Preparation of ammonium dinitroamide (ADN) crystals, ADN crystals and energetic composites containing them

1. A process for the preparation of ammonium dinitroamide (ADN) crystals from a solution containing said ADN in a solvent, comprising:

including an effective and non-excessive amount of at least one crystal habit modifier capable of reducing the shape factor of the crystals in the solution; and

performing crystallization in said solution containing said at least one crystal habit modifier by any appropriate treatment.

2. The process according to claim 1 wherein said crystallization is carried out by at least one selected from the group consisting of increasing the concentration of ADN in said solution, adding a non-solvent for ADN to said solution, and cooling said solution.

3. The process according to claim 1 wherein the solvent of said solution is selected from alcohols and mixtures thereof.

4. The process according to claim 1 wherein said effective and non-excessive amount is greater than or equal to 0.005% by weight based on the weight of ADN in solution.

5. The process according to claim 1 wherein said effective and non-excessive amount is greater than or equal to 0.01% by weight.

6. The process according to claim 1 wherein said effective and non-excessive amount is greater than or equal to 0.1% by weight.

7. The process according to claim 1 wherein said effective and non-excessive amount is less than 5% by weight, based on the weight of ADN in solution.

8. The process according to claim 1 wherein said at least one crystal habit modifier is selected from the salts of alkaline earth metal cations.

9. The process according to claim 1 wherein said at least one crystal habit modifier is selected from calcium and/or magnesium salts.

10. The process according to claim 1 wherein said at least one crystal habit modifier is selected from the following calcium salts:

Name

Formula

calcium butyrate

Ca(C 4 H 7 O 2 ) 2 •H 2 O

calcium carbonate

CaCO 3

calcium perchlorate

Ca(ClO 4 ) 2

calcium chloride

CaCl 2

calcium cinnamate

Ca(C 9 H 7 O 2 ) 2 •3H 2 O

calcium citrate

Ca(C 6 H 5 O 7 ) 2 •4H 2 O

calcium formate

Ca(CHO 2 ) 2

calcium fumarate

CaC 4 H 2 O 4 •3H 2 O

calcium d-gluconate

Ca(C 6 H 11 O 7 ) 2 •H 2 O

calcium glycerophosphate

CaC 3 H 5 (OH) 2 PO 4

calcium isobutyrate

Ca(C 4 H 7 O 2 ) 2 •5H 2 O

calcium lactate

Ca(C 3 H 5 O 3 ) 2 •5H 2 O

calcium laurate

Ca(C 12 H 23 O 2 ) 2 •H 2 O

calcium linoleate

Ca(C 18 H 31 O 2 ) 2

calcium malate

CaC 4 H 4 O 5 •2H 2 O

calcium dihydrogen malate

Ca(HC 4 H 4 O 5 ) 2 •6H 2 O

calcium maleate

CaC 4 H 2 O 4 •H 2 O

calcium malonate

CaC 3 H 2 O 4 •4H 2 O

calcium α-methylbutyrate

Ca(C 5 H 9 O 2 ) 2

calcium nitrate

Ca(NO 3 ) 2

calcium oleate

Ca(C 18 H 33 O 2 ) 2

calcium oxalate

CaC 2 O 4

calcium palmitate

Ca(C 16 H 31 O 2 ) 2

calcium 1-phenol-4-sulfonate

Ca[C 6 H 4 (OH)SO 3 ] 2 •H 2 O

calcium hypophosphate

Ca 2 P 2 O 6 •2H 2 O

calcium metaphosphate

Ca(PO 3 ) 2

calcium di(sec)orthophosphate

CaHPO 4 •4H 2 O

calcium mono(prim)orthophosphate

Ca(H 2 PO 4 ) 2 •H 2 O

calcium tri(tert)orthophosphate

Ca 3 (PO 4 ) 2 •H 2 O

calcium hypophosphite

Ca(H 2 PO 2 ) 2

calcium diorthophosphite

2CaHPO 3 •3H 2 O

calcium propionate

Ca(C 3 H 5 O 2 ) 2 •H 2 O

calcium 1-quinate

Ca(C 7 H 11 O 6 ) 2 •10H 2 O

calcium salicylate

Ca(C 7 H 5 O 3 ) 2 •2H 2 O

calcium metasilicate

CaSiO 3

calcium diorthosilicate

Ca 2 SiO 4

calcium silicate

Ca 3 SiO 5 or (3CaO•SiO 2 )

calcium stearate

Ca(C 18 H 35 O 2 ) 2

calcium succinate

CaC 4 H 6 O 4 •3H 2 O

calcium sulfate

CaSO 4

calcium tartrate

CaC 4 H 4 O 6 •4H 2 O

calcium valerate

Ca(C 5 H 9 O 2 ) 2

and the following magnesium salts:

Name

Formula

magnesium acetate

Mg(C 2 H 3 O 2 ) 2

magnesium benzoate

Mg 3 (C 7 H 5 O 2 ) 2 •3H 2 O

magnesium bismuth nitrate

3Mg(NO 3 ) 2 •2Bi(NO 3 ) 2 •24H 2 O

magnesium diborate

Mg 2 B 2 O 4 •H 2 O

magnesium metaborate

Mg(BO 2 ) 2 •3H 2 O

magnesium orthoborate

Mg 3 (BO 3 ) 2

magnesium carbonate

MgCO 3

magnesium perchlorate

Mg(ClO 4 ) 2

magnesium chloride

MgCl 2

magnesium mono-H-citrate

MgHC 6 H 5 O 7 •5H 2 O

magnesium formate

Mg(CHO 2 ) 2 •2H 2 O

magnesium lactate

Mg(C 3 H 5 O 3 ) 2 •3H 2 O

magnesium laurate

Mg(C 12 H 23 O 2 ) 2 •2H 2 O

magnesium myristate

Mg(C 14 H 27 O 2 ) 2

magnesium nitrate

Mg(NO 3 ) 2

magnesium oleate

Mg(C 18 H 33 O 2 ) 2

magnesium oxalate

MgC 2 O 4 •2H 2 O

magnesium palmitate

Mg(C 16 H 31 O 2 ) 2

magnesium orthophosphate

Mg 3 (PO 4 ) 2

magnesium mono-H-orthophosphate

MgHPO 4 •3H 2 O

magnesium salicylate

Mg(C 7 H 5 O 3 ) 2 •4H 2 O

magnesium stearate

Mg(C 18 H 35 O 2 ) 2

magnesium sulfate

MgSO 4

magnesium d-tartrate

MgC 4 H 4 O 6 •5H 2 O

magnesium hydrogen d-tartrate

Mg(HC 4 H 4 O 6 ) 2 •4H 2 O

magnesium thiosulfate

MgS 2 O 3 •6H 2 O.

11. The process according to claim 1 wherein said at least one crystal habit modifier is selected from calcium carbonate (CaCO 3 ), calcium nitrate (Ca(NO 3 ) 2 ) and mixtures thereof (CaCO 3 +Ca(NO 3 ) 2 ).