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IG!JXPLOS IVE DETONATION VELOCITIES FROM PHEIR JOMPOSITION AND STI(OCTU'E 112)

RED ICT ING

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UNLLAbI ILU
Uoterd) t"SWCUIRITY CLASSIFVICATION OF THIS PAGE ("oin 0Vte

~I.RPORT
4

NUMIREf

AGEREAD D"UMNTATON REPOT DO REPOT 'JENTAION AGEBEFORE j2. GOVT ACCESSION NO.
___________

COMPLETING FORM
V. RECIPIENT'$ CATALOG 14UMERR
__________

U45TRUC'YIONS

NWSY TR 78-4k
TITLE~ (andI Subtitle)

I.

YYPe Or REPORT a PERIOD covxftft

PREDICTING HIGH EXPLOSIVE DETON4ATION VELOCITIES FROM THEIR COMPOSITION AND

STRUCTURE (II)
S7. AUTHOR(s).

Addendum Report
A . PE9RFORuIN Q Otto. REPORT. plum FER
OATpfMTuE~

Lewis R. Rothstein Robert Petersen

ME
P~ROGAM WOI( UIT

I.

Naial Weapons Station Yorktown, Virginia 23691

(Code 50)
_______________

PERFORMING ORGANIZATION NAME AND0 ADDRESS

-0.

1.CONTftOLLINGO,"7IcENAMP

JEORTplAT

'November 1978
IS.
____ ___ ___ ____ ____ ___ ____ __

NUMBER Of PAGES

-ii and 1-6

It.

14.MOITORING

AGENCY NAME & ADDRESS(ff diffeednt from Coeifreling Office)

SECURITY CLASS. (0i this oport)

UNCLASSIFIED
ISW.. DEC&LASSI F1 CATION/
SCHEDULit IS. DISTRIBUTION STATEMENT (of tbis Report) DOWNGRADING

Approved for public release; distribution unlimited.

17.

DISTRIBUTION STATEMENT (of the abstract entered In Block 20, it different from, Report)

SO. SUPPLEMENTARY NOTES

19.

KEY WORDS fContinus on reverse. side if necessaajy dind idonltiy by block numuber)

Explosives Detonation velocities, prediction of

20. ABSTRACT (Consinue an reverse oid* if iueoeewy and idenftiby block maybe,)-

See reverse side of this form.

DD

A14"f

1473

EUWTION OF I NOV SO 1S O9USOLETE

E/N~oIUNCLASSIFIED

SIF

"tNELASUTEF'l
..Lut'mrry CLASSIFICATION OF THIS PAGQWIw.,en DateSne

"0.-ABSTRACT A previous technical report described a s1 e empirical relationship between detonation velocity at the etical maximum density and a factor, F, that is dependent sole y upon chemical composition and structure. The explosives ran d from nitroaromatics, cyclic and linear nitramines, nitra e esters and
nitro-nitrato aliphatics to zero hydrogen exp osives, carbonless
'".

"

explosives and hydrogen rich explosives. Mi or modifications have been made to the equations presented i that report, Including a correction factor for liquid expl sives, that have resulted in an improved predictive nodel i which: 95% of the predicted detonation velocities lie withi 5% of experirmental,

the absolute error for 64 explosives is 94~2.3%; and the corre-' latlon coefficient for the linear regres on relationship is
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NWSY TR 78-4

FOREWORD

1. This is an addendum report to NWSY TR 78-3 documenting the postulate that a simple, empirical linear relationship exists between detonation velocity and a factor, F, that is dependent solely upon the chemical composition and structure for a gamut of explosives, with a correction factor to be used for liquid explosives.

Released by

W. McBRIDE, Director Naval Explosives Development Engineering Department

Under authority of LEO A. HIBSON, JR. Comnanding Officer

November 1978

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78-4 NWSY TR

CONTENTS

Page FOREWORD ........ ..... ........................

TEXT: PREDICTING HIGH EXPLOSIVE DETONATION VELOCITIES FROM THEIR COMPOSITION AND STRUCTURE (II) ...... ...................

TABLE:

Predicted Detonation Velocities ........

Ii

NWSY TR 78-4

PREDICTING HIGH EXPLOSIVE DETONATION VELOCITIES FROM THEIR COMPOSITION AND STRUCTURE (II)

In a previous report' it was shown that a simple, empirical linear relationship existed between detonation velocity for ideal explosives at theoretical maximum density and a factor, F, dependent solely upon chemical composition and structure. At that time, it was also noted that the calculated detonation velocities for tetranitromethane (TNM) and TNM/nitromethane (NM) mixtures did not fit the proposed model despite their known ideality and that liquid explosives in general calculated to anomalously higher detonation velocities than measured. It should now be added that if there is a reasonable expectation that a given explosive will be a liquid, a further simple correctin can be made in calculating F which substantially reduces the error between predicted and observed detonation velocities. This revised equation for calculating F is

F n(O)
(1) F [100 0 x where

+ n(N)

__ C)2.5
4

1
-G

.7

G = 0.4 for liquid explosives, for solid explosives G A z I if the compcund is aromatic, otherwise A 0

and where, as before, for one mole of the composition: n(0) n(N) n( H n(B) = = = = number of number of number of number of available oxygen atoms nitrogen atoms hydrogen atoms oxygen atoms in excess of those already to form CO 20 2 and H

'Lewis R, Rothstein and Robert Petersen, NWSY TR 78-3, Predicting Righ Explosivc Detonation Velocities From Their Composition and Structures Sep 1978.

NWSY TR 78-4 r.(C) = number of oxygen atoms doubly bonded directly to carbon as in carbonyl - 0 n(D) = number of oxygen atoms singly bonded directly to carbon as in a -0 - R linkage where R can equal -H, -NH 4 , -C, etc. n(E) = nui ber of nitrato groups existing either in a nitrate ester configuration or as a nitric acid salt such as hydrazine mononi trate. Minor changes to the A, B, C and E fractions have been made over those originally published. Thus, where F previously was reported as 100 x 2nX 4MW

nH. 2

'

the principal changes are that: the aromaticity correction factor, (A), is not based, as before, on the number of aromatic rings present but merely upon whether or not the compound is aromatic; additionally, the correction for oxygen in excess of that required to form C02 and H20, (B), is weighted more heavily, whereas carbonyl oxygen, (C), and nitrato, (E), corrections are de-emphasized slightly. These modifications were made arbitrarily to further
* mn~ -e

4-S-

h^+

of D' experimental versus F. Molecular weights and atomic compositions for composited explosives were derived respectively from the sum of the weighted average molecular weights and the weighted 2 average sums of each elemental mole fraction as previously described. Table I lists the experimental detonation velocities previously reported 3 and the detonation veiocities predicted from the newly generated linear regression equation (2) or (3) = F - 0.26 .' 0.55 F 0.55 D' + 0.26

where, as before. D' is the detonation velocity at theoretical maximum density in millimeters per microsecond (mm/1.isec).
2 1bid., 3 Thid.,

Appendix, p. 13. Tables I and II, pp. 6-9.

NWSY TR 78-4 Substantial improvements in predicted versus experimental 0' values are apparent over those previously reported.4 * The absolute error for all 64 data points is now + 2.3% versus 2.8%. Sixty-on' of sixty-four calculated D' values., 95%, lie within 5% of the experimentally reported values.
0 Sixty-three of sixty-four D' values,

98%, lie within 7% of

experimental. * Only one value, NM, is discrepant by -13%. * The correlation coefficient for the linear regression plot of all data resulting in Eq. (3) is >0.96. * For the liquid explosives, the percent error between calculated and experimental D' values determined with and without the 0.4 correction factor are as follows: Explosive: From NWSY TR 78-34 (w/o liquid correction): From Eqs. (1) and (3): NIBTN +5% -1% TNM +20% +3% TNM/NM +26% +4% NG +6% -3% EOUn +11% +3% 0% -13%

No attempt has been made to reconcile this basically empirical relationship to more formal theories. Investigators such as Martin and Yallop 5 earlier tried to weight oxygen balance and the strength of the type bonds with detonation velocity. However, Price 6 showed shortly thereafter that their treatment had only limited applicability. 7 More rce'n& inve,, LAt%,-n- appear to be merely variations of the theme first introduced by Kamlet, et al., 9 10 11 12 n3mely where fairly

4T7id., pp. 6-7. 5A.R. Martin and H.J. Yallop, Trans. Faraday Soc 54 257 (1958). 6 D. Price, Chem. Rev. 59 801 (1959). 7 1.N. Aizenstadt, transl-atei from Fizika Goreniyva, Vol 12, No. 5, pp 754-8, Sep-Oct 1976, copy written by Plenum Publishing Corp., New York, NY. 6 V.I. Pepekin and Yu. A. Lebedev, DOKLADY AKADEMII NAVK, Vol 234, No. 6 (1977), Consultants Bur. Translation, .zbid., p. 460. 9M.J. Kamlet and H. Hurwltz, J. Chem. Phys. 48 3690 (1968 1 0 M.J. Kamlet and C. Dickinson, J. Chem. Phys. 48 43 (1968 (1968 4" 36 (1968). Chem. Phys Phys. J. Chem. J.E. Abalard, IAM.J. Kamlet 12M.J. Kanflet and and.S.J. Jacobs, J. . 4T.-23 3

o4

12 b

NWSY TR 78-4

simple relationships between heats of formations of chosen detonation products, explosive density, p0, and the sought for detonation velocity It was shown earlier that at least one of these were demonstrated. later treatments, that of Aizenstadt was inferior to both Kamlet's and that presented in NWSY TR 78-3.15 Since the even simpler relationship presented here and in NWSY TR 78-31 is based exclusively upon composition and structure (that is if one allows for predictive knowledge of whether or not an explosive is a liquid or a solid) - it is concluded, inescapably, that this compositional/structural relationship, albeit highly empirical, must be more than casually correlatable to the nmre fundamental thermochemical (AHf) and physical (Po) factors just mentioned. However, since any empirical relationship may be found wanting with increased data dvailability, additional experimental detonation velocity and theoretical maximum density data would be welcomed by the authors for further testing of the relationships presented here. Of particular interest would be detonation velocity data on the many heterocyclic nitroaromatics that have been synthesized in recent years but for which no detonation velocity data has been published.

I
1 30p

cit.., Addendum, pp.

14-15.

NWSY TR 78-4

TABLE I. No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16
It

PREDICTED DETONATION VELOCITIES Elemental composition H N- -0 2 8 6 8.26 6 4 5 9.41 7.14 5.86 7.82 5.73 6.94 6 6 8 8 8 7.73 6 8 3 6 7.55 6.53 12 10 8 13 8.09 6 14 3 6 7.73 7.44 5.86 5.55 5.98 5.55 14 I z 18 4 2 6 10 5.96 8 6 8 11 j3 26 9 6 6 12 10 Exptl talc'd Mol D' I Factor D' % (m/psec) error wt ((J/psecl F 348 322 296 386 296 222 388 95 25Z 296 278 222 222 223 222 386 316 452 150 104 232 326 221 240 258 287 286
1/4

Xpl HNB SORGUYL HMX BTNEU 9404 RDX BTNEN HN BTF 9011 OCTOL 9010 COMP C-4 CYCLOTOL 9205 TNETB
Ft

TMD (l/cc) 2+ 2.01 1.90 1.86 1.87 1.83 1.96 1.64 1.90 1.80 1.83 1.82 1.59(?) 1.77 1.72 1.78
K.i 7/

C 6 4 4 5 4.20 3 4 0 6 5.12 4.94 3.35 4.02 3.96 4.04 6 6 2 1 4 6 4.53 4 6 7 15 3 2 6 12 5

9.50 9.15 9.14 9.00 8.89 8.85 8.85 8.69 8.61 8.59 8.54 8.49 8.04 8.33 8.32 8.30 8.29 8.26 8.23 8.16 8.15 8.10 8.05 8.00 7.94 7.91 7.86
7.80

5.27 5.13 5.24 5.28 5.17 5.18 5.04 4.88 4.89 4.96 4.68 5.05 4.65 4.85 4.72 4.97 4.71 4.70 4.83 4.81 4.69 4.75 4.71 4.63 4.59 4.54 4.54
4.b0

9.11 8.85 9.05 9.13 8.93 8.95 8.69 8.40 8.42 8.55 8.40 8.71 7.98 8.35 8.11 8.56 8.09 8.07 8.31 8.27 8.05 8.16 8.09 7.95 7.87 7.78 7.78
7.89

-4 -3 -1 +1 +1 +1 -2 -3 -2 -1 -2 +3 -1 0 -3 +3 -2 -2 +1 +1 -1 +1 +1 -1 -1 -2 -1
+1

18 19 20 21 22 23 24 25 26 27
Z8

MHN EDNA NQ DINGU DNPN COMP B-3 DINA TATB TETRYL NIBTN
K-SAL

1.73 1.71 1.72 1.94 1.73 1.74 1.67 1.94 1.73 1.64
.b

5.86 5.44 5.24 6.50 6 4 8 6 4 6 4 4 6 4 6 10 5.56 4.78 8 6 5 6 24 G 10 5 4 9 4 6 r 4 8 3 4 5 8 3

29 30 31 32 33 34

TPEON NG EDD DATB HNAS PETRIN

1.58 1.60 1.60 1.84 1.77 1.54(?

732 227 186 243 452 271

7.71 7.70 7.69 7.67 7.65 7.64

4.29 4.35 4.71 4.49 4.40 4.32

7.34 7.44 8.09 7.69 7.53 7.38

-5 -3 +5 0 -2 -3

__

--

_--__I____-

NWSY TR 76-4

TABL.
-

I.

PREDICTED DTONATION VELOCITIES (cont'd)

Elernent~
MITosijtonC

No. 35 36 37 38 39 40 41 42 43 44

Xpl DNPTB TNPON DPEHN PIC ACID DIPAM TNA XPL D GTNB EGDN TNB

TMD (q/cc) 1.68 1.68(?) 1.63 1.76 1.79 1.76 1.72 1.63 1.48(?) 1.64(?) 1.85 1.64?) 1.70 ?. 1.74 1.52(?)
,..,...

Y ~~

T12 10 19 7 12 6 7 16 6 6 8 12 13 12 6 5 13

Factor 0' Mol wt (Lmlpsec) F ( 355 318 524 229 454 228 246 472 152 213 7.63 7.60 7.53 7.50 7.49 7.42 7.36 7.34 7.30 7.27 7.25 7.20 7.18 7.12 7.10 4.50 4.27 4.41 4.31 4.35 4.38 4.33 4.31 4.38 4.26 4.14 4.36 4.30 4.02 4.2P.

'

-a

ITEc D' error 7.71 7.29 7.55 7.36 7.44 7.49 7.40 7.36 7.49 7.27 7.05 745 7.35 6.84 7.20 6.7 7.22 7.07
6.67 7.16 6.49

7 8 10 6 12 6 6 10 2 6 12 12 12 14 4

9 6 16 3 6 4 6 12 4 3 4 5 4 6 6

5 4 6 3 8 4 4 6 2 3 8 7 6 6 4 4 6

+1 -4 0 -2 -1 +1 +1 0
43

0 -3 +4 +2 -4 +1 -4
43

45 TACOT 46 HNDP 47 HNDPO 48 HNS 49 DNDMOA 5.. FIvONITE . 51 52

53 54

12 n

I.

WiAZ HNDS*

TNT NM/TNM* ONPEN

6 1.63 1.65(?) 12
1.65 ...

7 1.00

2 4

5 2.40

3 1.60 3

55 56 57 58 59

TNC

1.68(?) 7 1.60(?)l 8 1.60(?) 8 1.61(?) 7 1.38 4 1.65 1 1:60"' 1.16 ... 1 i 1

10

5 7 7 5
8

17

6 3.20

388 439 440 450 20f 3I4 210 456

227 88

7.04

3.99

7.00 7.00
6.96 6.88

4.23 4.15

+1
-4 +4

3.93 4.20

243 273 257 243 196 380 61 2631

96

6.85
6.80

4.00

3.133 3.97

6.80 6.31 6.80

6.75

-1
-5

ET PIC TNAN DEGN

3 3

7 7
8 12 2 6

6.80 6.80
6.76

3.73 4.00

-7 0
0

60 TNM 61 TMPTN J62 DNPF 63 MM 64 TNN

0 4 15001LO 12 1 3 3 5

6.55 6.44 6.38 6.32 6.00

3.97 4.01 3.74 3.29 3.39

6.75 6.2 6.33 5.51 5.69

+3

I+6
-13 -5

"*Sulfur atom treated as an oxygen. **1:025 mole ratio.

Note: (?) indicates that the reference value given is at the experimental condition and TMD data is not listed.

T.,

- ., ..

.77 -;.

NWSY TR 78-4

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