medina? [Archive] - The Explosives and Weapons Forum

cutefix

June 6th, 2002, 02:36 AM

Qoute:
---------------------------------------------------------------------
In PATR 2700 vol 2, HMX is said to have a relative brisance ( to TNT ) of 125-155 in the sand crush test, a VOD of 9124 at 1.84 g/cc and a Trautzl test of 159-165 relative to TNT.
MeDINA was rated as follows: Relative brisance 127-131 in the sand test, VOD 8500 at 1.68 g/cc and Trautzl test of 188-210 again relative to TNT.
---------------------------------------------------------------------
I still think that HMX is the stronger explosive and not Medina..
Lead block test is not an efficient test for true explosive power specially for military application .
True power of a pure military explosive is related by its ability to accelerate metals which corresponds to detonation velocity and detonation pressure.
If HMX can give a calculated detonation pressure of about 390 kbar while the MEDINA can provide only 345 kbar .
These second value,indicates that methylenedinitramine is comparable to cyclonite which gaves similar values if based upon its similar detonation velocity of 8500meters per second.
Implying its power is just average for a nitramine explosive.
Meanwhile these lead block values are unreliable indicator of explosive power.
For example RDX has a lead block volume of 480 cubic centimeter at a detonation rate of 8500 meters pers second.While PETN gives a value of 520 cc at VOD of 8400 m/s.
This proportionate relation are applicable to aromatic explosives TNT,TNP and Tetryl.
Explosive Lead block Value(cc)/ Detonation velocity(m/s)
TNT
300 / 6900
Picric Acid 315 / 7250
Tetryl 400 / 7500
And not to nitramine explosives like HMX and MEDINA
The Nitric esters even show discrepancies:
Nitroglycerine 520 / 7500
Nitroglycol 620/ 7300
Methyl nitrate 600/ 6500

So how can we believe that the explosive expansion of lead block reflects true explosive power…,and be used to relate how many percent more powerful if compared to the so called standard explosive-TNT.

[ June 06, 2002, 01:48 AM: Message edited by: cutefix ]

cutefix

June 6th, 2002, 05:32 AM

Even if MEDINA is less interesting to me than other nitramine explosives,I found to have in my old files a copy of its recipe made from its precursor formamide and hexamethylenetetramine on a preparative scale.
This is an interesting comparative procedure.

.The formula originated as typed on its reference,was derived from US patent files.#2856429 & 2713594
.
Preparation of precursor: Methylenedinitroformamide:
In a 1 liter reaction vessel place-A mixture of 70 grams of hexamine(0.5mole) and 270 grams(6mole) of freshly distilled formamide were heated to 140 deg C and maintained for 4 hours.
On cooling the crystals were separated.
Initial yield is 87.8 grams(29% of theory)

To obtain more crop,the mother liquor was retained and to it was added 23.5 grams of hexamine and 90 grams of formamide.Heat the mixture to 140deg C for 5 hours.Cool the mixture and separate the resulting crystals.
Succeeding yields range from varies from 80-100 grams per reaction run.
If you desire to obtain more precursor,Repeat this procedure for 8 times using similar quantities hexamine and formamide(23.5grams & 90 grams respectively).This will takes about 50 hours consuming totally 281.5 grams of hexamine and 1080 grams of formamide.The total yield of methylenediformamide is 1034 grams(nearly 78%of theory).
Reaction equation
(CH2)6N4 + 12 HCONH2 -----> 6H2NC=O-CH2-C=O-NH2

The pure product is a white crystalline material melting at 140-141degC.It is soluble in water at an extent of 100 grams per 100 cc.and 6.6 gram per 100 cc of isopropanol.

Preparation of Methylenedinitramine:
Place the 2-3 liter reaction vessel preferably in a dry ice-kerosene bath so as to much better control the temperature of the exothermic reaction between nitric acid,acetic anhydride and methylenediformamide.
Nine moles( 380 grams) of 100% HNO3 was added as rapidly as possible at +-2deg C. to a well stirred suspension of 102 grams (1 mole) of methylenediformamide in a 380 ml(4 mole) of acetic anhydride.
Upon completion of the nitric acid addition,remove the dry ice-kerosene bath,and replace it with an ice-bath.Allow the reaction to age over this ice bath for 4 hours.
You will notice that after the application of the ice -bath,the temperature of the reaction will rise to 8deg C for 15-30 minutes and then fell to +2deg C where it remained during the aging period.
At the end of the aging period the reaction mixture was poured slowly with stirring into a mixture of one liter water and 1000-1500 grams of cracked ice.
The methylenedi(nitroformamide) was immediately collected on a filter and washed with three 100 ml portions of ice –water.The filter cake was pressed with a rubber dam.The yield at this point was 190-220 grams of damp material.
This methylenedi(nitroformamide) is stirred into 100 ml of formic acid and the resulting paste allowed to stand overnight.
The following day the mixture was warmed to 65 deg C to dissolve the methylenedinitramine which has crystallized. Filter and cool to ice temperature(and seed it preferably to cause crystallization.One way of doing this is to rub gently the end of the stirring rod inside the walls under the crystallizing solution).This crystallization will take 5-6 hours.The crystals were collected on a filter and washed with benzene (or toluene).
The yield at this point is 70-80 grams of pure methylenedinitramine(50-60% based on methylenediformamide.
To obtain a second crop of methylenedinitramine,the mother liquor(with formic acid) was concentrated under reduced pressure and cooled to ice temperature and seeded to cause crystallization.The calculated total yield was 75-85% of theoretical based on the amount of methylenediformamide,about 100-115 grams of MEDINA.
Reaction equation
Formation of methylenedi(nitroformamide).
H2NC=O-CH2-C=ONH2 + (CH3CO)2O + 2HNO3--> H2N-NO2-CHO-CH2-CHO-H2N-NO2 + CH3COOH
Hydrolysis with formic acid
H2N-NO2-CHO-CH2-CHO-H2N-NO2 + H2O ( in HCOOH)-->HNNO2-CH2-NNO2H
For further purifications of Methylenedinitramine.Recrystallize it from a 9/1 by volume mixture of either of these solvents composition:
ethylenedichloride/isopropanol,
ethylenedichloride/2-nitropropane
ethylenedichloride/95%acetic acid

The purified Methylenedinitramine melts at 105-106deg C.It begins to decompose with the evolution of gas at 110degC.

[ June 06, 2002, 04:41 AM: Message edited by: cutefix ]

Microtek

June 6th, 2002, 09:39 AM

I'd say that the intended use should decide the most appropriate test. For instance, if someone needed to blow cavities in blocks of metal, I think the Trautzl test would be excellent....

CFV

June 17th, 2002, 08:31 PM

Theoretical stuff: In a class of explosives like nitramines, the higher density, bigger molecules will give more power because more realizable energy can be packed in the same space. Bigger molecules using the same proportion of elements are more dense because the formation of covalent bonds makes atoms come closer together than if they were just pushed together but from different molecules. HMX is a big ring molecule, same as RDX but with an extra CH2NNO2 unit. It has higher density (TMD 1.902) than RDX, 1.806, its det. vel is 9.11 km/sec vs. 8.70 for RDX. It is considered more powerful. Medina is a small molecule. I don't have a density for it, but the already posted det. vel. is in line with its expected lower density than either of those famous military explosives.

The new king is likely HNIW, also known as cl-20. Its the first explosive to clock at over 10 km/sec. It is a big cage molecule, looks a bit like hexamethylene tetramine but with six ring nitrogens fixed with NO2s like HMX. Within a class of explosives, detonation speed and brisance correlate well.

cutefix

June 17th, 2002, 10:54 PM

Indeed the trend today is to explore the vast possibilities that HNIW can provide to munitions;from high performance gun propellants , shaped charges etc,.I think the only limitation is the cost of its production.Even there had been practical methods to nitrate the special reactant (acetyl Isowurtzitane derivatives) with mixed acids;but the effort of debenzylation of the condensation products of glyoxal and benzylamine still requires the expensive palladium catalyst.
Therefore it will take some time before it can reach the level of comparatively lower cost needed to make HMX.

megalomania

June 17th, 2002, 11:46 PM

That statement of MEDINA being the most “powerful” is misleading, it does relate to only one aspect of an explosives performance. It is not the most powerful in the typical sense of detonation velocity.

The current winner in the most powerful explosives debate is heptanitrocubane (HpNC). It has beat out the theoretically more powerful octanitrocubane (ONC) in actual tests recently performed. ONC has only been synthesized in the last year, but it has been calculated to have the greatest density of any explosive we could make. In reality ONC does not achieve this theoretical density. Since it has existed for such a short time, researchers conclude that they simply have yet to find its most dense crystalline form. The default winner is the next best thing, HpNC. Further conjecture into nitro cubane chemistry has hypothesized at the possibility of polynitrocubane molecules which could achieve even greater densities.

For furthur reading on the subject, check out these titles:
P.E. Eaton, M.X. Zhang, Propellants, Explosives, Pyrotechnics 27, 1-6 (2002)
M.X. Zhang, P.E. Eaton, and R. Gilardi, Angew. Chemie Int. Ed. Engl. 39, 401-404 (2000)
J. Kortus, M.R. Pederson, and S.L. Richardson, Chemical Physics Letters 322, 224-230 (2000)
M.X. Zhang, P.E. Eaton, and R. Gilardi, Advanced Materials 12, 1143-1148 (2000)

There are many others, I have a big stack sitting right next to me. I will be sifting through all these over the summer to add the synthesis of tetra-, hepta, and octanitrocubanes to my website.

CFV

June 22nd, 2002, 01:04 AM

Much thanks for the replys to my recent post. If I may refer to members by their member number (a la Spectre), I appreciate Number 3's reference to cubane very much. I know this molecule was a tour-de-force effort by the mil. labs since it had the factors they were looking for in an explosive candidate-- molecular size, giving density, a cage shape (cubane is just that - a cube of carbon atoms), and one more thing, strained bonds for a positive heat of formation (more energy released on detonation). The second item works against the last to stabilize the molecule. Strained bonds of cubane are more likely to break but if each atom at a cube corner is held in place by three bonds, the rupture of one bond is more likely to repair itself. Contrast this with Medina. If a bond breaks the molecule is kaput.
I did not know that cubane turned out to be more than a lab curiosity. Is there any performance data for the nitro versions of it that can be divulged on a public site?
Is it true that ADN, Ammonium dinitrimide, was discovered in the process of cubane synthesis research?

cutefix

June 23rd, 2002, 06:17 AM

Qoute:

“If a bond breaks the molecule is kaput.”

Indeed the low stability of these MEDINA is one major cause,that (in some laboratories) it produced superior lead block test results as compared to related nitramines.Just visualize one methylene carrying the double nitramines(four nitrogen vs.a single carbon) .
When initiated,more gaseous products are formed rapidly with none or lesser tendency to form finely divided carbon which tend to lessen explosive performance in other complex structured and multi-carbon explosives.
This is similar reason why astrolite G(which is not very stable also) has better explosive property than RDX or HMX of comparable density)because most of the explosion products are gaseous(N2 and H2O).

Its interesting to see developments in these cubane chemistry.specially as applied to explosives.
Somehow they are a more difficult to synthesize;maybe more than preparing hexanitroadamantane from its precursors….

Regarding ammonium dinitramide;I think its development is more connected in the study of nitro-and dinitroureas.

CFV

June 25th, 2002, 02:09 AM

"Pop the champagne cork!" I shouted to my significant other. "I have been quoted, in print. Finally I'm on my way." There must be value to swaddling one's language in earthy tones.
It will be exciting to see how cubane is gotten together. The NIST webbook quotes its heat of formation as +129.5 Kcal/mole. (http://webbook.nist.gov/chemistry). It was done in the '60s. I'll bet those chemists could also figure out how to get the front coil springs into a 60s Buick without using a spring compresser. Like azide, cubane is a compressed q.m. spring ready to snap back to its elements. Even without the nitro substitutions it is still a zippy thing. But is it just too hard to make?

cutefix

June 25th, 2002, 02:45 AM

Cubanes are interesting material,because of its peculiar structure and the potential it can offer,however the octanitrocubane was never synthesised;and its supposed exemplary performance are just theoritical speculations.
I think Mega made a mention of these in much ealier posts...I hope he can present more interesting information in this area.
Some referrences:
<a href="http://www.ch.ic.ac.uk/local/projects/b_muir/Cubane/Cubanepro/Applications.html" target="_blank">http://www.ch.ic.ac.uk/local/projects/b_muir/Cubane/Cubanepro/Applications.html</a>
<a href="http://www.chem.ox.ac.uk/dhtml/default.html" target="_blank">http://www.chem.ox.ac.uk/dhtml/default.html</a>

Della, E. et al., Journal of Amer.Chem.Soc. 114(27) 10730-8 1992. Castaldi, G. et al., Tetrahedron Letter32(19), 2173-6, 1991.
Eaton, P. E. et al., Journal of Amer.Chem.Soc 112(2) 876-8 1990.
US patent #5998661
But for the time being MEDINA looks easier to make because ingredients are easier to procure then...
BTW most of the info available on explosive properties of these nitrocubanes are theoritical...

CFV

July 2nd, 2002, 03:16 PM

Another contender could be the N5+ ion, reported in the Dec. 2001 AFRL Technology Horizons magazine. Search gave only a request for the patent. This material is only in the basic R&D phase, but could be the beginning of a series of Nitrogen only explosives and propellants. According to the report, N5+ is a chain of nitrogen atoms, bent at the center, meaning the central atom could be negatively charged and sp2 or sp3 hybridized. On either side, positively charged N's of sp hydrid form a single bond to the center atom and form triple bonds with the nitrogens on the ends of the chain. The Delta Hf was calculated to be +350 Kcal/mole. With AFOSR support, N5+ Sb2F6, a 'surprisingly stable' powder was produced, the first new form of nitrogen since azide was discovered in the ninteenth century. Other theorteical minima (read 'potentially stable molecules in qm calculations were tetrahedral N4 and cubic N8 - N-cubane, but these exist only in cyber space (unless one of them is the infamous 'Red Mercury'). N5+ was suggested to be a possible precursor to these. More info-- <http://www.afrl.af.mil/techconn/index.htm>

cutefix

July 3rd, 2002, 02:21 AM

So you are really interested with these exotic materials,eh?
I think I have seen this article before..
<a href="http://www.afrlhorizons.com/Briefs/Dec01/PR0106.html" target="_blank">http://www.afrlhorizons.com/Briefs/Dec01/PR0106.html</a>
Well ,it is still in early development stage.
Let us see what fellow members can reckon from this item. <img border="0" title="" alt="[Wink]" src="wink.gif" />

Hex

July 3rd, 2002, 07:38 AM

N5- probably isn't far away either. Theoretical calculations predict it's more thermodynamically stable than benzene. Various phenyl pentazoles have been made (from the phenyl diazonium salt and an azide) but no-one's managed to successfully shake out the N5- yet, but it has been detected in the mass spec. It's hoped they'll be able to isolate it as a ferrocene-stylee sandwich using Mg2+
(Synthesis and Characterisation of Phenylpentazoles, A. Hahma et al, 33rd ICT International Conference of Energetic Materials, Karlsruhe, Germany, June 2002)

Medina can also be made from methylene bisacetamide, which is easy to make from a melt of acetamide and paraformaldehyde. This nitrates quite easily in 100% nitric. The acetyl groups hydrolyse easily with ammonia, and Medina can be trapped as the barium salt on addition of BaCl2.

[ July 03, 2002, 06:48 AM: Message edited by: Hex ]

cutefix

July 6th, 2002, 05:55 AM

Somehow the practical value for this material looks slim at the moment.A lot of these novelties are only good in theory.
Anyway ,its interesting to keep in touch with developments in explosive chemistry.

[ July 06, 2002, 04:56 AM: Message edited by: cutefix ]

CFV

August 20th, 2002, 02:38 PM

You are right that theoretical explosives are my primary interest, since this is a part of my effort to understand the impossible--the future of military technology and its impact on overall strategy and the relative positions of power between great and small human "groups." For instance, an N6 "ultra powerful" explosive could be the basis of a "peach can" nuke, since the greater squeezing energy of such an explosive would make the chain reaction militarily effective using smaller amounts of Pu or explosive or both. But this affirms that technology really empowers the little guy more than the superpower. We would really have to sit down with a future Osama and listen to his grievance if we knew he had peachcan nuke suicide bombers. I haven't seen a topic broached on theoretical explosives, but would like this very much. Since my status as a "newbie" precludes my posting of a new topic, I would like to suggest that an interested senior member consider opening one. The community may well provide much more interesting info if the subject is given more exposure than here, couched under the title, "medina."

simply RED

September 4th, 2002, 05:37 PM

H2NC=O-CH2-C=ONH2 + (CH3CO)2O + 2HNO3--> H2N-NO2-CHO-CH2-CHO-H2N-NO2 + CH3COOH
Hydrolysis with formic acid
H2N-NO2-CHO-CH2-CHO-H2N-NO2 + H2O ( in HCOOH)-->HNNO2-CH2-NNO2H

As i will try to prepare MEDINA soon, i have to ask some questions about these formulas...
I don't understand the first one: where is the NO2 attached?
is it :

H2N-C(OH)(NO2)-CH2-(OH)(NO2)C-H2N

Or it is a nitramine?

[ September 04, 2002, 04:38 PM: Message edited by: simply RED ]

megalomania

September 4th, 2002, 07:08 PM

Go ahead, CFV, and start a thread about any theoretical explosive that you wish. You will not be violating any rules now, and it sounds like you know your stuff. I don’t go in much for theory as I love the synthesis game. I prefer to exist in that world where theory becomes reality in the form of a nice synthesis. I like to keep my eye on the cutting explosives, but invariably they are never published as explosives (in big flashing red letters), so I miss them from time to time. It is nice to look at the theory stuff and track the inevitable synthetic publication.

I guess that’s why the current octanitrocubane is so interesting. After several years of research it is finially synthesized and it falls flat on its face with respect to actual explosive velocity vs. the theory. The surprising winner is heptanitrocubane, easier to make by far. Even if they do find a crystalline structure of ONC that gives predicted det velocities, will it be worth it?

Incidentally I have noticed that recent literature no longer compares any new explosive to TNT. The new standard is TATB with a det velocity of 8000 m/s. I don’t even know what that is, but I will soon enough that I am aware of it :D The wave of the future it seems are insensitive explosives that contain no halogens, metals, and such that combust into little more than air. The explosives of tomorrow will be cheap, stable, non toxic, and cheap.

Al Koholic

September 4th, 2002, 08:54 PM

TATB stands for Triaminotrinitrobenzene. I think its arrangement is 1,3,5-triamino-2,4,6-trinitrobenzene. I know it is very commonly found in modern nuclear warheads due to its extreme stability. Its stability is actually greater than that of any other known material of comparable energy. Somewhere on my harddrive I believe I have an article on its manufacture and use in the industrial/military world but I'm not sure. If I can find it I'll upload it.

Due to my lack of extensive knowledge on the subject of theoretical or cutting edge explosives research I would like to ask the knowledgeable viewers of this post whether or not any nitrated aromatic polymers have been explored?

Al

hedm

September 5th, 2002, 06:10 AM

the most powerfull explosive, I`ve ever heard is dinitroazofuroxan
formula :C4N8O8
hydrogen free molecule
denisity =2.0g/cc
OB=0
heat of explosion 1788 kcal/kg
detonation pressure:46 GPa
velocity of det:
at 1.94=9700m/s
at 2.00=10000m/s(experimental)
CL-20 or HNIW has v detonation =9400m/s, but in high pressed formulation 9270m/s could be obtained

Alchemist

September 5th, 2002, 11:45 AM

Hello all,

Found this on the net a while back and saved it to my hard drive, but I can NOT find the link again. Seems as though it has been removed!!!

TATB (1,3,5-triamino-2,4,6-trinitrobenzene) is easily prepared by ammoniating TRICHLOROTRINITROBENZENE in a benzene or xylene solvent. The TATB immediately precipitates upon the addition of dry ammonia gas, and continues through out the ammonia addition. After the addition is complete, the TATB is then filtered, washed and dried!

More later! I hope...

Check this link for other process;
<a href="http://www.llnl.gov/str/Pagoria.html" target="_blank">http://www.llnl.gov/str/Pagoria.html</a>

[ September 05, 2002, 11:21 AM: Message edited by: Alchemist ]

simply RED

September 5th, 2002, 12:52 PM

What is the structure formula of dinitroazofuroxan?
Tell us more about it

megalomania

September 5th, 2002, 04:59 PM

As far as I know the only energetic polymers are explosive plasticizers and binders. They are not aromatic molecules of course. There has been some speculation of being able to polymerize nitrocubanes, like hexanitrocubane. Again cubanes are not aromatic molecules. Come to think of it there are not many aromatic polymers at all, perhaps they do not react well enough.

simply RED

September 5th, 2002, 06:43 PM

rushed the whole net, could not even find what furoxan is?!

Mr Cool

September 6th, 2002, 01:45 PM

A furoxan (often attached onto the side of a benzene ring, like in CL-18 (aminonitrobenzodifuroxan), and potassium dinitrobenzofuroxan (KDNBF), formed by reacting two -NO2's on consecutive C's on the ring with NaN3 (CL-18 is made by reacting pentanitroaniline with NaN3 for example)) is (I'll explain later) -C=(N->O)-O-N=C-. The two C's are joined to form the furoxan ring, and they also form part of the benzene ring in the compounds mentioned above for example, although I don't think it'd be right to call it a benzene ring still because it'd mess up the resonance since the C's have double bonds to the N's. A furazan is similar, but without the N->O bond.

Microtek

September 9th, 2002, 02:35 AM

If Hedm's empirical formula and Mr Cool's structure of furoxan are both correct, then it's probably di(nitrofuroxan) instead.

Hedm: Where did you get info about this compound ? It seems very interesting and I had never heard of it, so I'm inclined to think that it's either a very new compound or something that doesn't exist. If it's very new, then you must have some nice info sources...
Please share!

hedm

September 11th, 2002, 06:02 AM

here is a link:

<a href="http://www.pirotechnika.one.pl/hedm/" target="_blank">http://www.pirotechnika.one.pl/hedm/</a>
(look at directories: DNAFSYNTH,explosives and others to find informations you need)
(note!:I use Adobe Photoshop 4.0 to open dnaf.tif in correct resolution)
hedm

Microtek

September 11th, 2002, 09:23 AM

First of all I'll just urge everyone to follow that link and download the pdf's from the explosives directory. They are VERY interesting. Imagine that there are that many explosives in the HMX or CL-20 league....
Secondly, the .tif article appears very small in my browser, I can barely see the letters. I do think that they are not ordinary latin letters but rather russian ones, so enlarging would do little good.
I can see that 10000 m/s is mentioned several times, and I can also see the structural drawings, so at least that is settled.
Thirdly, there is four .gif images named foron1-4. They detail something called diforonepentaperoxide which is supposedly made by some sort of condensation of acetone with HCl then reacting with H2O2 30% to produce the peroxide ( the text is in german which I barely understand so don't take my word for it ). The product is said to detonate at around 9000 m/s !!!
This seems much too good to be true, in fact I would dismiss it as kewl if not for the fact that it looks a lot like papers from the german patent office. It could still be a fraud of course but it seems like too much trouble. Anyway, take a look and judge for yourselves.

PS. Hedm: That is really something. Have you tried any of those explosives yet ? And which books/papers do the articles come from and how have you gotten access to them ? I'm really curious.

nbk2000

September 11th, 2002, 09:40 AM

Perhaps someone who knows german *COUGH*mach*COUGH* <img border="0" title="" alt="[Wink]" src="wink.gif" /> could read this file and give us a breakdown of the info contained therein. :)

Microtek

September 11th, 2002, 01:43 PM

Allright, I'm afraid I got quite un-scientifically impatient to find out more about the diphoronepentaperoxide, hereafter referred to DPPP, so after slowly and carefully reading through the pages, I searched the german patent database and found that the .gifs were copies of those pages. I then made a synthesis as outlined in the patent: 5 mL acetone was mixed with 5 mL part HCl 30%, heat was evolved and very slight bubbling was observed ( I know that it is most likely parts by weight, but as I said I was impatient ).
Once the liquid had cooled, 0.5 mL was transferred to a test tube and 0.5 mL H2O2 40% was added. At first drop by drop, then as nothing untowards was happening, I added the rest.
A white precipitate immediately appeared and the mix was allowed to sit undisturbed for 10 min. After this period the product was filtered off, washed and dried.
Then I started examining the it and found that it smelled exactly like acetone peroxide, but was a fine amorphous powder like HMTD. Upon ignition from flame it flashed like HMTD or AP, but if placed on a piece of Al foil above a flame, the powder melted and then detonated violently. Thus far, everything except morphology pointed at AP, but then I did the impact sensitivity tests. I performed my standard qualitative test which consists of placing the sample in a piece of Al foil which has been folded to form a small envelope. This envelope is then placed on a steel anvil and a carpenters hammer is used to pound the sample. It was quite hard to get the sample to detonate; it took blows consistent with what PETN requires, and when the flat, un-exploded samples still in their envelopes were held into a flame they didn't detonate but only flashed as before.
The final test I did was to pack about .25 gram into a 2 mm pipe attach a fuse, and ignite - no detonation, only flashing which ejected the rest of the fuse. Further testing will follow.

HNIW

September 11th, 2002, 04:58 PM

Ok I decided to convert these text about DNAF to more usefull format. You can find them using the same link as before.
<blockquote>quote:<hr />I do think that they are not ordinary latin letters but rather russian ones, so enlarging would do little good. <hr /></blockquote>Yes this formula is in russian. As many of you I can't even read it because I don't know russian alphabet <img border="0" title="" alt="[Frown]" src="frown.gif" />

Mr Cool

September 11th, 2002, 05:08 PM

Sounds interesting Microtek!
Hehe, and I told myself I'd never make another organic peroxide... well I'm going to have to try this one!

xoo1246

September 11th, 2002, 05:47 PM

Doesn't that mean people at this forum must have made it by accident before? Wouldn't they have noticed?
And the patent sais 9000m/s, that sounds very interesting and almost unbelivable.

[ September 11, 2002, 04:57 PM: Message edited by: xoo1246 ]

hedm

September 12th, 2002, 07:46 AM

Here is a short synthesis of medina:

<a href="http://www.pirotechnika.one.pl/hedm/medina.jpg" target="_blank">http://www.pirotechnika.one.pl/hedm/medina.jpg</a>

To obtain Acetone Peroxide (AP) in the form of wheat (crystals are very small) use:

50ml of acetone
100ml of 30%H2O2

These liquids were mixed at 0-5 degree and 25ml of 65-68%HNO3 was added below 10 degrees with stirring and cooling. After adding the mixture was allowed to stand at room temperature and AP precipitated.

Next, filter it and wash several times with water to neutrality and suck it to dryness using a water pump (aspirator). The peroxide obtained really contains about 50% water.

[ September 12, 2002, 08:23 AM: Message edited by: nbk2000 ]

nbk2000

September 12th, 2002, 08:49 AM

Isn't this just yet ANOTHER way of making AP? :rolleyes:

ALSO...do NOT refer to Acetone Peroxide by any other name here. It is NOT TCAP, CTAP, Tricyclo***, whatever. JUST AP or Acetone Peroxide. This prevents confusion.

BrAiNFeVeR

September 16th, 2002, 05:13 AM

Maybe it is ...

But then again, maybe it isn't !!!
And it is our job to study it and find out :D

The thing that makes me sceptic is that there is just no other source out there then that german patent ... (according to google that is)

The best way to find out (in my opinion) is first to make phorone, filter and clean these yellow prisms (mp= 28°C) and then try to peroxidise it. This would give you pure DPPP with no trace of AP left in it :cool:

If this turns out well, it looks like I'll have a new favourite peroxide ...

Edit: Just when I was going to depart for my lab to do some tests, it came to mind that this may deserve a seperate thread ...

[ September 16, 2002, 04:16 AM: Message edited by: BrAiNFeVeR ]

VasiaPupkin

September 16th, 2002, 05:01 PM

He-he. Nitrofurazanes is a interesting subj.
I read that many nitrofurazans and nitrofuroxanes is a very promising HE and energetic materials.
But max. experimental VoD=9700m/s I knew only for 4-membered linear nitrofurazane
O2N[(fur)-N=N(O)-]3(fur)NO2. There are something like 10-15 potentially promising things.
About papers:
First page is a overall info about DNAF. DNAF is a first solid matter with really measured stable VoD=10000m/s and other unique parameters. But not all so fine.
One thing is something strange. I think they get 10000m/s on large monocrystal. And that experiment they wrote is not from this paper area.
Because they wrote that it can be practically pressed only up to 1.94.
Hmmm. Its sufficiently stable for using with flegmatizer. Be sure VoD maybe some lower with flegmatizer.
I suppose 9300-9500m/s for real mix - something like HNIW alternaive. Its interesting if it would to be less expensive than HNIW...
I can try to translate this report into English. Maybe almost all this papers and place it here...

By the way hedm, do you have any info about 3,4-dinitrosofuroxane ON(C2N202)NO?
I know only that its yellowish powder with m.p. 102C with decomp. density 1.94g/cc, and vod up to 9700.
Maybe something else interesting about nitrofuroxanes. Do you have access to Russian chemical journal 1997's vol 2 and 4?

[ September 16, 2002, 07:08 PM: Message edited by: VasiaPupkin ]

Mr Cool

September 17th, 2002, 02:17 PM

Something I've been thinking about recently, similar in structure to the furazans (NH not O), is 4,5-dinitro-1,2,3-triazole: (join the ends up): -C(NO2)=N-NH-N=C(NO2)-
1,2,3-triazole can be prepared by reacting ethyne and HN3, or probably ethyne and NaN3 soln., then add dil. HCl.
It is brominated in high yield by heating with bromine at 50*C to 4,5-dibromo-1,2,3-triazole, then this could be dissolved in a solvent, e.g. DMF, and reacted with XNO2 to produce the 4,5-dinitro-.
It'd be quite sensitive, but dense, powerful, and yielding lots of gas...
I'm thinking about maybe having a go at making 1,2,3-triazole, and if I do I'll probably try making 4,5-diiodo-, and maybe then the dinitro, but I'm not sure. If I have to use HN3 then I probably won't.

Edit: I wrote NaNO3 instead of NaN3...

[ September 17, 2002, 01:19 PM: Message edited by: Mr Cool ]

VasiaPupkin

September 17th, 2002, 05:03 PM

If it would be useful then we would be heard something about 4,5-dinitro-1,2,3-triazole.
Theories are always sounds well. But very often new theories does not work on practice.
Because we could not estimate (or merely dont know) other more significant principles.
There are numerous cases where real properties was opposite to predicted.
I think even if this triazole is stable it would be something like 3,5-dinitro-1,2,4-triazole.

Mr Cool

September 18th, 2002, 02:35 PM

1,2,3-triazole is stable, although the book does discourage the use of ethyne and an azide to make it as it's a dangerous procedure. They recommend using ethyne (or a different alkyne for substituted 1,2,3-triazoles) and some other azide compound. I don't have the book with me at the moment so I can't tell you what it was.
The only step in the procedure that might not work is the substitution of Br with NO2 (I admit that this is obviously a crucial step!), I know that 1,2,3-triazole is "remarkably stable" and that it is "brominated in high yield by treating with bromine at 50*C" (they are two exact phrases from the book that I can remember).
I can't see any reason why it wouldn't work, but that doesn't mean that it does!
I think probably it would work, but it isn't used because it's too sensitive, or too expensive etc, i.e. it has no advantages over other alternatives.

VasiaPupkin

September 18th, 2002, 06:15 PM

Sure 1,2,3-triazole is stable. Its solid matter with m.p. 23C.
Take into account that common organic azide-ethyne reaction condensation works at higher temperatures.
For example ~100C. If you want to make non-substituted 1,2,3-triazole it maybe a really dangerous procedure. You know HN3 (and its fumes) is extremely sensitive and toxic.
One breathe of HN3 fumes is enough to lose consciousness. But maybe this concrete reaction will drive at room temperatures. I know only 1,2,3-triazole preparing from HN3 and C2H2 is exist. I dont know about conditions.
But I doubt about 4,5-dinitro-1,2,3-triazole.

Hex

September 19th, 2002, 04:50 AM

Here is a useful looking abstract from a search for nitro triazoles -
Can anyone from Russia get hold of / translate this? I know some Seriya Khim articles end up in English in the Russ J Organic Chem...

Bibliographic Information

Gem-dinitro compounds in organic synthesis. 3. Syntheses of 4-nitro-1,2,3-triazoles based on gem-dinitroethylenes. Baryshnikov, A. T.; Erashko, V. I.; Zubanova, N. I.; Ugrak, B. I.; Shevelev, S. A.; Fainzil'berg, A. A.; Laikhter, A. L.; Mel'nikova, L. G.; Semenov, V. V. Inst. Org. Khim. im. Zelinskogo, Moscow, Russia. Izv. Akad. Nauk, Ser. Khim. (1992), (4), 958-66. CODEN: IASKEA Journal written in Russian. CAN 118:101883 AN 1993:101883 CAPLUS

Abstract

Several chemoselective approaches to the title triazoles I (R = H, Me, Bu) are developed from NaN3 and gem-dinitroethylenes, readily available from the transformation products of dinitroacetic acid esters, N-(b,b-dinitroethyl)-N,N-dialkylamines, 2,2-dinitroethanol acetate, mixts., of dinitroacetic acid esters with aliph. aldehydes, or 1,1,1-trinitroalkanes. Hitherto unavailable 4-nitro-5-amino- and 4,5-dinitro-1,2,3-triazoles were prepd. via successive transformations of the Me group in 4-nitro-5-methyltriazole. Nitration of 4-nitro-1,2,3-triazole with nitronium tetrafluoroborate or acetyl nitrate gave the novel 2,4-dinitro-1,2,3-triazole.
_

VasiaPupkin

September 19th, 2002, 08:31 AM

You can send this articles by mail. Maybe I'll try to do something.
But I can translate it if anybody would get it <img border="0" title="" alt="[Wink]" src="wink.gif" />
This article looks like is not from Rus. Chem. journal but journal which hedm provided.
Its only 1992. N4

I can translate papers about DNAF. Or its not interesting for all?

binary mz

September 19th, 2002, 02:50 PM

Has anyone looked in to what Microtek found ? diphoronepentaperoxide looks interesting and i would like to experiment with it. Was there a patent # for it ? Either way, I'm going to do what Microtek did and see if I can get anything in the end.

binary mz

September 19th, 2002, 02:53 PM

Microtek

September 19th, 2002, 04:24 PM

I've been experimenting some more and I have some findings to share.
First of all a warning: The impact sensitivity is somewhat greater than I have reported. This was due to a systematic error in my testing procedure, and it has now been rectified. The actual sensitivity is only slightly less than that of HMTD so be careful if you make this.
Now I reported that the product ( which I will refer to as DPPP even though the identity of the substance has not been satisfactorily established ) smelled exactly like AP, but I placed a small amount of
it in an open cup to find out how volatile it is.
After standing for a few days, it had lost all of its odor, which could be interpreted as the AP impurities having evaporated.
There has been some doubt in my mind as to whether it was actually DPPP or simply AP that I had made, but speculation aside, a number of characteristics of this substance makes it quite unlikely that it is finely divided AP:

Inability to perform DDT. This pretty much convinces me; in all the years that I used AP it has never failed to detonate when pressed into a tube, even if the ID was below 1 mm and even if the AP had been finely divided. Also, I prepared a sample in a tube 2 mm ID and with a charge of lead styphnate directly on top. when the styphnate was ignited and detonated, the DPPP simply flashed as when ignited directly by a fuse.

Scentlessness. The AP that I have been using has never stopped smelling, and the smell has been very unique.

The manner of its preparation. I made three batches all in all. Two very small ones and one that was larger. The second of the small batches was made by adding HCl to acetone as usual, but then after the rection had subsided, the mix was placed on a hot-plate for quite a long time. This was done in an attempt to drive off any remaining acetone, but the volume was not reduced by much.
In the larger batch, the mix heated up quite a bit and a lot of precipitate was formed. This precipitate became greenish-yellow after a short while, but turned white when disturbed.

Initiating ability is very good; a coloumn 2.5 mm in diameter and 2 mm in height ( corresponding to 10 mm3 ) pressed at about 500 psi and initiated with 0.5 mm coloumn of double salt was capable of initiating PETN and seemingly also RDX though that test was not entirely conclusive. At an estimated density of 1g/cc 10 mm3 corresponds to 0.010 g. Thats about what lead azide can do.

On a final note, I think I can say that brisance is not as good as the patent would have you believe. VOD may or may not be up to the 9000 m/s mark, but shattering power is not much better that HMTD and neither is density.

Alchemist

September 20th, 2002, 05:26 PM

Hello all,

there has been some interest in Phorone on the <a href="http://www.sciencemadness.org/talk/" target="_blank">http://www.sciencemadness.org/talk/</a> web sight also. I have been following it for several days now. Seems the goal is to make Diphoronepentaperoxide (DPPP). I agree that we need to isolate Phorone in a pure form first then make the Peroxide, but I have found very little on the Web or several Oraganic chem books as well. I have seen a FEW references that state it is made by heating Acetone with acid (both HLC or H2SO4) where mentioned. The problem is that these are just that and nothing more. No data on acid concentration, amounts, how long to heat, how to isolate and purify, etc.. The second problem is I believe mesitylene, mesityl oxide, diacetone, etc. are all formed to some degree and maybe others. So if ANYONE has a good procedure for producing Phorone, please post it, or any ideas you may have! Thanks all.............

[ September 20, 2002, 04:29 PM: Message edited by: Alchemist ]

Mendeleev

November 28th, 2003, 01:35 PM

On mega's site the Vod of HNIW is 10300 m/s, but others claim it is 9,300 m/s. I'm confused, which is it? Or are these different Vods for different isomers? If so which isomers has the highest vod and what is it :confused:? Also, I searched the net for N4 and N8 and found something more interesting N60. In 1985 reasearchers synthesized and allotropic form of carbon, C60, shaped like a soccer ball and now they are trying to do the same with nitrogen, which would yield one hell of an explosive. Heres the link http://www-cms.llnl.gov/s-t/ex_soccer.html Also I was wondering what if instead of making N60 you fully nitrated C60 with NO2 groups on each carbon? That would most likely be close to impossible to to the electron repulsion :mad:, but still a full nitrated C60 would have 120 C-C single bonds, 60 C=C double bonds, 60 C-N bonds single bonds, and 120 N-O single bonds. According to a bond energy table in my chemistry book bond energ table heres what the bond enery (which is the amount of energy needed to break a bond, not how much energy is in the bond):

This is all in kJ/mol

C60

Reactants
20 C-C = 20(347)= 6940
10 C-C = 10(614)= 6140
60 C-N = 60(305)= 18300
120 N-O = 120(201)= 24120
---------------------------------------------------
55500 kJ/mol

Products
60 CO2 = 120 C=O = 120(799)= 95880
60 N triple bond N = 60(941) = 56460
--------------------------------------------------------
152340 kJ/mol

N60 by comparison is much weaker...

Reactancts
20 N-N = 20(160)= 3200
10 N=N = 10(418)= 4180
---------------------------------------------------
7380 kJ/mol

Products
30 N triple bond N = 30(941) =28230
---------------------------------------------------
28230 kJ/mol

Subtracting 152340 from 55500 yields a change in energy of -96840 kJ. That means that one mole of fully nitrated C60 would release 96840 kJ or roughly 23145.3 kcal :eek:. Whereas N60 would only release 20850 kJ/mol. Just to give you an estimate TNT only releases 1147.5 kJ/mol according to the same calculations using the same bond energy table. Damn it'll take a lot of HNO3 to nitrate C60... :D

Mendeleev

November 28th, 2003, 09:00 PM

In the Russian article about dinitroazofuroxan it said that its vod was 500 m/s higher than hexanitrobenzol which is the same as hexanitro benzene. I've never even heard of hexanitrobenzene, and I always wondered why nitrate toluene three times when you could nitrate benzene 6 times? Anyway does anybody know anything about hexanitrobenzene or how to synthesize it? If it requires six nitrations that would be a shitload of acid gone.

simply RED

November 29th, 2003, 04:44 PM

"Mendeleev" you are very weak in chemistry!

Ever heared of : stress energy, torsion angles, thermochemistry equations, electron density, chemistry of aromatics .......
There is no way to nitrate benzene directly to HNB using nitric acid.

Mendeleev

November 29th, 2003, 08:54 PM

Yes, I am weak in certain areas of chemistry, not all though, we just haven't done too much bonding dynamics in AP chemistry yet, we mostly do chemical kinetics, equilibrium, and electrochemistry. Anyways, I was just making sure, notice how I said "if" it requires six nitrations. Sorry for my mistakes. The actual process, I found in US patent 4,262,148 was to add pentanitroaniline to pure H2SO4 with 20% dissolved SO3 content at room temperatur 25-30 degrees Celsius and then adding 98% H2O2. Stirring for 6-24 hours yields a precipitate, which hexanitrobenzene. However hexanitrobenzene is hygroscopic and thus must be washed with pure sulfuric acid after it is filtered out. This is also why is not so suitable for military applications. Damn that sucks its got a pretty damn good VOD. Of even greater curiosity to me is the Russian compound Dinitrodiazofuroxan. With a VOD of 10000 m/s it is more powerful than the alleged octanitrocubane, which megalomania said was the most theoretically powerful, yet whose VOD is only 9800-9900 m/s. Does anybody also know anything about 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatricyclo(7,3,0,0)dodecane-5,11-dione (HHTDD)? It was mentioned in the New Energetic Materials pdf on the hedm site. Its VOD is 9700 m/s. Oh and by the way here is a site with the VODs, lead block tests, and densities of just about any explosive you could possibly want to know about: http://mihailru.freeservers.com/shopping_page.html

simply RED

November 30th, 2003, 05:14 PM

DNAF is sensitive and unstable (according to the info i have) (maybe stable enough to make shaped charges but it will require lots of plasticizer).

Mendeleev

April 16th, 2004, 02:38 AM

Microtek

April 16th, 2004, 09:10 AM

I would like to see that paper. Although it's not practical for me when fluorine is involved, it is always interesting to follow the new developments in the field. My e-mail is kast314@hotmail.com

cutefix

April 18th, 2004, 03:23 AM

hana12

April 18th, 2004, 10:14 AM

I would like to see that paper if you please

my email : fadi_ward@yahoo.com

Mendeleev

April 18th, 2004, 09:45 PM

Hey, cutefix, what is your e-mail, the forum's email system doesn't do attachments. I sent the other two candidates their papers, can you guys confirm if you got them?

Microtek

April 19th, 2004, 01:05 PM

I got it. Haven't had a chance to read it yet though.

cutefix

April 20th, 2004, 01:26 AM

Hey, cutefix, what is your e-mail, the forum's email system doesn't do attachments. I sent the other two candidates their papers, can you guys confirm if you got them?

Hello Mendeleev.
Just use rdickens@x-mail.net. Thanks

cutefix

April 24th, 2004, 09:50 AM

Does anybody have any data on HNFX performance in terms of vod and brisancy? I believe the proper name for this compound is 3,3,7,7-tetra(difluoramino)-1,5-dinitro-1,5-diazo-cyclooctane. I am currently interested in fluorine-nitro explosives. Fluorine being the most electronegative atom on the table, it is a double whamy because it increases density as well as energy release due to the low enery H-F bond. I have a paper on it, from the journal of organic chemistry, it is to large to upload here, but if anybody would like I can e-mail it to you. It's about 110K.

That article was more about the unique nitration procedures to produce the HNFX ( which I call simply as cyclotetrakisdiflouraminodinitramine. which is considered a unique explosive with good potential for both propellant as well as explosive oxidizer in the same line as HMX and RDX.
That explosive from its structural appearance is difficult to prepare and needs alternative methodology to attain the most practical yield. Requiring virtually anhydrous nitration using the HNO3-TFA and triflic acid a unique precursor. In the end the end product will remain a scientific curiosity….
But having flourine as part of the structure do offer lots of promises....

simply RED

April 25th, 2004, 05:44 AM

I'd also like to see the paper.

sulphur@abv.bg

Hystrix

May 15th, 2004, 01:20 AM

Flourine containing explosives are very interesting as previous by Cristie in high energy explosives did show that the presence of flourine compound as part of the composite explosive would dramatically improve its explosive performance.
I am also interested to see that paper, please send me an e-mail.

I think difluoroamines are not so interesting. Yep, they have rather good density but at the same time they have poor oxygen balance, are sensitive to impact and friction, and their raw materials are very dangerous (highly toxic and explosive). But if you need, I have a bit of info on DP-12 (2,2-bis-difluoroamino-propane). Also I've read that gem-tris-difluoroamino compounds and tetrakis-difluoroamino-methane C(NF2)4 were synthesized but their sensitivity is too high for practical use.

PS Thus I think it's more useful to have an additional nitro group instead of -NF2

Microtek

May 15th, 2004, 10:23 AM

Oxygen balance may be low, but fluorine is an excellent oxidizer itself.
Take a look at these reactions:
2C + 2O2 --> 2 CO2 + 787 kJ
C + 2 F2 --> CF4 + 930 kJ

2H2 + O2 --> 2 H2O + 480 kJ
H2 + F2 --> 2 HF + 540 kJ

So the NF2 moeity will give oxidize the C's and H's of the molecule to give better energy release and, as fluorine is monovalent as opposed to oxygen, will require only half as much fuel atoms to do so. This means that more ( twice as many in fact ) NF2 groups can be attached without getting a positive OB.
I my opinion, the only disadvantages are the unpleasantness of the precursors and detonation products and the unavailibility.

cutefix

May 16th, 2004, 09:04 PM

I think its nor about oxygen balance that is the main issue here. OB is an academic interest with regards to powerful explosives.
If you will look carefully at many military explosives almost all of it have negative oxygen balance but it does affect its performance? :)
OB value is of practical interest for commercial explosives where fume formation from incomplete combustion may pose hazard to worker exposed in the space being blasted with explosives.
Going back to that work of Christie he did offered some interesting values with the addition of fluorine containing materials in common well known explosives, RDX.,TNT, HMX etc
In fact China lake ,Lawrence Livermore laboratory, Los Alamos are silently looking at this very interesting potential how fluorine can influence and dramatically improve the explosive performance .

Microtek

May 17th, 2004, 06:45 AM

OB plays a substantial role in determining the performance of explosives because the formation of carbon-oxygen or hydrogen-oxygen bonds supplies most of the energy ( along with nitrogen-nitrogen bonds of course ) in traditional CHNO explosives. That energy release is important is demonstrated by such things as NG or EGDN which have great performance despite poor density. Especially in applications where some amount of heaving effect is desirable does the energy content ( and therefore the OB ) play a part. Applications such as torpedo or depth-charge warheads as well as large fragmentation warheads benefit from increased energy output.
Another case in which OB is seen to be important is such a thing as tetranitromethane which has rather mediocre performance on its own, but really shines in mixtures with fuels such as toluene or nitrobenzene.

Of course it is not necessary for an explosive to be at or near an OB of 0 to be a high performing explosive, but all other things being equal the explosive with the best OB will be the highest performer.

The thing in this case, is that the oxidizer doesn't have to be oxygen ( and in fact fluorine is a more energetic oxidizer as well as the NF2 or SF5 groups giving other advantages ).

cutefix

May 17th, 2004, 08:57 AM

nitroglycerine has a positive OB butits military value is just a one of the component for smokekess powder.EGDN is just of commericail significance either.
Now if you talk about underwater explosives , the conditions due to the absence of air needs that another oxygen supplying oxidizer to improve the rapid combusiton of the explosive components that are responsible for the better underwater detonation and bubble energy that contribute substantially to the destructive effect of such explosives to its target by prolonging the explosive effect for more time due to the rhythymic serieis of formation of generation and collapse of bubbles.
Hence even if the amount of self oxidizing explosive such as RDX is very mnimal such as in the current underwater explosive PBX 115 which is low but is compensated by more than 40% of ammonium perchlorate and considerrable aliuminum powder bound by a polymer binder and plasticizer.Indeed This particular explosive is estimated to be twice the power of composition B if detonated underwater but is lower powered if detonated above ground.
It has nothing to do with oxygen balance ; it is just the conditions needs it.
And the presence of ammonium perchlorate will also cut down the cost of explosive without affecting its underwater performance.
And you cannot relate the underwater explosion to detonation above ground in power; they are different in conditions of explosive performance.
Now the so called Torpex and the related high blast explosive series HBX1-&3 as well as the H-6 are not oxygen supported explosives ;They are just plain mixture of RDX/TNT/Al with some stabilizers. And they are distinctiively oxygen deficient.
Here we can compare their performance above ground and underwater due to the effect of aluminim. But what is the difference in oxygen balance ,they are both considerably oxygen negative. but very powerful..
Now lets look at tritonal 80/20 TNT/Al. That mixture is more oxygen negative than TNT itself which has an OB value of more than -70.But look it has more blast perforrnance than the same amount of TNT,
It should be that if you add more fuel the explosive powerr should decrease due to less oxygen;
But its the opposite.
The same thing with thermobaric explosives which are usually highly oxygen negative.
Explosive power has nothing to do with the oxygen content and the power rating can have variied meaning depending upon the explosive appilication.
It means the merit of OB is meaningless but looks nice on the clipboard of the theorist.
Who can deduce a this leisure that 'Ahh this is good' the oxygen balance is just nearing the positive value' biut in real life situtation it is not.
If you talk about of TETAN or tetranitromethane which has positive oxgyen balance but if mixed with toluene that will decrease its oxygen balance ( or increase oxygen consumption )which in consequence increase its power.
Another is hydrazine nitrrate, by its own its not a very high velocity explosive; but in the presence of hydrazine which will have an affect on the oxygen consumption, will dramatically improve its explosive power.
Therefore the mixing of fuel to cut down the oxygen in a slightly oxygen excess in an oxidizer to reduce the oxygen fuel ration resulting in negative oxygen balance of the composite explosive disagree with the fact of oxygen balance theory that a good explosive should have a high oxygen content to be a powerful explosive.
In the end the oxygen balance issue does not hold much water if viewed in the totality of explosive performance.
It is just an obsolete concept then. that has a limited application in a broader scale of explosive performance application.

In then end the thesis that oxygen balance should be required in order to be able to produce a good explosive has no merit but an iidea(brought by experrience in commerrcial blasting) by commercial explosive users who share the same sentiment that an explosive to be commercially useful should have a good oxygen balance; which actually means that if the explosive manufacturer can provide an item which will n ot leave toxic fumes during detnnation in enclosed spaces sells more and they are less likely to pay huge liability fee if their products does harm the users themselves due to toxic fumes.
I would say the the idea of oxygen balance is good for composite rocket propellants where that term has more usefullness if the composite propellant has good oxygen balance , it will likely improve its specific impulse which will affect the thrust and propelling power.
But if its so oxygen negative it will show that the rocket has poor fuel due to incomplete combustion, which is due to the lack of oxidizer.

Microtek

May 17th, 2004, 05:02 PM

Your last argument is exactly the point I'm trying to make: You can get more energy out of an explosive molecule if all the fuel is consumed without leaving behind any excess oxidizer. No one ever said that OB should be as high as possible; that would leave a lot of unused oxidizing power. Instead OB should be close to zero, meaning that the present oxidizers will exactly consume all the present fuel.
The reason I mentioned the underwater explosives is that total energy release is more important in these applications than brisance. The point is that a high energy release will give good heaving power but not necessarily a good brisance, so as you say, a compound that is optimized for energy release may not be the best for all applications.
Concerning the aluminized mixtures, performance ( in this case blast ) is not increased because OB goes down, but rather because energy release goes up. Combustion of aluminum is a much more energetic process than combustion of carbon or hydrogen, so the availible oxygen is simply used more efficiently to release a greater amount of energy.

I still maintain that, all other factors being equal, the more energetic explosive will give the better performance. Making OB approach zero is just one way of increasing the energy output of a composition.

cutefix

May 17th, 2004, 07:22 PM

Well professor .....do not forget your clipboard :p Please, a have a back up of your OB files, calculations if its stilll in hard copy.

It might get accidentally placed near an explosive ( your testing)and blown away while you ( acting like an accountant ) is trying to balance( calculate) the fuel/oxidizer ratio of a that explosive( if its up to your satisfaction):cool: :D

Microtek

May 18th, 2004, 02:52 AM

Yes I admit that I do take a rather scientific perspective on the field of explosives, never just throwing "a little of this and a little of that" together to see how it works. And I also admit that I work hard to squeeze that last iota of performance from the materials, when it would be easier to just use a little extra explosive to get the same effect.
However, I like the synergistic effect of using OB +ive and OB -ive materials such as MHN and PETN to get a compound that performs better than either of the components.

cutefix

May 18th, 2004, 03:52 AM

Well its nice to hear , how you manage to scrimp on playing with ( amidst huge pile of )your energetic toys!

Sweeper

February 21st, 2008, 09:13 PM

Hi guys, I`ve thinking around and around to some nitramide or nitramine reactions. Some nice suggestions came up to the stuff of MEADINA (methylene dinitramine). Might it`s seems somewhat costly but the result shloud be more then clean. My thoughts came from the picramic acid and what you can do by a strong nitration of an amin.

Step 1:
Method 1:
Synthesis of dinitromethane
1 mol of nitromethane is mixed with 4 mol of 96 % sufuric acid in an 1000 mL
beaker and 2 mol of 70 to 80% nitric acidis slowly stirred in by standing the
beaker in a cold water bad. Slowly the berkaer is heated on an stirrer to around 120 degrees centigrade and stirred at this temperature for one hour.
The solution is chlilled and the dinitromethane is extracted with four 300 mL
portions of anhydrous methylene chloride by stirring it rapidly, the methylene
chloride is careful vaporized at 35 to 38 degrees centigradeby stirring the
stuff with a glass rod.

Method 2:
1 mol of nitromethane is stirred to a 5 degrees centigrade chilled solution of
around 2 mol disslolved sodium nitride powder in 4 mol of 25 % HCl, the temperature is held for 20 to 30 minutes and the mix is stirred rapidly. Let the mix stand for any hours in a fridge and a small amount of dinitrosomethane should precipitate. The crystals are dryed on a filter paper and stirred into 2 mol of 80 % HNO3. Stirr it for one hour and dilute it with 500 mL of water. Crystals of DNM should form by standing the liquid in a fridge. Wash it with a smal portion of ice water and dry it on a paper.

Step 2:
Synthesis of diaminomethane
Method 1:
The yielded DNM from the step one is stirred in 2 mol of concentrated NaOH
solution in an 500 mL beaker by standing in a cold water bad, 4 mol of very fine powdered sulfur is stirred into the mix and and the solution is slowly heated in a hot water bad and stirred rapidly with gloves and a glass rod that it not heat to much or boil. It better you make the step in outdoor or you have a good fume equipment. When the reaction is end, the result is diluted with around 2 mol of 25 % HCl, and the slurry is extracted by Step one or maybe by stiring 1000 mL of methyl- or ethyl alcohol to the chilled mixture, the mix is filtered and the liquid is vaporized by standing for instance in a oven by stiring it sometimes with a glass rod.

Method 2:
The diaminomethane is stirred into 5 mol of 25 % HCl by standing in an cold water bad, the solution is heated up to around 60 degrees centigrade and 2 mol of Sodium sulfide powder is stirred in small portions by stirring t rapidly and waiting for react. The yielded DAM is extracted by step 2 method 1. More beatiful is when you have a lot of sodium hyposulfide solution.

Method 3:
The DNM from the first step is mixed mit 700 g of household sugar in around 2000 mL of water in a large beaker, the beaker is careful heated up to around 90 degrees centigrade and stirred for six or seven hours. The stuff is extracted by methylene chloride or a lot of methanol. Mayby more solvents will work to extract the result from the water or from the last two methods. Have someone a little experience with some solvents of diamines ?

Step 3:
Synthesis of MEDINA
Method 1:
The dryed result from the yielded diaminomethane is dissolved in around 80 mL of 98 - 99 % HNO3 at room temperature. Teh mix is stirred for more than two or three hours and than chilled in a ice water bad. Crystals of MEDINA should precipitate when the ice is molten. Filter it out, wash it when correct with
a small amount of methyl alcohol and dry it. The product should be very pure and disstillation woulde be waste.

Method 2:
Prepare a solution of 30 mL of 99 % nitric acid and 35 g dinitrogen pentoxide by chilling t to 0 degrees celsius. The result of DAM is added is small portions to the mi and stirred at this temperature for more than 4 hours. Add around 200 mL of methylene chloride, let stand teh mix for any hours at 0 degrees centigrade and filter out the MEDINA.

Method 3:
I don`t know this will work over the reaction because it is sometimes questionable what the destroying properties of sulfuric acid and sodium hydroxide with the special chemical stuff will do. More than the stuff is not an aromatic and can not handled like an easy benzene stuff. I mean it will increase the yield only.

Prepare a very concentrated solution of sodium hydroxide by dissolving a quantity of 0,5 mol in minumum of water and boil it until a slight precipitation of a white tick will form on the beaker. Prepare near 4 mol of 100 % concentrated sulfuric acid by fuming out 96 or 98 % H2SO4 to sulfur trioxide. The sodium hydroxide solution is is transferd in a 500 mL bearker by chilling in an cold water bad. Stirr the sulfuric acid to the sodium hydroxide and mixing a while and let heat it to room temperature. Slowly add the DAM o the mix, stirr it and heat it up to 60 degrees cenigrade by stirring it for one hour. Let it cool and extract the MEDINA with four 600 mL portions of methylene chloride.

I hope it`s a little inspiration to make a nitramide by several methods.