatula.

Potassium bromide, infrared grade (Harshaw Chemical Co.,

Cleveland, Ohio).

2

2. Preparation of Potassium Bromide Pellets

Grind 1 - 2 grains of infrared grade KBr (in small portions)and store in a desiccator until needed.

Add 1 - 2 mg of sample to the mortar with a plastic micro-s atula (this is most conveniently done by first taring the mortar).Weigh 300 mg of the preground KBr into an aluminum balance pan and addall the KBr to the mortar. Using the plastic microspatula, thoroughlymix the KBr with the sample. Grind the sample-KBr mix for about threeminutes. Scrape the sample-KBr mix loose from the mortar surface withthe plastic microspatula and transfer it to the die. Level the sample-KBr mix with the microspatula and insert the plunger. Evacuate thedie for three minutes with a vacuum pump without applying pressure, thenapply 18,000 pounds pressure with a hydraulic press for five minutes.

Disassemble the die and push out the KBr pellet with a gentleapplication of the hydraulic press. Mount the pellet on an adapterand scan the spectrum from 2.5 to 50 microns with a blank KBr pelletin the reference beam. Use a dry air purge for the far infrared region(30 to 50 microns). The following settings were used on the Perkin-Elmer Model 621 infrared spectrophotometer: slit program, 1000; gain5.1; attenuator speed, 1100; scan drive, 1; scan time, 16; supression,!8; scale, lx; source currene, 0.8.

B. RESULTS AND DISCUSSION

The spectra obtained for the 43 commonly used ingredients of primers,tracers, igniters, incendiaries, boosters, and delay compositions areshown in Figures 1 to 43. These ingredients are arranged (Table I)according to function as follows: primary explosives, high explosives,oxidizers, color intensifiers, binders, and miscellaneous. Compoundshaving more than one usage are listed according to their major function;for example, polyvinyl chloride is used as a binder or color intensifierbut is listed under binders. Lead thlocyanate, the only fuel thatgives a spectrum, is listed under miscellaneous; other fuels (magnesium,aluminum, zirconium, titanium, boron, silicon, and metallic hydrides)do not give Infrared spectra.

3

The spectra of seven typical explosive compositions togetherwith the notation of the peaks identifying the principle constituentsare shown in Figures 44 to 50. The conclusions concerning theanalysis of these compositions drawn from these spectratarid the- emissionspectrographic analysis are shown in Table II.

It is seen that normal lead stypanate can be distinguished frombasic lead styphnate by infrared. The different oxides of lead, iron,and barium may also be distinguished (PbO, Pb304, Fe203 , BaO, and BaO2give unique spectra, while PbO and Fe30 give no spectra).

In some spectra there is evidence of light scattering in the high.frequency end of the spectrum. This is caused by inadequate grindingor the presence of such ingredients as antimony sulfide, magnjsium,aluminum or zirconium. However, in no instance was the problem severeenough to interfere with the qualitative use of the spectrum.

The majority of spectra indicated the presence of small amounts ofmoisture; hence, care must be taken to avoid misinterpreting peaksoccurring in the regions of 3420 cm"1 and 1630 cm

A special concentration procedure must be used to detect tetra-cene (2 to 4%) present in some lead styphnate primers. In this con-centration procedure, about 50 mg of the primer contained in a sinteredglass crucible is washed successively with ammonium acetate solution(20%), water, and acetone to remove lead styphnate, barium nitrate, andPETN. About 3 or 4 mg of the residue, which contains the tetracene andantimony sulfide is then used for the pellet.

It might be thought that preparing potassium bromide pellets from verysensitive explosive materials would be hazardous. This did not proveto be the case for the following reasons: (a) a very small amount ofthe explosive is used, (b) the potassium bromide acts' as a diluent.

In the emission spectrographic analysis of explosives, it iscustomary in this laboratory to first destroy the explosive by treat-ment with concentrated nitric acid and evaporation to dryness.

4

V. BBIORA'IIY

("1) Miller, F. A., Carlson, G. L., 'Bntly, F,. "F., and Jones, W. H.,Spectrpochim. Acta, 16, 135 (1960)..

(2), Airler, F. A., and Wilkens, C. I., Anal. Chem., 24, 1253 (1952-).

(3)- Pristera, F., and Fredricks, ,W., Picatinny Arsenal Technical

Hemorandum 1887, Septeiiber 1969.

4:.

F • 5

VII. TABLES

Table 1. Idfintification of Spectra -

'Spectrum 'Code

1. Lead a-ide Primary Explosive I

2. Mercury fulminate Primary Explosive 2

3. 'etracene Primary Explosive 3

,4. ,Nofnull 'lead stylphnAte Primary Explosive 4

'5. Ilasic lead- styphnate Primary Explosive, 5,

6. RDX (cycotrimethyIenetinlitranine), High Explosive I

7. HMX (cyclotetrametlylcncteiranitraine) High Explosive 2

8. Tetryl, (2,4,6-trinitrophenyIethy nitramine) High E xplosive 3

9. PETN (pentacrythrite tetranitratd) High Explosive 4

10. 'TNT (2,4,6-trinitrotoluene) High Explosiye 5

-11; 'Nitrocellulose High Explosive 6

,12. Styphnic acid High Explosive 7

13. 'Ammonium nitrate Oxidizer 1r

14. Sodium nitrate Oxidizer 2

15. Potassium nitrate Oxidizer 3,

16. Barium nitrate Oxidizer 4

17. Strontium nItrate- Oxidizer 5

18. Lead nitrate Oxidizer 6

19. Potassium chl'orate Oxidizer 7

20. Ammonium perchlorate Oxidizer 8

Table I. Identification eof Specra (cont d)

Spedtrum Code

21. Potassium perchlorate Oxidizer 9

22. BAridi wchromate Oxidizer 10

23., Lead, .ch r~ilatva Oxidizer -11

24. Biiriuii :perikide Oxidizer 12

25. Strontium perk,xlde Oxdizer 13

26. Lcad monoxide Oxidizer-14

27. Red lead (Pb304) Oxidizer 15

28. Ferric oxide Oxidizer 16

29. Molybdenum trioxlde Oxidizer 17

30. Dechlorane ,(perchloropentadyclodecane) Color Intensifier 1

1 31. 'Sodiuinl oxalate Color Intensifier 2

32. Strontlum oxalate CoLor Intensifier 3

33. Gum ira1ic Binder -1

34. Polyvinyl chloride Binder 2

35. Parlon (chlorinated rubber) Binder 3

36. Stearic acid Binder 4

37. Wax Binder 5

38. Calcium resinate Binder 6

39. Ethyl cellulose Binder 7

40. Oxamide Misc. 1

7

Table I. Identif-ication of 'Spectra (cont"d),

Spectrum Code,

41. 14ariuni monoxide 'Misc. 2

42. Load thiocynniate 'Misc. 3.

43. Calcium cArlcinati 'Mf se,. '4

44. Detonator Mix, 1

45. Igniter Mix 2

46. Primer Mix 3

47. Primer Mix 4

48. Primer Mix 5,

49. Detonator Mix 6

50'. Detonator 'Mix 7

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liib1)h! I,,I Analy.,;I ,, of Typicil1 Coinposi tions.

infraredd Spec troscory ;&6nbined- Aialygis44

ARX DXTNT

TNT

45 BaCrO4 Pb, -Cr, 'Ba, Zr -BACrO4Pb 3 04 Pb3O4

Zr

46 'Hg Fulminate 'K, Sb, Hg Hg FuminateKCIO3 KC.,D

S b2 S3-

47 fig Fulminate KBa, Sb, Hg Hg FulminateKC10 3 KC10 3Ba(003)2 Ba(NO3 ).-

Sb2S3

48 Normal PbStyphnate AL, Sb, Pb,, Ba Normal Pb StyphnatePEWN

PETN

Ba(N03)2Ba(N03)2

Alf Sb2S3

49 Pb Azide Pb Pb AzideP UN

PETN

50 RDX RDX

Stearic Acid Stearic Acid

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