Sciencemadness Discussion Board

DIAMINOURONIUM (DI)NITRATE

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MineMan - 4-6-2019 at 22:13

I am really excited to find this tonight, I hope everyone else will be too. It’s VOD and Vdet is equivalent to RDX, however, it is less sensitive and seems to be very easily prepared.

Diaminourea is nitrated at RT with 30%NA. That’s pretty much it... if 2 moles of NA is used the dinitrate is formed. The only downside of the dinitrate is it decomposes at 115C, a problem for industry but not for us...

The Dinitrate has a OB of 10 percent... I have not calculated the VOD of the mononitrate...

This looks very promising! Diaminourea seems to sell for about $15/kg in bulk. If anyone can find a US supplier I can investigate.

Love to hear your thoughts.

Fulmen - 5-6-2019 at 00:39

Interesting.
This has some basic info:
https://onlinelibrary.wiley.com/doi/pdf/10.1002/prep.2011000...
(scihubbed for convenience)


Attachment: fischer2011.pdf (344kB)
This file has been downloaded 715 times

underground - 5-6-2019 at 05:50

Well, i can not seen anywhere anyone selling diaminourea that cheap

Boffis - 5-6-2019 at 08:08

Diaminourea is known as carbohydrazide (as mono-aminourea = semicarbazide) and it has been discussed severasl time before on SM (UTFSE). If you have access to hydrazine hydrate or are prepared to make it from hydrazine salts the preparation is simple. Simply treat either urea or dimethylcarbonate with slightly more than 2x its molar equivalence of hydrazine hydrate, the later requires that this is done in two stages. There is also a patent that describes the preparation from cyanuric acid and hydrazine hydrate. I have several paper on this compound.

Check out http://www.sciencemadness.org/talk/viewthread.php?tid=1128&a...

The last post by Rosco Bodine has a few link to useful papers. The patent is US 3258485 (cyanuric acid + HH)

MineMan - 5-6-2019 at 15:35

but has the nitrate been discussed here...

Can anyone calculate the performance of the perchlorate salt?

Both the perchlorate salt and the mononitrate have yields of 97 percent. I say sorry to the critics. Because yields which are in the high 90s, and only a need for dilute acid once the precursor is had... this looks like the best high performance EM comparable to RDX for us... and the sensitivity is very favorable... it contains less energy then RDX, I don’t know why as the molecule looks more favorable. But the volume of gas is impressive.

The dinitrate is a waste of time

[Edited on 5-6-2019 by MineMan]

underground - 6-6-2019 at 11:53

Have you ever consider melamine dinitrate ?


http://edoc.ub.uni-muenchen.de/12420/1/goebel_michael.pdf


https://patentimages.storage.googleapis.com/29/78/69/1bab837...

[Edited on 7-6-2019 by underground]

MineMan - 6-6-2019 at 19:47

Quote: Originally posted by underground  
Have you ever consider melamine dinitrate ?


http://edoc.ub.uni-muenchen.de/12420/1/goebel_michael.pdf


https://patentimages.storage.googleapis.com/29/78/69/1bab837...

[Edited on 7-6-2019 by underground]


Underground. I don’t see the advantage. The Detonation pressure is close to TNT.... I think it’s a good molecule, especially for very high tempatures, stable enough for space... but with those specialty applications money is not an issue and higher performance EMs can be used....

The diaminourea on the other hand has a very real potential to replace RDX in many applications, it’s safer, and obtains the same Dp... the only downside is the heat of explosion,but rest assured 15 percent Al powder can take care of that... and it will be out performing RDX in shape charge and propellant applications... while only needing dilute nitric acid... THATS HUGE. I am surprised at the lack of excitement....

twelti - 6-6-2019 at 20:58

So, I found carbohydrazide on eBay for around $2/g, so not the cheapest (coincidentally the same vendor selling aminoguanidine bicarbonate and several other interesting chems). Still, no WFNA needed, so that would offset some of the cost/effort required for RDX. Are you going to try it?

Fulmen - 6-6-2019 at 23:48

The lack of excitement is due to cost and availability. $15/kg doesn't sound bad, but that's in bulk. 1kg would probably cost closer to $1000. Even 1/10 of that would negate any benefit from simple nitration.

MineMan - 7-6-2019 at 00:48

Quote: Originally posted by twelti  
So, I found carbohydrazide on eBay for around $2/g, so not the cheapest (coincidentally the same vendor selling aminoguanidine bicarbonate and several other interesting chems). Still, no WFNA needed, so that would offset some of the cost/effort required for RDX. Are you going to try it?


I want to give it a go when I am done from my travels. I would like some advice from those more wise then me about recrystallization and measurements.... I can report back of course... or if you don’t hear from me you can assume it’s so amazing I am taking the secrets to my gave.

twelti - 7-6-2019 at 01:59

I found it for $20 / kg, min order 1 kg, on Alibaba. Not sure I trust that the min order is really 1 kg, but that is what it says.

[Edited on 7-6-2019 by twelti]

Microtek - 7-6-2019 at 05:39

In my experience you can probably trust the minimum order quantity, but the price per kg will likely be much higher.

Fulmen - 7-6-2019 at 12:42

yeah, that's probably the bulk price.

twelti - 10-6-2019 at 09:04

Right enough. I did get a quote for $100 for one kg. That's not too bad assuming you can use that much.

underground - 10-6-2019 at 11:03

It sounds cool. From where you got it from alibaba? Let us know how it does work after you got it.

twelti - 10-6-2019 at 11:31

Chemfine

No.1 Product information:

cas:497-18-7 carbohydrazide 99% boiler water treatment chemicals
Model no. carbohydrazide
Unit price
USD 100.0 /Kilogram/Kilograms
Order quantity
1.0
Product details
Place of Origin:CN;JIA Type:Dyestuff Intermediates Type:Pharmaceutical Intermediates Type:Syntheses Material Intermediates CAS No.:CAS NO.497-18-7 Other Names:1,3-diaminourea MF:CH6N4O EINECS No.:207-837-2 Purity:99.0%min Brand Name:ChemFine Application:watertreat chemicals Appearance:White Crystalline Powder Product name:Carbohydrazide 99% Appearance:White needle crystal powder Purity:99.9%min PH:7.2-9.7 Keywords:Carbohydrazide 99% Packing:25kg/bag HS Code:2928000090 Sample:Availiable

MineMan - 10-6-2019 at 19:35

That quote is too high unless it includes shipping.... they will likely charge 25-100 dollars for shipping. Most likely in the 80 range. Give it a try. I plan too.

underground - 11-6-2019 at 02:22

I also just buy 2kg for 120 USD from Alibaba (including shipping). The transaction was very smooth with very good service. 1kg was for USD70 while USD120 for 2kgs and USD640 for 25kgs because there is big discount on shipping cost for quantity above 20kgs. If anyone wants any details just send me a PM


[Edited on 11-6-2019 by underground]

twelti - 11-6-2019 at 07:57

Quote: Originally posted by underground  
I also just buy 2kg for 120 USD from Alibaba (including shipping). The transaction was very smooth with very good service. 1kg was for USD70 while USD120 for 2kgs and USD640 for 25kgs because there is big discount on shipping cost for quantity above 20kgs. If anyone wants any details just send me a PM


[Edited on 11-6-2019 by underground]


That is a bit better than the quote I got, who is your vendor?

underground - 11-6-2019 at 11:18

You have PM

underground - 11-6-2019 at 14:36

According to Fulmen's PDF, it may be a bit tricky to crystallize it out.

"Both nitrate salts, especially the monodeprotonated salt 2, cause major problems during their isolation since both remain as colourless liquids after the water has been evaporated. 3 crystallizes after the liquid has been taken up in methanol and slowly been evaporated again, whereas 2 solidified after the liquid was taken up in methanol and chilled to -20C for several days. Scratching the flask with a glass rod after the mixture was allowed to come to room temperature resulted in the crystallization of the product. "


"Diaminourea (0.90 g, 10 mmol) is dissolved in nitric acid (2 M, 5 mL, 10 mmol) at room temperature. The solvent is removed from the clear solution resulting in a colourless oil. Recrystallization from ethanol/water yields 2 as colourless solid (after long standing). Alternatively the compound was crystallized after storage at -20C under methanol for several days and scratching the flask with a glass rod after the mixture was allowed to come to room temperature. Yield: 1.48 g, 9.7 mmol, 97%."

It is said that the bis-perchlorate salt could not be isolated due to its high hygroscopicity, and the dinitrate forms a monohydrate so i believe the the mononitrate it should be quite hygroscopic too, but it is still quite interesting.


[Edited on 11-6-2019 by underground]

twelti - 13-6-2019 at 09:21

Quote: Originally posted by underground  
According to Fulmen's PDF, it may be a bit tricky to crystallize it out.

"Both nitrate salts, especially the monodeprotonated salt 2, cause major problems during their isolation since both remain as colourless liquids after the water has been evaporated. 3 crystallizes after the liquid has been taken up in methanol and slowly been evaporated again, whereas 2 solidified after the liquid was taken up in methanol and chilled to -20C for several days. Scratching the flask with a glass rod after the mixture was allowed to come to room temperature resulted in the crystallization of the product. "


"Diaminourea (0.90 g, 10 mmol) is dissolved in nitric acid (2 M, 5 mL, 10 mmol) at room temperature. The solvent is removed from the clear solution resulting in a colourless oil. Recrystallization from ethanol/water yields 2 as colourless solid (after long standing). Alternatively the compound was crystallized after storage at -20C under methanol for several days and scratching the flask with a glass rod after the mixture was allowed to come to room temperature. Yield: 1.48 g, 9.7 mmol, 97%."

It is said that the bis-perchlorate salt could not be isolated due to its high hygroscopicity, and the dinitrate forms a monohydrate so i believe the the mononitrate it should be quite hygroscopic too, but it is still quite interesting.


[Edited on 11-6-2019 by underground]


The freezing method should be doable, right? Once you have some crystals of diaminouronium dinitrate, maybe you could use them to seed the chilled liquid.
My question is, since this is less sensitive than RDX, and RDX is already not that sensitive, would it be hard to initiate?

Tsjerk - 13-6-2019 at 09:24

Quote: Originally posted by twelti  

The freezing method should be doable, right? Once you have some crystals of diaminouronium dinitrate, maybe you could use them to seed the chilled liquid.
My question is, since this is less sensitive than RDX, and RDX is already not that sensitive, would it be hard to initiate?



You could also use a seed crystal with a comparable structure, or use a piece of dust.

Initiation could be done with some lead azide or something.

MineMan - 13-6-2019 at 23:17

Quote: Originally posted by underground  
According to Fulmen's PDF, it may be a bit tricky to crystallize it out.

"Both nitrate salts, especially the monodeprotonated salt 2, cause major problems during their isolation since both remain as colourless liquids after the water has been evaporated. 3 crystallizes after the liquid has been taken up in methanol and slowly been evaporated again, whereas 2 solidified after the liquid was taken up in methanol and chilled to -20C for several days. Scratching the flask with a glass rod after the mixture was allowed to come to room temperature resulted in the crystallization of the product. "


"Diaminourea (0.90 g, 10 mmol) is dissolved in nitric acid (2 M, 5 mL, 10 mmol) at room temperature. The solvent is removed from the clear solution resulting in a colourless oil. Recrystallization from ethanol/water yields 2 as colourless solid (after long standing). Alternatively the compound was crystallized after storage at -20C under methanol for several days and scratching the flask with a glass rod after the mixture was allowed to come to room temperature. Yield: 1.48 g, 9.7 mmol, 97%."

It is said that the bis-perchlorate salt could not be isolated due to its high hygroscopicity, and the dinitrate forms a monohydrate so i believe the the mononitrate it should be quite hygroscopic too, but it is still quite interesting.


[Edited on 11-6-2019 by underground]


I believe the mononitrate is the only worthwhile salt. The dinitrate has far to low energy of explosion.

underground - 13-6-2019 at 23:28

The dinitrate does not worth cause it forms a mono-hydrate. I have seen some other compounds with the same properties from NileRed. When a solution is super saturated sometimes it does not crystallize out. Scratching the container by pressing the crystals it will crystallize out. Also by dropping a single crystal it will crystallize out too. I don't think so we will have any issues. Also he used vacuum to drive off the water. I guess he did not dry the compound completely with vacuum cause he was afraid for decomposition. As long as i do not have any vacuum distillation set up, i will just use some cacl into a desiccator bad to drive all the water off. It may take a while but i believe it will remove all the water completely to dryness.

twelti - 14-6-2019 at 11:30

Quote: Originally posted by underground  
The dinitrate does not worth cause it forms a mono-hydrate. I have seen some other compounds with the same properties from NileRed. When a solution is super saturated sometimes it does not crystallize out. Scratching the container by pressing the crystals it will crystallize out. Also by dropping a single crystal it will crystallize out too. I don't think so we will have any issues. Also he used vacuum to drive off the water. I guess he did not dry the compound completely with vacuum cause he was afraid for decomposition. As long as i do not have any vacuum distillation set up, i will just use some cacl into a desiccator bad to drive all the water off. It may take a while but i believe it will remove all the water completely to dryness.

Any idea on whether a cheap vacuum pump (not rated for corrosive chemicals) would be ok to use for that?

Yamato71 - 15-6-2019 at 23:21

If this product feels more comfortable existing as an oil after nitration, who are we to insist that it conform to a rigid crystalline structure? If I've learned one thing about EM's, it's that trying to make them do anything they don't want to do is not the path to true enlightenment. I know what you're thinking. "But we like our product to be nice and solid and dense and not runny and stuff".

So do I.

Say hallo to my leedle frenn. Fumed silica. This stuff is about the best thing to come along since perforated toilet paper. In the 1860's Alfred Nobel discovered that nitroglycerine would adsorb onto diatomaceous earth, simultaneously turning it into a pasty mass that could be extruded into paper cartridges and lowering its sensitivity. In 2017, Yamato71 discovered that adsorbing nitroglycerine onto fumed silica, another form of silica with a ridiculously high surface area to weight ratio, converts it into a non Newtonian fluid with some amazing properties. Only 5-7% by weight fumed silica added to NG converted it to a free standing gel that would not weep or puddle, even at elevated temperature. This form is easily dispensed from a syringe into places where liquid NG would leak out. !0% SiO2 stiffens it into a fair approximation of a translucent plastique. You might try that with your oily nitrate. I suspect that it will eventually crystallize in a fumed silica matrix anyway, but maybe not. In the meantime you will be able to tailor the final compound to any viscosity you desire.

Y71

Tsjerk - 16-6-2019 at 02:56

Quote: Originally posted by twelti  

Any idea on whether a cheap vacuum pump (not rated for corrosive chemicals) would be ok to use for that?


Get something like this, literally translated it would translate to "water jet pump", they are cheap (10 dollar-ish) and go down to the vapour pressure of the water being used.

JohnDoe13 - 16-6-2019 at 04:32

Quote: Originally posted by Yamato71  
If this product feels more comfortable existing as an oil after nitration, who are we to insist that it conform to a rigid crystalline structure? If I've learned one thing about EM's, it's that trying to make them do anything they don't want to do is not the path to true enlightenment. I know what you're thinking. "But we like our product to be nice and solid and dense and not runny and stuff".

So do I.

Say hallo to my leedle frenn. Fumed silica. This stuff is about the best thing to come along since perforated toilet paper. In the 1860's Alfred Nobel discovered that nitroglycerine would adsorb onto diatomaceous earth, simultaneously turning it into a pasty mass that could be extruded into paper cartridges and lowering its sensitivity. In 2017, Yamato71 discovered that adsorbing nitroglycerine onto fumed silica, another form of silica with a ridiculously high surface area to weight ratio, converts it into a non Newtonian fluid with some amazing properties. Only 5-7% by weight fumed silica added to NG converted it to a free standing gel that would not weep or puddle, even at elevated temperature. This form is easily dispensed from a syringe into places where liquid NG would leak out. !0% SiO2 stiffens it into a fair approximation of a translucent plastique. You might try that with your oily nitrate. I suspect that it will eventually crystallize in a fumed silica matrix anyway, but maybe not. In the meantime you will be able to tailor the final compound to any viscosity you desire.

Y71


Glad to hear you again. Keep the good work and ideas.

twelti - 16-6-2019 at 09:31

Quote: Originally posted by Tsjerk  
Quote: Originally posted by twelti  

Any idea on whether a cheap vacuum pump (not rated for corrosive chemicals) would be ok to use for that?


Get something like this, literally translated it would translate to "water jet pump", they are cheap (10 dollar-ish) and go down to the vapour pressure of the water being used.

Yes, an aspirator. Unfortunately for me, I don't have running water closeby. I should probably put in a sink?

Tsjerk - 16-6-2019 at 09:56

You can use a water pump and a with a big bucket where you collect the water to reuse.

twelti - 16-6-2019 at 15:56

Quote: Originally posted by Tsjerk  
You can use a water pump and a with a big bucket where you collect the water to reuse.

True, but I think you need a a strong water pump.

MineMan - 16-6-2019 at 17:39

Quote: Originally posted by Yamato71  
If this product feels more comfortable existing as an oil after nitration, who are we to insist that it conform to a rigid crystalline structure? If I've learned one thing about EM's, it's that trying to make them do anything they don't want to do is not the path to true enlightenment. I know what you're thinking. "But we like our product to be nice and solid and dense and not runny and stuff".

So do I.

Say hallo to my leedle frenn. Fumed silica. This stuff is about the best thing to come along since perforated toilet paper. In the 1860's Alfred Nobel discovered that nitroglycerine would adsorb onto diatomaceous earth, simultaneously turning it into a pasty mass that could be extruded into paper cartridges and lowering its sensitivity. In 2017, Yamato71 discovered that adsorbing nitroglycerine onto fumed silica, another form of silica with a ridiculously high surface area to weight ratio, converts it into a non Newtonian fluid with some amazing properties. Only 5-7% by weight fumed silica added to NG converted it to a free standing gel that would not weep or puddle, even at elevated temperature. This form is easily dispensed from a syringe into places where liquid NG would leak out. !0% SiO2 stiffens it into a fair approximation of a translucent plastique. You might try that with your oily nitrate. I suspect that it will eventually crystallize in a fumed silica matrix anyway, but maybe not. In the meantime you will be able to tailor the final compound to any viscosity you desire.

Y71


Very interesting ideas! If you want I can send you some diaminourea?

twelti - 17-6-2019 at 07:42

What exactly is the liquid component left after the dinitrate is crystalized out? Would it be an inert if left in and absorbed like Yamato suggests? Also, won't it be even less sensitive? If it is already less sensitive that RDX, maybe hard to detonate?

Tsjerk - 17-6-2019 at 08:08

I wouldn't call RDX insensitive, any blasting cap can set it off.

twelti - 17-6-2019 at 14:32

Quote: Originally posted by Tsjerk  
I wouldn't call RDX insensitive, any blasting cap can set it off.

Yes, it as all relative i suppose. Still, you are including an inert if you don't crystalize the dinitrate out and just absorb it all into the fumed silica.

Tsjerk - 17-6-2019 at 15:04

I think the point made by Yamato71 is that you don't need to crystallize it. And does it really matter if you add 10% of something inert? It got Nobel rich enough to have the most prestigious price named after him by paying for them.

MineMan - 17-6-2019 at 18:26

Quote: Originally posted by Tsjerk  
I think the point made by Yamato71 is that you don't need to crystallize it. And does it really matter if you add 10% of something inert? It got Nobel rich enough to have the most prestigious price named after him by paying for them.


True. But dynamite was the first truly usable high powered EM...

underground - 18-6-2019 at 02:32

By having 10% inerts it will drop the performance for sure. I can not see any reason why not to crystallize it and keep it as a liquid.

Yamato71 - 20-6-2019 at 16:33

I've described my experience with fumed silica in another thread since it doesn't relate directly to the subject of this thread. Having said this, I'll drop one more little nugget about fumed silica. When mixed with a stoichemetric amount of 325 mesh magnesium powder it makes an interesting flash powder. For one thing, it only flashes. Igniting a pile of it on a plate will result in a very intense flash of white light... and not much else. There will be a puff of white smoke, but almost no report. It can be packed into clear plastic tubing and will act as a fast fuse without rupturing the tubing. Have fun coming up with novel uses for this.

MineMan - 30-6-2019 at 14:33

All,

I am confused. If 65 percent nitric acid is used will the dinitrate form? Is 30 percent needed for the mononitrate??

Both sources from Klaptoke seem a little contradictory. Must I dilute the 65 percent nitric to ensure the dinitrate does not form? How do I choose one over the other?

MineMan - 30-6-2019 at 15:26

All. The carbohydrazide has an ammonia like odor that is very strong when the bag is opened. Is this a hydrazine odor or ammonia? Any safety precautions like a mask, or is this not necessary, this is new territory for me?

underground - 30-6-2019 at 18:25

It is quite normal to smell like ammonia since it is made out of hydrazine. Try not to smell it and use protective equipment. The concentration of nitric acid is not important as long as you use 1:1 molar ratio of NA and DU.

MineMan - 30-6-2019 at 22:41

But if I don’t add it all at once the concentration changes. But the tempture won’t allow adding all at once. So. I don’t understand...

Because with the first gram addition the concentration is 10M to 1M

Tsjerk - 30-6-2019 at 23:32

The formation of the mono and the di-nitrate are equilibrium reactions, so if you add the carbohydrazide to the nitric acid you will form the di-nitrate first. But when more carbohydrazide is added the not nitrated molecules will pick up the second nitrate from the di-nitrated molecules which will make you end up with a batch of mono-nitrated carbohydrazide.

twelti - 4-7-2019 at 12:27

Quote: Originally posted by underground  
By having 10% inerts it will drop the performance for sure. I can not see any reason why not to crystallize it and keep it as a liquid.

Just wondering what those "inerts" are? I am not a chemist, but in looking at the equation, DAU just picks up an H and a nitrate group from the HNO3. I'm guessing the water takes part in the equilibrium process, but at the end there should just be DAU mononitrate and water. SO, can higher strength NA be used so there is less water at the end? Also, if we tried yamato's fumed silica idea, would the water just evaporate anyway? I would think it would evaporate rather quickly, due to the large surface area. Then no inerts. Maybe density would then be low though...?

underground - 4-7-2019 at 12:29

Read that PDF out and all your questions will be answered.

http://www.sciencemadness.org/talk/files.php?pid=614532&...

twelti - 4-7-2019 at 12:57

Quote: Originally posted by underground  
Read that PDF out and all your questions will be answered.

http://www.sciencemadness.org/talk/files.php?pid=614532&...

I have read it. I may not understand all of it, not being a chemist. I don't see the answers to my questions there. For example it says that the DAU is a strong base, so only weak NA is needed. It doesn't say you can't use stronger NA (less water to get rid of at the end). I'm also wondering if the solution could be heated to drive off water, since it does not decompose until 240 degrees. If I understand correctly.

underground - 4-7-2019 at 13:12

The mononitrate and dinitrate can be made by adjusting the nitric acid molar ratio. 1:1 molar ratio of DAU and NA will produce the mononitrate, while 1:2 molar ratio will produce the dinitrate. We may have to dilute the NA a bit too and keep it cool. From PDF, they used 2M NA witch actually contains 22.2 mmol per 11.1 mL. It may dry out by heating once the mononitrate decomposes at 242 C. Also a desiccator bag may drive off all the water too. We have to both them out.

To give you an idea, distilled water was added to 97gr of 65% NA (1MOL) until 500ml reached. Then 90,09g of DU (1MOL) was added to that solution.

Now i am not sure if the NA have to be diluted that much, another person with some better knowledge in chemistry is welcome to answer.

[Edited on 4-7-2019 by underground]

twelti - 4-7-2019 at 16:13

Quote: Originally posted by underground  
The dinitrate does not worth cause it forms a mono-hydrate. I have seen some other compounds with the same properties from NileRed. When a solution is super saturated sometimes it does not crystallize out. Scratching the container by pressing the crystals it will crystallize out. Also by dropping a single crystal it will crystallize out too. I don't think so we will have any issues. Also he used vacuum to drive off the water. I guess he did not dry the compound completely with vacuum cause he was afraid for decomposition. As long as i do not have any vacuum distillation set up, i will just use some cacl into a desiccator bad to drive all the water off. It may take a while but i believe it will remove all the water completely to dryness.

I thought we were after the mono nitrate. That is 5 ml 10 mmole 2M NA.

underground - 4-7-2019 at 16:38

Quote: Originally posted by twelti  

I thought we were after the mono nitrate. That is 5 ml 10 mmole 2M NA.


You can use either 5 ml 10 mmole 2M NA and 10mmole DU or 2 M, 11.1 mL, 22.2 mmol and 22.2mmol DU for the mononitrate salt. It is the same. Molar ratio is what it matters.

[Edited on 5-7-2019 by underground]

underground - 7-7-2019 at 05:16

I just got some carbozydrazide and react it with some 65% Nitric acid . 97 grams of 65% NA (1 mole) was reacted with 90,1g of DU (1 mole). The reaction produces quite a bit of heat so i put the NA into an ice bath and add DU. Everything was dissolved really quick leaving an oil like substance. Trying to boil off the water does not work as it looks like it decomposes before even it crystallize out. The more water is removed the more like syrup became. It is a bit tricky to crystallize it out. I will try to put some into -20C and bring it back to room temp few times. Also i will put some into a desiccator bag to see if it will dry out.

[Edited on 7-7-2019 by underground]

twelti - 7-7-2019 at 09:33

I mixed some up using the 2M acid. Not much, if any, heat. Put it in a dessicator for a couple of days, then vacuum for half an hour. I added approx equal volume of Methanol to it. Then into the freezer overnight. So far no luck getting it to crystalize though. Tried dropping a couple of crystals of PETN in to seed it. Nothing yet...

[Edited on 7-7-2019 by twelti]

underground - 7-7-2019 at 12:26

I removed as much water as i could with just gentle boiling. It become very thick. I added some ethanol, it actually was not dissolving a lot, remaining mostly on top. After adding methanol from clear solution become white. Put it into the deep freeze and became like honey consistency, like a white honey. From pdf that i have read it claims to remain at that low temp for couple of days. I will keep it freeze for about 4-5 days and i will bring it back to room temp and scrach the flask to see if i got anything.

[Edited on 7-7-2019 by underground]

MineMan - 7-7-2019 at 13:45

It’s like being a little kid and waiting for your parents to get up in the morning on Christmas Day.

twelti - 7-7-2019 at 15:16

Quote: Originally posted by MineMan  
It’s like being a little kid and waiting for your parents to get up in the morning on Christmas Day.

What did YOU get for Christmas? Some very insensitive, cheap an powerful secondary explosive? Ok, go play with the other kids!

Seriously:

I'm wondering if using a larger amount would help it start to crystalize. Are there any other nifty chemistry tricks? Ultrasound? Microwave?
I read in one place to scratch with glass rod at the liquid/air interface (i.e. not at the bottom of the container like I was). Also another trick, dip in the glass rod and remove, allowing liquid on it to evaporate or at least crystalized, then put it back in the liquid. Finally, what about colder temps. Salt/ice bath or even dry ice/alcohol?

twelti - 7-7-2019 at 15:18

Quote: Originally posted by underground  
I removed as much water as i could with just gentle boiling. It become very thick. I added some ethanol, it actually was not dissolving a lot, remaining mostly on top. After adding methanol from clear solution become white. Put it into the deep freeze and became like honey consistency, like a white honey. From pdf that i have read it claims to remain at that low temp for couple of days. I will keep it freeze for about 4-5 days and i will bring it back to room temp and scrach the flask to see if i got anything.

[Edited on 7-7-2019 by underground]

Did you get an emulsion then?

underground - 7-7-2019 at 15:23

Yea it is still an emulsion. The stuff will not crytalize if you made the trick with the glass rod. I have made 2 bunches of 1 mole each. I got almost 2 moles of DUN, it is a bit big scale. For now i will just try to do whatever pdf say. In general they claim to keep it at -20C for several days as i said above. It is just few hours till now.

[Edited on 7-7-2019 by underground]

twelti - 7-7-2019 at 15:58

Quote: Originally posted by underground  
Yea it is still an emulsion. The stuff will not crytalize if you made the trick with the glass rod. I have made 2 bunches of 1 mole each. I got almost 2 moles of DUN, it is a bit big scale. For now i will just try to do whatever pdf say. In general they claim to keep it at -20C for several days as i said above. It is just few hours till now.

[Edited on 7-7-2019 by underground]

Yeah it is strange that they say to let it go up to RT, then scratch. I would have thought it would crystallize at lower temp first.

I just put in a larger amount of PETN crystals in there as seed. Still only a fraction of a mg though.

twelti - 8-7-2019 at 11:20

Is there any way the uncrystalized oil could be used, as a straight liquid explosive?

Tsjerk - 8-7-2019 at 12:16

Maybe it is an idea to take a known weight small sample, say a couple of grams, smear that out in order to form a big surface area and put that in a desiccator to see if there is still water in your sample. Maybe a last little bit of water is making things hard for you guys.

Quote: Originally posted by twelti  
Is there any way the uncrystalized oil could be used, as a straight liquid explosive?


As long as your container and your detonator are watertight you can probably set it of while it being a liquid, why not?

[Edited on 8-7-2019 by Tsjerk]

underground - 8-7-2019 at 14:14

Quote: Originally posted by Tsjerk  


As long as your container and your detonator are watertight you can probably set it of while it being a liquid, why not?

[Edited on 8-7-2019 by Tsjerk]


I was thinking the same in worst case scenario, but it may be quite hard to ddt and the extra water may drop the performance. We have to try a desiccator bag too and maybe with some strong drying agents like concentrated H2SO4.

[Edited on 8-7-2019 by underground]

twelti - 8-7-2019 at 14:39

Quote: Originally posted by underground  
Quote: Originally posted by Tsjerk  


As long as your container and your detonator are watertight you can probably set it of while it being a liquid, why not?

[Edited on 8-7-2019 by Tsjerk]


I was thinking the same in worst case scenario, but it may be quite hard to ddt and the extra water may drop the performance. We have to try a desiccator bag too and maybe with some strong drying agents like concentrated H2SO4.

[Edited on 8-7-2019 by underground]


I tried with silica gel. So H2SO4 is better? What about P2O5?

underground - 8-7-2019 at 15:05

I dunno about P2O5. Try cacl/NaOH/H2SO4. You can put them all together separately into the same bag. Although h2so4 is the strongest.

Edit: After searching a bit i found that P2O5 is very strong desiccant agent, possibly even more than concentrated H2SO4. You can give it a try.

[Edited on 8-7-2019 by underground]

twelti - 8-7-2019 at 19:25

So, I attempted to dry it some more, using gentle heat and then vacuum. I got it down to a fairly small amount of liquid. I think it was nearly water free. I added more methanol and put it back in the freezer for a day. Today there was something there. I thought maybe ice, and in fact some did melt, although reluctantly. Still 2 hours after I took it out, it has been at RT for a while now and Ive still got about half of the mass unmelted. May be a mix of DAUDN and water? Strange also since the first time I had it in the freezer for a day and a half and got NO crystals or ice. If anything there should be less water in it now, yet I'm getting this:





thumbnail (20).jpg - 150kB thumbnail (21).jpg - 130kB

most of that has melted but there is still some that is definitely a solid, at RT for 3 hours now.

[Edited on 9-7-2019 by twelti]

Microtek - 8-7-2019 at 23:45

Do you know what the solubility of DAUDN is in this solvent system? The "melting" that you see may actually be the product dissolving as the temperature rises and the solubility therefore increases.

About the dessicants: P2O5 is certainly a stronger dessicant than concentrated sulfuric acid. In fact also stronger than SO3, since P2O5 can dehydrate sulfuric acid to form SO3 and phosphoric acids of diferent kinds.

MineMan - 9-7-2019 at 01:05

Good job twelti! You made history! Now do a witness plate test:D

underground - 9-7-2019 at 05:51

Good job twelti. Step by step we getting closer to our goal.

wessonsmith - 9-7-2019 at 07:15

Quote: Originally posted by twelti  
So, I attempted to dry it some more, using gentle heat and then vacuum. I got it down to a fairly small amount of liquid. I think it was nearly water free. I added more methanol and put it back in the freezer for a day. Today there was something there. I thought maybe ice, and in fact some did melt, although reluctantly. Still 2 hours after I took it out, it has been at RT for a while now and Ive still got about half of the mass unmelted. May be a mix of DAUDN and water? Strange also since the first time I had it in the freezer for a day and a half and got NO crystals or ice. If anything there should be less water in it now, yet I'm getting this:







most of that has melted but there is still some that is definitely a solid, at RT for 3 hours now.

[Edited on 9-7-2019 by twelti]


Not sure if this helps:


16.DIAMINOURONIUM DINITRATE
We recently investigated diaminouronium nitrate, which is a new secondary explosive. With
regard to development of new high-oxidizers the double-protonated compound
diaminouronium dinitrate (DAU_2NO3) was synthesized starting from cheap available
diaminourea, which is protonated with two equivalents of dilute nitric acid according to

Synthesis of diaminouronium dinitrate monohydrate.
The water is removed in vacuo and the product is isolated as a colorless solid after addition of
methanol to the evaporated residue. The compound crystallizes as a monohydrate although
showing an oxygen balance of 10.3 %. However, the water can be removed at 75 °C using
vacuo. DAU_2NO3 is completely insensitive towards impact and friction but, unfortunately,
decomposing already at 115 °C. Latter property retards probably all possible applications.

p44 https://www.serdp-estcp.org/content/download/10799/136954/fi...

twelti - 9-7-2019 at 08:41

Quote: Originally posted by wessonsmith  
Quote: Originally posted by twelti  
So, I attempted to dry it some more, using gentle heat and then vacuum. I got it down to a fairly small amount of liquid. I think it was nearly water free. I added more methanol and put it back in the freezer for a day. Today there was something there. I thought maybe ice, and in fact some did melt, although reluctantly. Still 2 hours after I took it out, it has been at RT for a while now and Ive still got about half of the mass unmelted. May be a mix of DAUDN and water? Strange also since the first time I had it in the freezer for a day and a half and got NO crystals or ice. If anything there should be less water in it now, yet I'm getting this:







most of that has melted but there is still some that is definitely a solid, at RT for 3 hours now.

[Edited on 9-7-2019 by twelti]


Not sure if this helps:


16.DIAMINOURONIUM DINITRATE
We recently investigated diaminouronium nitrate, which is a new secondary explosive. With
regard to development of new high-oxidizers the double-protonated compound
diaminouronium dinitrate (DAU_2NO3) was synthesized starting from cheap available
diaminourea, which is protonated with two equivalents of dilute nitric acid according to

Synthesis of diaminouronium dinitrate monohydrate.
The water is removed in vacuo and the product is isolated as a colorless solid after addition of
methanol to the evaporated residue. The compound crystallizes as a monohydrate although
showing an oxygen balance of 10.3 %. However, the water can be removed at 75 °C using
vacuo. DAU_2NO3 is completely insensitive towards impact and friction but, unfortunately,
decomposing already at 115 °C. Latter property retards probably all possible applications.

p44 https://www.serdp-estcp.org/content/download/10799/136954/fi...

Yes, that and the Fischer paper seems to be the only source on this synthesis that we are all using, as far as I know (and I have looked). There is one older, similar ref by the same author(s).

[Edited on 9-7-2019 by twelti]

twelti - 9-7-2019 at 08:44

Quote: Originally posted by MineMan  
Good job twelti! You made history! Now do a witness plate test:D

Right now I'd need to use aluminum foil as my witness plate, as I don't have a lot of material here. But I'm gonna make a much bigger batch.

twelti - 9-7-2019 at 08:46

Quote: Originally posted by Microtek  
Do you know what the solubility of DAUDN is in this solvent system? The "melting" that you see may actually be the product dissolving as the temperature rises and the solubility therefore increases.

About the dessicants: P2O5 is certainly a stronger dessicant than concentrated sulfuric acid. In fact also stronger than SO3, since P2O5 can dehydrate sulfuric acid to form SO3 and phosphoric acids of diferent kinds.

That is what confuses me. What IS the solvent system. There should only be maybe some water, and if one removes that, DAUDN only. Maybe there was a small amount of water still in my mixture.

Microtek - 9-7-2019 at 12:23

Didn't you add methanol? This may function as a solvent or maybe an anti-solvent in conjunction with water, I can't really tell.

underground - 9-7-2019 at 12:48

I also did evaporate carefully as much water as i could (atmospheric pressure). It was like honey at room temp. I transfer it into deep freeze and i got few crystals. I checked it again after a while and more crystals came out. I will leave it all day there and check it after. Evaporating the water as much as possible and transfer it into deep freeze looks to be the way to go.


[Edited on 9-7-2019 by underground]

twelti - 9-7-2019 at 13:57

Quote: Originally posted by Microtek  
Didn't you add methanol? This may function as a solvent or maybe an anti-solvent in conjunction with water, I can't really tell.

Right, of course, I forgot about that. It just seems weird to be adding a solvent to an oil.

Tsjerk - 9-7-2019 at 14:34

It could be the one molecule of water is actually needed to crystallize the mono-nitrate monohydrate. Or is only the the di-nitrate crystallizing as the mono-hydrate?

twelti - 9-7-2019 at 15:31

Quote: Originally posted by underground  
I also did evaporate carefully as much water as i could (atmospheric pressure). It was like honey at room temp. I transfer it into deep freeze and i got few crystals. I checked it again after a while and more crystals came out. I will leave it all day there and check it after. Evaporating the water as much as possible and transfer it into deep freeze looks to be the way to go.


[Edited on 9-7-2019 by underground]

Did you add the methanol? It would be interesting to try some other (anti?) solvents.

underground - 9-7-2019 at 16:25

Only the dinitrate salt form a monohydrate.

I did not add any solvent. Most of ethanol was evaporated. After that i did not add any another.

[Edited on 10-7-2019 by underground]

underground - 10-7-2019 at 04:02

Today i checked it out and everything was solid like a rock. I had to broke my beaker to take it out. Next time i will use a blastic bottle. It is quite hygroscopic, the surface became wet in about 2 minutes.





[Edited on 10-7-2019 by underground]

twelti - 10-7-2019 at 09:12

Quote: Originally posted by underground  
Today i checked it out and everything was solid like a rock. I had to broke my beaker to take it out. Next time i will use a blastic bottle. It is quite hygroscopic, the surface became wet in about 2 minutes.





[Edited on 10-7-2019 by underground]

WOW! That looks about as much different from mine as it could possibly be. For mine, it has now mostly dried out, and there doesn't seem to be much material there, considering i started with a gram. What I do have is crystalline. I'm going to make a bigger batch and split it up into smaller containers and try different things. In the paper it mentions as the first option Crystallizing with ethanol/water, sitting for a long time at RT I think.

underground - 11-7-2019 at 05:11

I just melt it again and filter with a screen to remove any glass and transfer it into a greaseproof paper. I seal it airtide and put it into -20 C.


https://i.ibb.co/fH878ZC/20190711-155346.jpg

The good things is that it can easily casted. Aslo during casting, most of water evaporates. The bad thing is that it is very hygroscopic. There is no way to keep it as a dry powder. It can be casted though into some small airtide containers, like 5g, and use it accordingly. The next step is actually to see how easily it goes ddt, but it will take a bit to test it myself.

[Edited on 11-7-2019 by underground]

MineMan - 16-7-2019 at 20:49

Anyone have any updates? I know magnesium sulfate readily crashes the DAUN.

twelti - 18-7-2019 at 05:49

Quote: Originally posted by MineMan  
Anyone have any updates? I know magnesium sulfate readily crashes the DAUN.

Where did you see that? i am out of town so no further work yet.

twelti - 23-7-2019 at 15:50

Can someone help us understand what this means:

"The water is removed in vacuo and the product is isolated as a colorless solid after addition of methanol to the evaporated residue. The compound crystallizes as a monohydrate although showing an oxygen balance of 10.3 %. However, the water can be removed at 75 °C using vacuo. DAU_2NO3 is completely insensitive towards impact and friction but, unfortunately, decomposing already at 115 °C. Latter property retards probably all possible applications. "

What does adding the methanol accomplish? If we remove the water first, how can it crystalize as a monohydrate? Or is it just confusingly written? Or am I just an idiot? Don't answer that!

MineMan - 23-7-2019 at 19:09

That’s the dinitrate. We have been after the monk nitrate.

twelti - 23-7-2019 at 23:14

Quote: Originally posted by MineMan  
That’s the dinitrate. We have been after the monk nitrate.

It sounds very similar to what they say about the mononitrate though.

MineMan - 24-7-2019 at 05:00

Quote: Originally posted by twelti  
Quote: Originally posted by MineMan  
That’s the dinitrate. We have been after the monk nitrate.

It sounds very similar to what they say about the mononitrate though.


Oh. For crystallizing. Yes.

Is it Christmas?

twelti - 28-7-2019 at 09:14

Back from business trip, doing some experiments on DAUN. I have noticed some things.
1. DAUN seems to not not dissolve in water once crystalized. I have my first small batch is floating in water for days now, still crystalized.
2. Crashing newly prepared DAUN ( no water removed) into saturated magnesium sulfate water solution had no effect.
3. I noticed before that DAUN did not dissolve in EtOH, so I tried adding that to the freshly prepared DAUN (no water removed). I got immediate milky crash, which then dissipated and went clear again. Overnight however, I got this. Now I put it in the freezer to see if any more crystals come out.

Seems promising.




20190728_083333.jpg - 3.7MB

[Edited on 28-7-2019 by twelti]

underground - 28-7-2019 at 09:41

I also got a milky thing after adding ethanol. Indeed it does not dissolve easily in water once it ppt out. I removed as much water as i could and then deep freeze. It solidified immediately. As i said above, it is quite hygroscopic, it become wet if you left it outside in for few minutes. When i got some time i will try to detonate few grams.

Edit: I used 1:1 molar ratio so i got mostly DU nitrate

[Edited on 28-7-2019 by underground]

twelti - 28-7-2019 at 21:50

Quote: Originally posted by underground  
I also got a milky thing after adding ethanol. Indeed it does not dissolve easily in water once it ppt out. I removed as much water as i could and then deep freeze. It solidified immediately. As i said above, it is quite hygroscopic, it become wet if you left it outside in for few minutes. When i got some time i will try to detonate few grams.

Edit: I used 1:1 molar ratio so i got mostly DU nitrate

[Edited on 28-7-2019 by underground]

Strange behavior too: It went from clear to milky when I did the initial crash, then eventually back to clear. THEN when I simply poured from one container to a larger one, it went milky again. Weird.

James Ikanov - 29-7-2019 at 14:43

This is just some speculation on my part, but in the one attempt of synthesizing nitroxylitol I made, I learned that the reason it is probably so obnoxiously liquid is that the different stages of nitration are soluble in each other. Could there be a similar behavior here? Perhaps when poured, the physical agitation separates it a bit? The only other thing I can think of is that there is some kind of shift in the "crystal" structure when agitated, and I don't know which would be more likely. I would think that the required temperature change in the presence of methanol lends itself more to the second one, but both seem plausible and maybe not even mutually exclusive....

twelti - 29-7-2019 at 18:06

Quote: Originally posted by James Ikanov  
This is just some speculation on my part, but in the one attempt of synthesizing nitroxylitol I made, I learned that the reason it is probably so obnoxiously liquid is that the different stages of nitration are soluble in each other. Could there be a similar behavior here? Perhaps when poured, the physical agitation separates it a bit? The only other thing I can think of is that there is some kind of shift in the "crystal" structure when agitated, and I don't know which would be more likely. I would think that the required temperature change in the presence of methanol lends itself more to the second one, but both seem plausible and maybe not even mutually exclusive....

It is an equilibrium reaction, so entirely plausible I guess. Makes me also wonder about the method used by Underground. He did the same reaction (1 equivalent of precursor and of acid) but with undiluted acid (65%) so less water. I wonder if that affects the equilibrium process, since his results were somewhat different than mine. I stuck to the exact reaction in the Fischer paper.

For me, I feel like if I added enough EtOH, it would all crystalize out, but it would take a large volume. Not sure though.

Latest

twelti - 30-7-2019 at 23:04

I made a larger batch, using the 2M nitric acid as per Fischer. Using 9 g of the DAU. Diluting the product with a lot of Ethanol, I got around maybe 3 gram to crystalize fairly quickly. I have tried a few experiments with the remaining liquid, which must have a lot of DAUN still in it. I tried various diluants to see if any caused crystallization. The last thing I just tried was I took around 25 ml of the remaining liquid and added 2 drops of sulfuric acid (conc.). I though maybe it would suck up the water and force crystalization. Well, a whole lot of white solid did crystalize out. I've no idea what it might be. DAUN? or something else.

underground - 31-7-2019 at 07:37

You may have dehydrated your DUN, maybe aminonitrourea is produced. I just use 65% NA cause i really dont want to boil all tha water out. Try to carefully boil out all the water to the point you may decompose few of the salt. Put it into a deep freeze and i am sure you will get what i got. What is happening is that you mostly got molten DUN and by freezing it, it become solid. The is no need for crystalization as long as you use pure nitric acid, just evaporate all the water out.

[Edited on 31-7-2019 by underground]

twelti - 31-7-2019 at 10:01

Quote: Originally posted by underground  
You may have dehydrated your DUN, maybe aminonitrourea is produced. I just use 65% NA cause i really dont want to boil all tha water out. Try to carefully boil out all the water to the point you may decompose few of the salt. Put it into a deep freeze and i am sure you will get what i got. What is happening is that you mostly got molten DUN and by freezing it, it become solid. The is no need for crystalization as long as you use pure nitric acid, just evaporate all the water out.

[Edited on 31-7-2019 by underground]

But then why did they use dilute NA in the Fischer paper? You said it generated a lot of heat.
Have you done any testing on your product? you also got a single solid chunk, did you not? Are you sure it is working correctly?

underground - 31-7-2019 at 11:44

It looks good το me, i have not tried yet to detonate. The melting point is correct. I also got some crystals at the walls of the beaker like umbrella, the rest at the bottom was like the photos above. By melting and rapid cooling it, crystals become really small, that is why you cant actually see any crystals at all.

[Edited on 31-7-2019 by underground]

twelti - 31-7-2019 at 19:25

BTW, I weighed the product I already got, using the standard procedure and crashing with EtOH (with some dying first but still some water in it). I was surprised that I actually had around 9 g of DAUN. Starting form 9 g of DAU, that's not as bad as I thought. I want to try your method with 70% NA, but now that I think of it, that is physically not a lot of liquid for the given amount of solid precursor. to try to mix.

MineMan - 31-7-2019 at 23:15

This is exciting!

Sorry for my recent silence on this thread and DMs. I feel at this time I am unable to contribute.

underground - 31-7-2019 at 23:22

Cool the NA and then add it to the DAU. You can even add some ice. This is what i did. I dont see any reason why 65% NA will not work and 2% will work. 65% still got plenty of water to do any nitration.

twelti - 1-8-2019 at 08:50

Quote: Originally posted by underground  
Cool the NA and then add it to the DAU. You can even add some ice. This is what i did. I dont see any reason why 65% NA will not work and 2% will work. 65% still got plenty of water to do any nitration.

Sounds good. Have you tried to cast it yet?
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