1. Primary Explosives Manufacture
12th CAD/PAD Technical Exchange Workshop
May 15-17, 2018
Bradley Sleadd, Ph.D.
DISTRIBUTION STATEMENT A (18-039). Approved for public release; distribution is unlimited.

2. Primary Explosives
LMNR
Current projections indicate an annual requirement of ca. 3 kgs of each 2
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

3. Diazodinitrophenol (DDNP)
DDNP (Diazodinitrophenol)
CAS #:
Picramic acid is commercially available
Simple diazotization reaction gives DDNP in high yield (80-90%)
When stored under 40% water has 1.4E hazard classification
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

4. Diazodinitrophenol (DDNP)
First diazo compound produced
Subsequently used to make dyes and explosives.
Forms yellow crystals in pure form
Impure forms may vary from dark yellow to green to dark brown
Less sensitive to impact but more powerful than mercury fulminate
Almost as powerful as lead azide
Friction sensitivity is much less than that of mercury fulminate, but approximates that of lead azide
Used with other materials to form priming mixtures, particularly where a high sensitivity to flame or heat is desired
Often used as an initiating explosive in propellant primer devices and is a substitute for lead styphnate in what are termed "non-toxic" (lead free) priming explosive compositions
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

5. Diazodintrophenol (DDNP)
Multiple 20 gram batches have been prepared
JAN-D -552 (1948)
Only one grade of DDNP is used for military purposes. This complies with the following requirements:
Color: Greenish yellow to brown.
Form: Tabular crystals having a maximum length of 0.2 millimeter.
Granulation: 100 percent shall pass through a No. 100 US standard sieve.
Bulk density: Minimum, 0.4 grams per milliliter.
Acidity: Maximum, 0.01 percent as hydrochloric acid.
Sand test: 0.40 gram shall crush not less than 33 grams of sand.
Recrystallization (acetone/water) is required to pass Form and Bulk Density tests.
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

6. Potassium dinitrobenzofuroxan (KDNBF)
KDNBF (Potassium dinitrobenzofuroxan)
Benzofuroxan (BF) is commercially available
Nitration of BF with mixed acid gives DNBF in high yield (85-90%)
DNBF has performance and sensitivity properties
consistent with a secondary explosive (i.e., TNT, RDX)
Reaction of DNBF with potassium bicarbonate in acetone/water
gives KDNBF in good yield (70-75%)
Morphology of KDNBF can be tuned with crystal habit modifiers
CAS #:
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

7. Potassium dinitrobenzofuroxan (KDNBF)
MIL-P-50486(AR), dated 19 March 1971 and Validation Notice 1, dated 29 August 1991, is inactive for new design and is no longer used except for replacement purposes.
ASSIST: Notice 3 dated 13 Nov which specifies it is still inactive for new designs.
Bulk density: 0.2 grams per milliliter, minimum.
Forms: KDNBF shall be in the form of plate-like crystals. In addition, the dried KDNBF powder shall be easily dispersible.
Granulation: Through a No. 50 US standard sieve, 98 percent minimum. Retained on a No US standard sieve, 4 percent maximum. Retained on a No US standard sieve, 10 to 75 percent.
Retained on a No US standard sieve, 85.0 to 100 percent.
Vacuum stability: Not more than 1.0 milliliters of gas shall be evolved at 120° ± 0.5°C in 40 hours.
Nitrogen content: percent ± 0.20 percent.
Differential thermal analysis: The DTA graph of the tested KDNBF sample shall show only one major exotherm and that exotherm shall occur between 210°C and 225°C.
Nuclear magnetic resonance: The NMR spectra of the tested KDNBF sample shall have five distinct peaks, one each at 5.77, 5.93, 6.13, 6.27, and 8.63 ppm. The average amplitude of the peaks at 5.93 and 6.13 ppm shall be greater than thirty percent of the peak at 8.63 ppm. In addition, there shall be no peak at 9.22 ppm greater than five percent of the peak at 8.63 ppm.
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

8. Potassium dinitrobenzofuroxan (KDNBF)
Less sensitive to impact and friction than lead azide and lead styphnate
Very high electrostatic discharge sensitivity
Combined with tetrazene or DDNP in percussion cap primers
Often used as an initiating explosive in propellant primer devices and is a substitute for lead styphnate in what are termed "non-toxic" (lead free) priming explosive compositions
NASA, MDA and contractors have an interest in a KDNBF supply
DNBF has been prepared at the 20 gram scale
KDNBF has been prepared at the 5 gram scale
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

9. Barium styphnate monohydrate (BS)
CAS #:
Simple metathesis reaction
Styphnic acid, ammonium hydroxide (ammonium styphnate)
Reaction with water soluble barium salt
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

10. Barium styphnate monohydrate (BS)
1,3-dihydroxybenzene (resorcinol) is too “hot” for direct nitration!
Must first be nitrosated to give the dinitroso intermediate
Slurry containing the dinitroso compound is added to hot nitric acid
Oxidizes the nitroso groups to nitro, adds third nitro group
Styphnic acid (trinitroresorcinol)
Styphnic acid has performance and sensitivity properties
consistent with a secondary explosive (i.e., TNT, RDX)
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

11. Barium styphnate monohydrate (BS)
Styphnic acid is treated with ammonia to deprotonate the acid
Gives the diammonium salt
Aqueous solution of barium chloride is then added
Barium styphnate monohydrate precipitates out
Washed with acetone and water
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

12. Barium styphnate monohydrate (BS)
WS A Material Specification
Color and appearance: Yellow brown to yellow.
Crystal Form and Dimension: Small discrete crystals having a maximum L/D (aspect ratio) of 5.
Granulation: Maximum of 20 percent shall remain on a No. 60 US standard sieve. Maximum of 60 percent shall remain on a No. 325 US standard sieve.
Apparent density: gm/cc.
Acidity, pH:
Purity: 98% minimum.
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

13. Barium styphnate monohydrate (BS)
Forms a trihydrate, a monohydrate and an anhydride
Anhydride is not stable in air and quickly picks up a water molecule
Trihydrate is formed initially during the metathesis reaction with the diammonium salt-treatment with dilute nitric acid dehydrates to the monohydrate
Monohydrate has three polymorphs, yellow labile, red labile and yellow stable
Both labile polymorphs will convert to yellow stable, which is much less water soluble
Morphology of BS can be tuned with crystal habit modifiers
Production process and crystal morphology determine the application
Most of the available information on BS is very old
Used in delay compositions, compositions for electric primers or igniters, or an ingredient in primary compositions
Styphnic acid has been prepared at the 5 gram scale
BS has been prepared at the 1 gram scale
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

14. Lead mononitroresorcinate (LMNR)
LMNR (Lead mononitroresorcinate)
CAS #:
Exactly four available references in SciFinder!
None included preparation
Only preparation reference was a British patent (circa 1930)
The actual structure of this material is difficult to determine
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

15. DEPARTMENT OF THE ARMY TECHNICAL MANUAL
MILITARY
EXPLOSIVES
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

16. Lead mononitroresorcinate (LMNR)
Molecular Formula: C12H8N2O8Pb
Odor / appearance: Not Available
Lower Flammability Limit: Not Available
Upper Flammability Limit: Not Available
Specific Gravity: Not Available
Evaporation Rate (Butyl Acetate = 1): Not Available
Viscosity: Not Available
pH: Not Available
Molecular Weight: g/mol
Manufacturing
Company
MIL-L-46496
LMNR must meet the following requirements for military use:
Color and appearance: LMNR shall be light brown in color.
Apparent density: 0.20 to 0.35 grams per milliliter.
Acidity: The pH shall be between 5.0 and 6.5 for a solution of one gram of the material in 150 milliliters of water.
Lead content: 70.5 to 72.5 percent.
Nitro group content: 7.2 to 7.6 percent.
Vacuum stability at 120°C: 0.4 milliliters of gas in 40 hours with a 2.3 gram sample, maximum
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

17. Lead mononitroresorcinate (LMNR)
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

18. Lead mononitroresorcinate (LMNR)
British patent preparation reference is not clear on how to prepare the basic LMNR preferentially
Will likely require some Edisonian research to nail down spec-compliant LMNR
Will need to confirm with customers what type/form of LMNR they actually want
Basic LMNR
Normal LMNR
Acid LMNR
Additional tests?
Function testing (Sand Test, etc.)?
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

19. Specification Testing
Primary explosives have not previously been a product of NSWC IHEODTD
Analytical labs have no experience dealing with primary explosives
All of the specifications are ancient!
Some are inactive for new designs
All have archaic chemical analyses
Most call out large samples ( grams) for drying and testing
We will need to “renegotiate” spec requirements with customers
Smaller sample sizes
Waive certain spec requirements
Communicate with customers to define what their actual needs/desires are:
“We don’t care as long as it works!”
Particle size/morphology
Flowability
Function testing
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

20. Primary Explosives
NSWC IHEODTD will be a supplier of some critical primary explosives:
Diazodinitrophenol (DDNP)
Potassium dinitrobenzofuroxan (KDNBF)
Barium styphnate (BS)
Lead mononitroresorcinate (LMNR)
Will collaborate with individual customers to determine project specific specifications and acceptance criteria
Code A material should be available for purchase in Q1-Q2 FY19
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.

21. Acknowledgments
Navy Energetics Manufacturing Technology Center Charles Painter NSWC Indian Head EOD Technology Division Patrick Greer Chemical Development and Manufacturing Branch Kim Csanadi Tod Ricks David Boruta Patrick Caruana Derek Reynolds
DISTRIBUTION STATEMENT A. Approved for public release; distribution is unlimited.