new limitation change to - dtic · ii the findings in this report are not to be construed as ......
TRANSCRIPT
UNCLASSIFIED
AD NUMBER
ADB060344
NEW LIMITATION CHANGE
TOApproved for public release, distributionunlimited
FROMDistribution limited to U.S. Gov't.agencies and their Contractors; Specificauthority; Aug 81. Other requests must bereferred to Commander, Army ArmamentResearch and Development Command, Attn:DRDAR-TSB. Aberdeen Proving Ground, MD21005.
AUTHORITY
ARL ltr, 18 Oct 2002
THIS PAGE IS UNCLASSIFIED
This DocumentReproduced From
Best Avaiablet Copy
MEMORANDUM REPORT ARBRL-MR-03121.
THE DETERMINATION OF HEXAHYDRO-1, 3,
5,-TRINITRO-S-TRIAZINE (RDX) AND OCTAHYDRO-
1, 3, 5, 7-TETRANITRO-S-TETRAZOCINE (HMX) BY
HiGH PERFORMANCE LIQUID CHROMATOGRAPHY
J. Omar DoaliArpad A. Juhasz
August 1981
US ARMY ARMAMENT RESEARCH AND DEVELOPMENT COMMANDBALLISTIC RESEARCH LABORATORY
ABERDEEN PROVING GROUND, MARYLAND
Distribution limited to US Government agencies only; Test andEvaluation; ALL.Ct J ,Other requests for this document must be
" referred to Director, USA Ballistic Research Laboratory,ATTN: DRDAR-TSB, Aberdeen Proving Ground, Maryland 21005.
L.÷
Ao
.. ~, f~ -, 1 ~'7W~g~p, ~ ..........-
Destroy this rTport when it is no longer needed.Do not return it to the originator.
Secondary distribution of this report by originatingor sponsoring activity is prohibited.
Additional copies of this report may be obtainedfrom the Defense Technical Information Center, CameronStation, Alexandria, Virginia 22314.
ii
The findings in this report are not to be construed asan official Department of the Army position, unlessso designated by other authorized documents.
?4 ue j.a* --inje ~se or ".sfacw.rer' owura ini ,his rloporJadenO~*i~ýa '14rsmenv of an aorwmaer-al pr~odt.
• • . ... • .., . . .. , , .• ,• . .. • , •z- .. ,, . . . . . )
• . ... • .... . • -'.. . • • ,••,,"•, -:•_-.:m" " .................. '" ..... "" " "'... . .. " ' " • •"" "" - II •L •_-"'•" "' .... .""•''.-- " ... .. .4..
UINCLASSIFIlED* ~~~SECURITY CLASSIFICATION OF THIS PAGE (ften Dots Ente0red) _________________
REPOT DCUMNTATON AGEREAD INSTRUCTIONSREPOT DCUMNTATON AGEBEFORE COMPLETING FORM
I. REPORT NUMBER1 Ia. GOVT ACCESSION NO. 3. RECIPIENT'S CATALOG NUMBER
MEMORANDUM REPORT ARBRL-MR-03171 £)O 914. TITLE (and 8ubtliti) 5. TYPE OF REPORT & PERIOD COVERED
THE DETERMINATION OF HEXAHYDRO-1, 3, 5,-TRINITRO- Memorandum ReportS-TRIAZINE (RDX) AND OCTAH-YDRO-1, 3, 5, 7-TETRANI-____________TRO-S-TETRAZOCINE (H-MX) BY HIGH PERFORMANCE 6. PERFORMING ORG. REPORT NUMBER
LIQUID CHROMATOGRAPHJY7. AUTMOR(a) 8- CONTRACT OR GRANT NUM BER(&)
J. Omar DoaliArpad A. Juhasz
*. PE9RFOAMING ORGANIZATION NAME AND ADDRESS 10. PROGRAM ELEMENT, PROJECT, TASK
US Army Balalistic Research Laboratory AREA & WORK UNIT NUMBERS
ATTN: DRDAR-BLI 1121A8Aberdeen Proving Ground, MD 21005 1121A8
11. CONTROLLING OFFICE NAME AND ADDRESS 12. REPORT DATE
US Army Armament Research & Development Command AUGUST 1931US Army Ballistic Research Laboratory 13. NUMBER OF PAGES
if~f~DJD LI around. MD 21005 314.MONITORING AGENCY NAME 41 ADORESS(If dift..rent from Conitrolling Office) I5. SECURITY CLASS. (of this report)
Unclassified
I~.DCLASSIFICATION/00OWNORADINGSCHEDULE
is. DISTRIBUTION STATEMENT (of tMle Report)
Distribution limited to US Government agencies only; Test and Evaluation;Aug 1981. Other requests for this document must be referred to Director,US Army Ballistic Research Laboratory, ATTN: DRDAR-TSB, Aberdeen ProvingGround, MD 21005.
17. DISTRIBUTION STATEMENT (of the abotract entered in Block 20, It different from Report)
IS. SUPPLEMENTARY NOTES
IS. KIEY WORDS (Continue an reverse side if naeesary and Identify by block number)
Nitramine AnalysisHMXRDXLiquid Chromatography
25. ABNIS ACrt (antll m-~o pevm eIfneoeaew' aid idoentif by block number) jimkA method is described, using high performance liquid chromatography, to
determine quantitatively hexahydro-l,.3, 5-trinitro-s-triazine (RDX) andoctahydro-l, 3, 5, 7-tetranitro-s-tetrazocine (HMX) in a mixture and aspropellant ingredients. Separations are achieved on a Micro Pak-CN cohlffin,
250-mm long x 2.1-mm internal diameter, using a mobile phase of 30-percentmethylene chloride/20-percent acetonitrile/SO-percent hexane. Under theseconditions, the two compounds are separated in approximately ten minutes.
DD jOA F". u nJ EviTsOm or 9 Nov as is OBsoLETE. UNCLASSIF IED)
I SECURITY CLASSI1FICATION OF THIS PAGE (When Date Entered)
4 4' .. t
u~t -"i
TABLE OF CONTENTS
Page
I. INTRODUCTION. . ............... ....... 5
II. EXPERIMENTAL. . . . . . . . . . . .............. 6
III. RESULTS AND DISCUSSION ............ .................. 8
A. Limits of Quantification ........... ............... 8
B. Synthetic Sample Analysis. . .............. 8
C. Determination of HMX in a Propellant ...... ......... 10
IV. CONCLUSION .................. ....................... 12
REFERENCES ............................ 13
APPENDIX A ............... ........................ 15
APPENDIX B ............... ....................... ... 19
APPENDIX C ............... ....................... ... 23
DISTRIBUTION LIST .................. ................... 29
Accossion For
NTIS ('' Fl
Ju z!LI '. .. .' . . . .
DV•i i;t. L t, ".,
DI 't
3//,
1.
I. INTRODUCTION
The determination of octahydro-l, 3, S, 7-tetranitro-s-tetrazocine(HMX) and hexahydro-l, 3, 5-trinitro-s-triazine (RDX) in mixtures andespecially the determination of RDX as an HMX contaminant has been acontinuing problem because of the structural similarities of the compounds.This has been an especially important problem because it has been demon-strated that the i pure compounds exhibit lower thermal stability thanthe pure compounds . The structures and pertinent physical .propertiesof these nitramines are presented in Appendices A and B.
Due to the difficulties involved in the analyses, a variety oftechniques including wet chemical procedures and instrumental methods 2-4
.• !have been applied to the problem with varying degrees of success. Reviewsare available which digcuss the various techniques. Recently, a gaschromatographic method and an infrared spectrophotometric method weredevelopea to perform the analyses. However, both procedures are onlyapplicable to the determination of RDX.
Within the Ballistic Research Laboratory, interest developed inprocedures to determine RDX and HMX due to the advent of low vulnerabilitypropellants containing these nitramines. Additionally, an on-goingproject involving thermal decomposition studies of RDX and HMX necessitatedthe development of procedures to determine the purity of the parent
IJ. Stahls, "Report on the Basic Chemistry of RDX and a-and a-HMX andIts Application", (U) Defense Standards Laboratories Report 400 (Australia),November 1970, (CONFIDENTIAL).
H.J. Scullion, "A Survey of the Methods Available for the Analysis of
HMX/RDX Mixtures", Ministry of Defense, UK Army Department, ChemicalInspectorate Memorandum No. 169, 1965.
3Earle F. Reese, "Resume of Analytical Methods for the Determination ofRDX and HMX 1943-1965", Picatinny Arsenal Technical Report No. 3309,December Y965.
4Mortimer Schwartz and Elizabeth A. Mark, "Quantitative SpectrophotometricDetermination of Hexahydro-1, 3, 5-Trinitro-s-Triazine in Octahydro-1,3, 5, 7-Tetranitro-s-Tetrazocine", Anal. Chem., 38, pp. 6i0-612, April1966.
5 M.L. Rowe, "Determination of Hexahydro-1, 3, 5-Trinitro-s-Triazine inOctahydro-2, 3, 5, 7-Tetranitro-s-Tetrazocine by Gas Chromatography",J. Gas Chromatography, 5, pp. 531-532, October 1967.
6 8.W. Grindlay, "Determination of Hexahydro-1, 3, 5-Trinitro-s-Triazine
(RDX) in Octahydro-1, 3, 5, 7-Tetranitro-s-Tetrazocine (HMX) by InfraredSpectrophometry", Anal. Chem., 44, pp. 1676-1678, August 1972.
5J
A
compounds. Previous experience in the analysis of er'.rgetic materialsusing high performance liquid chromatography (11PLC)" indicated t thesenitramines could be separated and possibly determined inu a straight-forward manner. This report presents the results obtained using an HPI.Cprocedure as a solution to the problem of nitramine aftalysi,.
* II. EXPERIMENTAL
The investigation was performed using a DuPont Model 830 LiquidChromatograph equipped with a fixed wavelength (254 nm) ultravioletdetector. A Spectra Physics Minigrator monitored the outpuz of thedetector and produced a printout of the retention times and peak areas.A Micro Pak-CN column (250 mm x 2.1 mm i.d.) was used to achieve theseparations. The mobile phase solvents were acetonitrile (UV), methylenechloride, and hexane (UV) obtained from Burdick and Jackson Laboratories,Inc.
The other important instrumental conditions are summarized below:
Mobile Phase: 30-percent CH2 Cl 2 /20-percent CH3 CN/S0-percent hexane
Mode: Normal (constant composition)
Pressure: 2.75 MPa, 400 psig
Flow Rate: 0.5 mL/min
Temperature: Ambient (21-22C)
Under these conditions, the separation of HMX and RDX was completein approximately ten minutes as shown in Figure 1. Injections weremade using a Disc Instruments sample valve which had an internal volumeof 10 PL. This valve has demonstrated a repeatability of better thanone percent relative.
Purification of HMX was achieved by repeated crystallizations fromacetone while RDX was purified by sublimation. The compounds wereconsidered pure when a 10 ng injection o,! either compound resulted in thedetection of only one peak at the highest sensitivity of the detector(0.01 AUFS).
7J. Omnar Doali and Arpad A. Juhaez, "High Speed Liquid ChromatographicSeparation8 of Thermally Labile High Energy Compounds. Part I App i-cation of High Speed Liquid Chromatography to the Qualitative Analysisof Compounds of Propellant and Exploeives Interest", Ballietio ResearchLaboratory Report No. 1644, Ballietic Research Laboratory, AberdeenProving Ground, MD, April 19?3. (AD #910482L)
6
-...
. ....
RDX
HMXz0
U"'
RUiLUJ
I--
0 10TIME (min.)
Figure 1. Chromatographic Separation of RDX and HMX
7
PPR • ! q 10' ...... 1M 1. 1. .1 Ig P, •:
Under these conditions, RDX would be detectable down to at least3 ng while the detectable quantity of HMX would be slightly higher dueto its lower molar absorptivity. The materials which passed this qualitycontrol procedure, were then used as standards in all of the analyses.
III. RESULTS AND DISCUSSION
A. Limits of Quantification
Four standard solutions of RDX in acetonitrile were prepared to covera concentration range of 12 ng to 103 ng per l0pL. Injection of thesesolutions with the detector at its highest sensitivity resulted in thecalibration curve shown in Figure 2. The curve is linear with a nearzero intercept and a correlation coefficient of 0.999. The 12-ng sampleappeared to be the lower limit of quantification due to the detector noiseat this high sensitivity; This means that the injection of a 10-Ug sampleof HMX would allow the determination of RDX contamination down to approx-imately 0.1 percent. Though 10-ug samples were chosen for this investi-gation, there is no reason why 20-pg samples could not be used whichwould increase the quantification of RDX down to approximately 0.05 percent.
The limit of quantification for HMX would be somewhat higher thanRDX because of its previously mentioned lower molar absorptivity.However, the detectability of both compounds would be improved if theanalyses were performed at a shorter wavelength by using a variablewavelength ultraviolet detector. The limiting factor would be the UVcutoff of the methylene chloride contained in the mobile phase whichoccurs at approximately 245 nm.
B. Synthetic Sample Analysis
To determine the accuracy and precision of the procedure with respectto small quantities of RDX, a solution was prepared which contained 5.54 ugof HMX per l0uL (99.08%) and 51.6 ng of RDX per lOuL (0.92%). Fourinjections were made into the chromatograph and the resulting peak areascompared with those resulting from the injection of RDX standards. Thepercent RDX was calculated using the following expression:
W • A%RDX *w • 100
5 t
where W and A are the weights and peak areas respectively, the subscriptsrefer to the standard (s), the "unknown" RDX (x) and the total sampleweight (t). Table 1 shows the mean values (i), the sample standarddeviations (s) and the relative standard deviations resulting from theanalysis. The results indicate good accuracy for RDX with acceptableprecision for the small RDX peaks.
8
8000 ,
6000
LU
S4000
2000
0 !Z0 24 48 72 96
RDX (ng)
Figure 2. Response of Detector to Small Quantities of RDX
9
I
S... .... ......... • • ' . .... • - ,• '•- •• • • : • •'r• • •'•" m•= : "'• L. •'• ' •4.
TABLE 1. RESULTS OF SYNTHETIC RDX/HMX MIXTURE ANALYSIS
RDX
% Added % Found I..I..
0.92 0.910.940.87
0.90x = 0.91s = 0.03
Rel. s = 3.2%
C. Determination of HMX in a Propellant
The propellant chosen for analysis was a low vulnerabilityformulation PPLA 6379 which had the following nominal composition:
75% HMX20% Cellulose Acetate4.5% Nitrocellulose0.5% Wax0.3% Ethyl Centralite
Four standard solutions of HMX were prepared to contain from 1.1 pgto 6.6 .g per 10 pL. Injection of the standards in duplicate and measure-ment of their peak areas resulted in a linear calibration curve with acorrelation coefficient of 0.999.
Duplicate 500-mg samples of the propellant weighed to + 0.1 mgwere placed in 1-liter volumetric flasks and filled to the mark withacetonitrile. Clear solutions were obtained after the flasks sat over-night with subsequent shaking. Injection of a sample into the chromato-graph resulted in only one peak (HMX) eluting after the solvent frontas shown in Figure 3. Under these separation conditions, the ethylcentralite would elute at the solvent front. Several injections weremade over a period of approximately three hours to determine if anyother peaks eluted. There was no evidence of either other peaks elutingfrom the column or a change in column characteristics.
In order to compensate for any fluctuations in flow rate, a standardwas injected prior to each unknown. Three injections of each propellantsolution were made and the percent HMX calculated using the sameexpression used for the RDX determination.
i10
HMX
LU
0CL
LUJ
0I--U
001
*
.II
TIME (min.)
Figure 3. Chromatogram of Propellant Solution
-- _ 11
- . --- . . - - - -.-
The resu s as presented in Table 2 indicate good precision and agreedwell witl the nominal HMX concentration in the propellant. The onlycomplications which may arise in the determination of the nitramines inthe new propellants are the variety of binders and additives used inthese formulations. Each propellant may have to be approached as aunique problem with respect to achieving sample dissolution and possibleinterferences due to other propellant ingredients.
TABLE 2. RESULTS OF PROPELLANT ANALYSIS
%HMX74.6276.1074.6273.9374.4475.4574.86
S = 0.78Relative s = 1.0%
Fortunately, during the course of the analyses, it was found tnatthe results obtained using peak heights agreed with those obtained usingpeak areas. Consequently, instrumental requirements for the procedureare simplified.
IV. CONCLUSION
The investigation demonstrates that HPLC can be successfully appliedto the quantitative determination of HMX and RDX in admixture or separately.The purity of either compound can be determined in a straight forwardmanner without complications. The procedure has been selected as atentative method for MIL-STD 286B, Propellants, Solid: Sampling,Examination and Testing and MIL-STD 650, Explosives: Sampling, Inspectionand Testing. Appendix C presents the method in its MIL-STD format. Theapplicability of the method to the determination of HMX in a lowvulnerability propellant has also been demonstrated. As a result, asimple quality control procedure is available to determine both of thecompounds in the new nitramine propellants.
12
i ••-A•.• ¸'': • ~~~~~~~~~ ~~~~~...... ............. • • • j • •, , r .... ....
REFERENCES
1. J. Stals, "Report on the Basic Chemistry of RDX and a-and-$-HMXand Its Application", (U) Defense Standards Laboratories Report 400(Australia), November 1970. (Confidential).
2. H.J. Scullion, "A Survey of the Methods Available for the Analysisof HMX/RDX Mixtures", Ministry of Defense, UK Army Department,Chemical Inspectorate Memorandum No. 169, 1965.
3. Earle F. Reese, "Resume of Analytical Methods for the Determinationof RDX and HMX 1943-1965", Picatinny Arsenal Technical Report No.3309, December 1965.
4. Mortimer Schwartz and Elizabeth A. Mark, "Quantitative Spectrophoto-metric Determination of Hexahydro-l, 3, 5-Trinitro-s-Triazine inOctahydro-l, 3, 5, 7-Tetranitro-s-Tetrazocine", Anal. Chem., 38,pp. 610-612, April 1966.
5. M.L. Rowe, "Determination of Hexahydro-l, 3, 5-Trinitro-s--Triazinein Octahydro-l, 3, 5, 7-Tetranitro-s-Tetrazocine by Gas Chromatography",J. Gas Chromatography, 5, pp. 531-532, October 1967.
6. J.W. Grindlay, "Determination of Hexahydro-l, 3, 5-Trinitro-s-Triazine (RDX) in Octahydro-l, 3, 5, 7-Tetranitro-s-Tetrazocine (HMX)by Infrared Spectrophometry", Anal. Chem., 44, pp. 1676-1678,August 1972.
7. J. Omar Doali and Arpad A. Juhasz, "Hight Speed Liquid ChromatographicSeparations of Thermally Labile High Energy Compounds. Part IApplication of High Speed Liquid Chromatography to the QualitativeAnalysis of Compounds of Propellant and Explosives Interest"Ballistic Research Laboratory Report No. 1644, Ballistic ResearchLaboratory, Aberdeen Proving Ground, MD, April 1973. (AD #910482L)
13//V
ki
a ~1-
APPENDIX A
STRUCTURE AND PHYSICAL PROPERTIES OF HMX
The following pages were copied from AMCP 706-177, EngineeringDesign Handbook, Explosives Series, Properties of Explosives of MilitaryInterest, January 1971.
-,
(I
S .. ... ... . . . . . . . ... • '. ",• ..... . , 1 i • " ' I ~ '• •' •'
beta-HNX (a), AMCP 706-177
Cempeoele:H 2 Me*Clee te Weight: (C-HO8N8 8) 29
c 16.2 0 X-N N-NO2 Oxygen .21.6c
H 2.7 HO CH CO%9 0.021 I 2
N 37 2 -N N-"O2 DeeuitY3 gm/cc Crysate- 1.90mak3al H2 t Mo*C Capillary muethod 2
0 43-2 er Mo ro. Hot StageC/H Ratio 0.095 Freezing Point: *C
impact Sensitivity, 2 Kg1 Wt: goling# 1`o1nt: 0CBureau of Minea Apparatus, cm 32
Sample Wt 20 mg Refmoetl** Imisi, nOPicotinny Arsenal Apparatus, in. 9 n.
Sample Wt, mg 23
Frcto Pa~la Toetl Vecuumw Stability Test:Steel Shoe HIbplodes cc/40 Mrs, atFiber Shoe Unaffected 901C
100*C 0.3TRifle gullet Impact Tent: Trials 120*C 0.45
%I35'C --Epalasios 1501C 0.62
Burned 200 Gram Bomb SaOi TOWtUnaffected Sand, gm 6o.4
Seod,0 ( ocp ue) 360 Minimu Deo aigCh re
I- Mercury Fulminate5 32T Lead Azide 0.30
10 306 Tetryl
20 -- sallistig Meeter. % TNT: 150
Trawl Te", % TNT: 145736C lnoat*le ael Hoot Toot: Plftbe ant Toest
% Lous In 48 Mrs eto
100C oot otE:Condition% Loss, I st 48 Mrs 0.05 Confined% Loss, 2nd 48 Hrs 0.03 Dniy mcExplosion In 100 Mrs None raneTN
Detonation Rte:111amobllit InoxiConfinement
Hygeeeolelt: %ConditionHylves % ce { citoyl Charge Diameter, In.
30,9%m000Density, gmn/cc 1.84Rote, meoters/second 9124
16
173
pA
AXCP 706-177 beta-ImX
loostor' Sweitlelviy Teeo. Deeseepositles aque#I..(elCondition Oxygen, atoms/s~c 0-
Tetryl, gm (Z/se)Heat, kilocalorie/mole 52.7Wax, in, for 50% Detonation (1HI, kcol/mol)
Wax, gm Temperature Range, *C 2T1- 314Density, gm/cc Phase. Liquid
Combustion, cal/gmn 2362 A m rfe .I p s ee
lExplosiont, cal/gm (a) 1356 60 asm MadrI~ Prejeetb:Gas Volumne, cc/gm 50% Inert, Velocity, ft/sec
Forniation, cal/gmn (a) -6o5 Aluminum FinerwessFusion, cal/gmn
___________________________________________ 5004lb Geneeral Purpose Sakntbe:Specifi "Oret Col/gm/*C Recrystall2ized (g)
__ 0 Plate Thickness, inches
-75 0.153 85 0.2880 0.228 90 0.290 1
25 0.248 100 0.29550 0.266 125 0.30775 0.282. 150 0.315
1%serirnig Rote
cm/seclsamb Deep Test
Theemel CmiduceivilysCol/sec/cm/*C TY, 20004lb Semi-Armor-Plew~cng llomb ve Coocrete:
Coeficint f Exensca:Max Safe Drop, ftLinear, %/*C 500lb Geneeral Pu pvse Bomb vs Concrete:
Volume, %/*C Height, ftTrials
Hardness, Melee' Scale: (e) 2.3 Uafce
Low OrderTeeig's edeees:High Order
E', dynes/cmlE, lb/inch2
100O-Ib Genseral Purpose 1msb vs Concrete:Density, gm/cc
Height, ftCompressove Steesgeb: lb/Inchg Trials
__________________________________ Unaffected
Van"p. ressures Low OrderCmmn Mercury High Order
1741 /8
/R
APPENDIX B
STRUCTURE AND PHYSICAL PROPERTIES OF RDX
The following pages were copied from AMCP 706-177, EngineeringDesign Handbook, Explosives Series, Properties of Explosives of MilitaryInterest, January 1971.
19
"" k4
. ... .. .~ . ..~ .4~ .4~, .*4~ >4 .-'~' ... ... .. ... .. .... . . . . . . . . . . . . . . . . .
S~..+
Cyclonlte* (,RX) AMCP 706I77
Compouitln: 2 Molecular Welght: (C3H6N606 ) 222
C 16.3 2 NNO Oxygen Belance:
H 2.-( 2 CO % 0.0
N 37.8 NDensity: gm/cc Crystal 1.82
0 43.2 ý2 Melting Point: 'C 204
C/H Ratio 0.095 Fezring Point: OC
Impoct Seomtivity, 2 Kg Wt: Bo"ling Point: °CBureau of Mines Apparatus, cm 32
Sample Wt 20 mg Refvective Index, nOPPicatinty Arsenal Apparatus, in. 8
Sample Wt, mg 18 nalno
Friction Prndulum Toot: Vacuum Stability Toot:Steel Shoe Explodes cc/40 Hrs, atFiber Shoe Unaffected 90°C
100"C 0.7
Rifle Bullet Impact Toot: Trials 1201C 0.9
.- •,*% 135ocExplosions 100Partials 0 1500C 2.5
Burned 0 200 Gram Bomb Seand Tst:Unaffected 0 Sand, gm 60.2
Exploeion Temperatuse: C Sensitilvity to InitiationsSeconds, 0.1 (no cap used) 405 Minimum Detonating Charge, gm
1 316 Mercury Fulminate 0.19*5 Decomnposes 260 Lead Azide 0.05*
10 24o0 Tetrvl -
15 235 Alternltive initiatin2 char=es.
20 - Bllislic Mortet, % TNT: (a) 150
Troull Test, % TNT: (b) 15775"C Intometlenel HMot Test:
% Loss in 48 Hrs 0.03 Plate Dent Tests (c)'i!•.Method A
1000C Heot Test: Condition Pressed
% Loss, 1st 48 Hrs 0.04 Confined Yes% Loss, 2nd 48 Hrs 0.00 Density, gm/cc 1.50
Explosion in 100 Hrs None Brisonce, % TNT 135Detenetlo" Rete:
Flammablity Index: (d) 2T8 Confinement NoneCondition Pressed
""OgaOPiitYl % 2500, 100% RH 0.02 Charge Diameter, in. 1.0
Density, gm/cc 1.65
V~edlieNy: Nl Rate, meters/second 8180
*Nsme given by Clarence J. Bain o-' Picatinny Arsenal. Germans call it Hexogen; Italians-callit T4; British, RFX.
20 69
+ ' ,.........
AMCP 706-177 Cyclonite (RDX)
Senator Sonseitvily Teat: Decovse,11000 Lvmwet (. 1.Condition Oxygen, atnms/oc18•5
Tetryl, gm (Z/sec)
Wax, in. for 50% Detonation Heat, kilocalorle/mciT
Wax, gm Temperature Range, CC 213-299Density, gm/cc Phase Liquid
Heat of:Combxution, cal/gm 2285 Anms. Pt Imlose Teat
Explosion, cal/gm 1280 60 Mortar Proljllk:Gas Volume, cc/gm 908 50% Inert, Velocity, ft/sec
Formation, ;al/gm -96 Aluminum FinenessSolution, cal/mol (28-55% H1.0) 7.169*
*Assuming cyclonite uwilmoleculai, 500.4b General Purpose lmrbs:
Spefif& heet: cal/gm/oC0C 0 C Plate Thickness, inches
20 0.298 100 o.4o6 I40 0o331 120 o.427 11460 0.36o 14o o.446
.Burning Ibs 1'V
.mse Bomb Drop Toot
S!Therm.il Coqluof: (h)cal/svc/cm/'C 1.263 6.9 : X 10-4 17, 200W-lb Seml.Armo.-Piercing Bomb vs Coacrte:Do•ensity, gm/ac 1.533 6 x ....
f oe, Max Sa Drop, ft
Einear, d %e/CLinear, h /'C 1SO0-lb General Purpose Bomb vs Concretet
Volume, %/1C Height, ftTrials
H__d_ _ _, Melia' S_ __t__ 2.5 _Unaffected
Youap'o Meemie: Low Order
E', dynes/m ru High Order
E, lb/inch2 lO00-1b General Purpose Bomb vs Concrete
Density, g,'n/cc
•" • Height, ft•!!Cormprealve Strainttt Ib/inch" Trials
!i,•{ Unaffec:ted• Vaorwrssure:• Low O.rdr
S, C mm Mercury High Order
T0 21 /
... .
APPENDIX C
Procedure For the Determination of RDX and HMX in MIL-STD Format
23
fl. ý- TDISPOSITION FORMPet useof thIs feel% see.AR 34-116 th pop ;: ;::c.jas alQu tittiv Deterinaton o
REPFERENCE ORt OFFICE SYMIOL $1.16JECT
Propellant Inrdet yHigh Performance LiquidChromotography (HPLC) ______________
To Director, PAFROM C , DRDARQk DATE IE a41'I CMT Ir.Gultzfjtf 5626
1. Per your note, dated 6 December 1978, the subject report was reviewed. ftCo~ents,concllusions and implementation actions"t are provided below.
2. Subject report contains test procedures (HPLC) for a number of ingredients thatare used in propellant formulations (i.e. DST, DEP, XG, EC, etc.). These methodshave already been implemented in MIL-STD-286, Propellants, Solid: Sampling, Examina-tion and Testing,
3. Subject report also, contains test procedures (HPLC) in connection with RDX andHMX. This Command has previously approved these procedures for use by HOLSTONi AAPas equivalent test procedures for specification testing of Composition B, RDX andHNX. Action has been initiated to include these procedures in MIL-STD-286 andMIL-STD-650, Explosives: Sampling, Inspection and Testing.
1 nci :-LEM3'G. BAKER ISubject rpt C, Artillery Tank Systems Division
24DA U I 49 PLACES 00 FORM 04,WHICH 15 OSIOLEIE9.
I'A
APPENDIX C
RDX AND HMX(LIQUID CHROMATOGRAPHIC METHOD)
1. SCOPE
1.1 This method may be used to determine HMX and RDX in a mixture orseparately.
2. SPECIMEN
2.1 The specimen shall consist of sufficient material to give a finalconcentration of 1 mg/mL of the major component in a puritydetermination of either compound as a major ingredient, a finalconcentration of 0.2 mg/mL to 0.8 mg/mL is required.
3. APPARATUS
3.1 High pressure liquid chromatograph (DuPont 830 or equivalent equippedwith an ultraviolet detector (254 nm).
3.2 Micro Pak-CN (10 p particle size) column 250 mm x 2.1 mm i.d. (VarianInstrument Division or equivalent).
3.3 Sample injection valve of 10-microliter volume (Disc InstrumentsModel 704-4-16 or equivalent).
3.4 Volumetric flasks as required.
3.5 Volumetric pipets as required.
4. MATERIALS
4.1 Acetonitrile (UV) (Burdick and Jackson, Inc. or equivalent).
4.2 Methylene Chloride (Burdick and Jackson, Inc. or equivalent).
4.3 Hexane (UV) (Burdick and Jackson, Inc. or equivalent).
4.4 HMX purified by crystallization from acetone or equivalent quality.
4.5 RDX purified by sublimation or equivalent quality.
4.6 Acetone, reagent grade or equivalent.
5. PROCEDURE
5.1 Instrument conditions.
5.1.1 Wave length of detector: 254 nm.
25
k• , • , .. . - . . - .. . . .. . . . . . . .. . . . . . . . .. . 7 - . _ _I ,- . . , ,
I.
[1
5.1.2 Column temperature: ambient.
5.1.4 Mobile phase: 30% methylene chloride/20% acetonitrile/50% Hexane,
5.1.5 Pressure: 2.75 MPa (400 psig).
5.1.6 Flow Rate: 0.5 mL/min.
5.1.7 Recorder Chart speed: 2.54 mm/min.
5.1.8 Under these conditions RDX will elute before IMX, see Figure C-i.
5.2 Sample Analysis.
5.2.1 All solutions shall be made using acetonitrile as the solvent.
5.2.2 All weighings shall be ± 0.1 mg.
5.2.3 RDX and HMX used in preparation of standards shall exhibit onlyone peak when 10 pg of each compound is injected into thechromatograph with the ultraviolet detector at a sensitivityof 0.01 AUFS.
5.2.4 Determination of RDX contaminant in HMX.
a) Prepare RDX standards in volumetric flasks to contain 1.0 mg,0.50 mg, 0.25 mg, and 0.12 mg per 100 mL. These standardscorrespond to a concentration of 1%, 0.5%, 0.25%, and 0.12%RDX in a l0-ug sample of HMX.
b) Allow liquid chromatograph to stabilize.
c) Set ultraviolet detector to 0.01 AUFS.
4) Inject the standards (10 UL) and obtain a linear calibrationcurve of peak height vs. weight of RDX.
NOTE: Once the linearity of detector response has beendetermined over the concentration range of interest,it is only necessary to run a standard prior to eachanalysis.
e) Dissolve 250 mg of the HMX sample in a 250-mL volumetricflask.
f) Inject standard solution into the chromatograph.
g) Make two 10-UL injections of the HMX solution into thechromatograph.
h) Calculate the percent RDX(x) in the sample using the followingexpression:
26
-- :•"" , ., ',. . . . . . • • - . .. • :,: • ,• ,• ..•..', •',:'.•.•:• • ,.•.• •/ •- •..•' •:• i• •;•i•,:, -... , I t.:•
%X = s xH *H
S XHs •*Wt
Where: W weightH peak heights standardt samplex = unknown
5.2.5 Determination of HMX contaminant in RDX
a) Follow procedure 5.2.4, substituting RDX for HNX and INXfor RDX where appropriate.
5.2.6 Determination of HMX and RDX as major ingredients.
a) prepare four standard solutions of each compound to contain0.2 mg to 0.8 mg per mL.
b) Adjust the detector attenuator so that all 10-pL injectionsresult in on-scale peaks.
c) Obtain linear calibration curves of peak height vs. weightof the nitramines.
d) Select weight of sample to be analyzed such that theweights of nitramines will be within calibration range.
e) Inject standard solution.
f) Inject duplicates (10 pL) and calculate quantity of nitramine(x) using the following expression:
Ws xW *Hx Hs
Where the symbols represent the same parameters described in the previousexpression.
27
RDX
LUHMX
0tLU
0I-ULU
o 10TIME (min.)
Figure c-1. Separation of HMX and RDXColumn: 250 mm x 2.1 mm i.d. Micro Pak-CNMobile Phase: 30% CH2 C02 /20% CH3 CN/hexanePressure: 2.75 MPa (400 pslg). Flow Rate: 0.5 mL/min.28
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