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Author: Subject: Diethylenetriamine trinitrate – Ammonium nitrate high-energy complex
Dr. Watson
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[*] posted on 7-3-2014 at 06:39
Diethylenetriamine trinitrate – Ammonium nitrate high-energy complex




Materials:
50 grams . ammonium nitrate
10 ml . diethylenetriamine ( DETA )
2 g . aluminum powder
10-15 ml . Water .

Synthesis was performed outdoors!
Ammonium nitrate is placed in a inox or glass heat-resistant container. Add to it Diethylentriamine. Reaction is exotermic ( formed diethylenetriamine trinitrate - high explosive, which in turn forms a high-energy complex with excess ammonium nitrate) and begins to emit a lot of ammonia gas . Add water and the container is placed on low heat until everything is dissolved and boil. Formed continuously more ammonia gas and the solution turns yellow. Without amplified heating , waiting the water to boil off - this is known by the termination of the release of steam and start lightly smoking . Twenty seconds after that stop heating and allow the solution to cool. When begin the crystallization, add aluminum powder. Stir vigorously to have wetting of aluminum, followed by crystallization and fragmentation of sticky agglomerates. Process is dirty - flies aluminum - and laborious , but the result is worth it.

Еxcuse my bad English and and poor pictures quality!

Test - 183g substance:

[000116].jpg - 24kB

[000117].jpg - 28kB 0,15g lead azide + 0,65g high-energy explosive.

[000118].jpg - 71kB

[000119].jpg - 75kB Crater with a diameter of one meter and a depth of 25 cm.

[000120].jpg - 74kB 12 liter bucket for scale.




[Edited on 8-3-2014 by Dr. Watson]
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[*] posted on 9-3-2014 at 03:15


The name "Diethylenetriamine trinitrate – Ammonium nitrate high-energy complex" is not true. On what complex are you talking about?? The mixture that you made is simply an ammonium nitrate based explosive. Based on weight of your ingredient, the NH4NO3 is in excess (approx. 2.3 time the quantity of Diethylenetriamine trinitrate). So the mixture uses the aluminium as a sensitizer and the Diethylenetriamine trinitrate as a detonation enhancer (the Diethylenetriamine trinitrate increase the detonation performance of the mixture).

Dany.
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Dr. Watson
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[*] posted on 9-3-2014 at 20:01


Really formed complex compound is described. See the highlighted yellow part of the attachment. This is not my idea:

Attachment: US4481048.pdf (1.2MB)
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The process of separation of the components takes 2-3 days.
Just thus giving an easy and simple synthesis.
Aluminum is an activator, because I do not like large initiating devices.

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[*] posted on 9-3-2014 at 23:35


Dr.Watson
U synthesized Diethylenetriamine trinitrate??? or u bought it???
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[*] posted on 9-3-2014 at 23:37


Dr.watson
U used 183 grams to make that hole???
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[*] posted on 10-3-2014 at 01:30


Quote: Originally posted by Dr. Watson  
Really formed complex compound is described. See the highlighted yellow part of the attachment. This is not my idea:




The process of separation of the components takes 2-3 days.
Just thus giving an easy and simple synthesis.
Aluminum is an activator, because I do not like large initiating devices.



I read the patent that you posted and the word complex is mentioned 1 time in the text to describe the decomposition process of the compound (and not to describe it) .If this was a real complex the authors should mentioned this in the text. It is clear that this mixture at certain ratio can form eutectic mixture. Other similar eutectic mixture can be formed using ammonium nitrate and ethylene dinitramine.

The aluminium that you used is a sensitizer or an activator call it whatever you want...

Dany.

[Edited on 10-3-2014 by Dany]
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[*] posted on 10-3-2014 at 09:51


Well, let's be a eutectic mixture.

Please administrator to delete this topic.
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[*] posted on 10-3-2014 at 11:14


Hmmmm. This is interesting, when does the heating occur? On mixture of the DETA and ammonium nitrate? Or after some water is added to this mix? How exothermic is this reaction? Any measurement of how much heat it gives off?

What I am trying to get a sense of here is the hazard level involved in merely mixing the DETA and AN together, i.e., is it liable to go off all by itself on scaling up a little or catch fire or something. It would seem from what I am reading there is an exotherm *before* addition of water, which would make me suspect that scaling up such a mix would be a *terrible* idea, especially with added aluminium to sensitize it... More details of how this stuff handles is desired.
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[*] posted on 10-3-2014 at 14:58


I have ethylen-diamine, di-ethylen-triamine and tetra-ethylen-pentamine at home.

The polynitrate salts are good ideas on their own...even better would be the polyperchlorate salts for a better OB, density and sensitivity! One might also consider polydinitramide, polynitroformiates and polytetranitroethandiate but this is one step further in the quest of the highest densities HEM.

A good idea would be the making of a polymeric-polyamine by addition of one equivalent of formaldehyde...and then the formation of polynitroso compounds with nitrous acid (the trinitroso brother of RDX is quite powerful so would be a polynitroso-polymer) or polynitramines compounds with concentrated HNO3/N2O5...such a polynitramine could outperform RDX and HMX!
NH2-CH2-CH2-NH-CH2-CH2-NH2 + CH2=O --> (-NH-CH2-CH2-NH-CH2-CH2-NH-CH2-)n + H2O
NH2-(-CH2-CH2-NH-)3-CH2-CH2-NH2 + CH2=O --> (-NH-(-CH2-CH2-NH-)3-CH2-CH2-NH-CH2-)n + H2O

Linear polymeric materials ensure better densities by increase of the Van der Waals intermolecular forces so the longer the chain, the better the explosive performances will be!




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[*] posted on 10-3-2014 at 15:56


One such polynitramine is this:

http://www.sciencemadness.org/talk/viewthread.php?tid=26459

However the synthesis is lengthy, I prefer working on cyclic and polycyclic based HEDM. Cyclic and polycyclic structure are known to have higher crystal density compared to their linear counterpart. The majority of HEDM bearing density >1.9 g/cm3 are cyclic or polycyclic. The trend today is to synthesize polycyclic high nitrogen content molecule which prove good explosive and propellant with good thermal and shock stability. Unfortunately, HEDM based on platonic hydrocarbon (e.g., cubane, adamantane...) are almost totally forgotten. I believe, that HEDM based on strained polycyclic hydrocarbon can be competitive with today nitrogen rich molecule even exceed the performance of the later. Theoretical Studies on homoleptic polynitrogen HEDM (HEDM containing only nitrogen atoms) shows that these structure possess very high performance exceeding 13-14 km/s, however these numbers should be handled with caution since the equation used to compute these velocity are calibrated with molecule totally different (in term of structure, energetic and composition of their detonation products). So large deviation may occur and the 13-14 km/s may be unrealistic.

Dany.
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[*] posted on 11-3-2014 at 08:01


Quote: Originally posted by Dany  
One such polynitramine is this:

http://www.sciencemadness.org/talk/viewthread.php?tid=26459

However the synthesis is lengthy, I prefer working on cyclic and polycyclic based HEDM. Cyclic and polycyclic structure are known to have higher crystal density compared to their linear counterpart. The majority of HEDM bearing density >1.9 g/cm3 are cyclic or polycyclic. The trend today is to synthesize polycyclic high nitrogen content molecule which prove good explosive and propellant with good thermal and shock stability. Unfortunately, HEDM based on platonic hydrocarbon (e.g., cubane, adamantane...) are almost totally forgotten. I believe, that HEDM based on strained polycyclic hydrocarbon can be competitive with today nitrogen rich molecule even exceed the performance of the later. Theoretical Studies on homoleptic polynitrogen HEDM (HEDM containing only nitrogen atoms) shows that these structure possess very high performance exceeding 13-14 km/s, however these numbers should be handled with caution since the equation used to compute these velocity are calibrated with molecule totally different (in term of structure, energetic and composition of their detonation products). So large deviation may occur and the 13-14 km/s may be unrealistic.

Dany.

I'm going to post a reply in that specific tread Dany ;-).

The "Ugly NG sister" is a fully primary nitramine thus holding -NH-NO2 groups and of the familly of compounds H-(CH-NHNO2)n-H
In this case you would end up with secondary amines and deviated nitrosamine and nitramines thus bearing the R-N(-NO)-R and R-N(NO2)-R' groups.

You would get linear molecules related to (-CH2-N(-N=O)-)3 (N,N',N"-sym-trinitroso cyclotriazahexane aka R-salt) and to RDX or HMX (-CH2-N(-NO2)-)3 and (-CH2-N(-NO2)-)4 but with a link to EDNA because of some ethylene (-CH2-CH2-) bridgings.

The chemistry of such linear polymeric polyamines is much easier than polycyclic nitramines or primary nitramines like 1,2,3-trinitramino-propane. ;)




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[*] posted on 11-3-2014 at 12:07



As you know PHILOU, the synthetic part of energetic materials is an important part of this science however, this is not all the story. You are telling me that ''The chemistry of such linear polymeric polyamines is much easier than polycyclic nitramines or primary nitramines''. Well you didn't post any reference to prove this (references are needed here). You cited above that Van der Waals increase density, and the longer the polymer the better the performance...This is not very precise. The Van der Waals interaction will increase density very little, for this reason the Van der Waals interaction is not taken into strategies to build new powerful HEDM. Van der Waals interaction are weak interaction, however hydrogen bonding (strong interaction) are much important for increasing crystal density (and thermal stability) as you know and as it is evident in current and past HEDM like FOX-7, TATB...The story of longer chain mean better performance and density is not appealing for me. For example nitrocellulose which is the "polymeric" form of the nitrated glucose do not necessarily have better density or performance over the pernitrated monomer or similar, sugar-like molecule like pernitrated inositol which is known to be a powerful explosive. Yes, by polymerizing you can get better mechanical, thermal, or shock properties (or even performance) but the rule of additivity (the more the monomer the bigger the performance) do not hold in this case or the nitrocellulose (or other energetic polymer) should be consider the most powerful HEDM. Of course this is not the case...

Dany.





[Edited on 11-3-2014 by Dany]
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[*] posted on 17-3-2014 at 03:38


Quote: Originally posted by Dany  

As you know PHILOU, the synthetic part of energetic materials is an important part of this science however, this is not all the story. You are telling me that ''The chemistry of such linear polymeric polyamines is much easier than polycyclic nitramines or primary nitramines''. Well you didn't post any reference to prove this (references are needed here).


Dany,
I don't like when you bite ("Dany the dog" ;-), just kidding).
I like your posts very much, those and the documents that you attach to them are always of value to me. I'm glad you are present in this forum.

I don't really need references, I only need facts.
The making of secondary nitramines and nitrosamines from R2NH is way more easy than the making of primary nirtamines...you provided the proof yourself with the "ugly sister of NG" (multisteps and exotic ingredients vs 1 or 2 steps and limited amount of common chems).

Quote: Originally posted by Dany  

You cited above that Van der Waals increase density, and the longer the polymer the better the performance...This is not very precise. The Van der Waals interaction will increase density very little, for this reason the Van der Waals interaction is not taken into strategies to build new powerful HEDM. Van der Waals interaction are weak interaction, however hydrogen bonding (strong interaction) are much important for increasing crystal density (and thermal stability) as you know and as it is evident in current and past HEDM like FOX-7, TATB...

I get your point and this is what most people think. I think I will write a Theorem rule about polymeric being the best to improve density because I do have a lot of proofs and if exceptions exists I haven't found yet...althoug I suppose there might be some due to steric hindrance.
Also, you provided me a wonderfull tool/document to prove that theorem I'm working on for two decades now. It will be subject of a specific tread.

Quote: Originally posted by Dany  

The story of longer chain mean better performance and density is not appealing for me. For example nitrocellulose which is the "polymeric" form of the nitrated glucose do not necessarily have better density or performance over the pernitrated monomer or similar, sugar-like molecule like pernitrated inositol which is known to be a powerful explosive. Yes, by polymerizing you can get better mechanical, thermal, or shock properties (or even performance) but the rule of additivity (the more the monomer the bigger the performance) do not hold in this case or the nitrocellulose (or other energetic polymer) should be consider the most powerful HEDM. Of course this is not the case...

Dany.

"The longer chain mean better performance and density" will be soon appealing to you by the simple facts and evidence I will submit to this forum.

If you want to speak about nitrocellulose wich is at maximum trinitrated per monomeric unit...you should compare it with monoses that are trinitrated and not more.
I don't have datas for trinitrosuggar sadly; but by comparison between nitrostarch (lower MW polymer of glucose) and nitrocellulose (higher polymer of glucose) of identical nitration level shows that nitrostarch has a density of 1,60 while nitrocellulose has a density of 1,67.
It is evident that glucose tetra, penta or hexanitrate will display better explosive performances than the glucose trinitrate. Also evident that inositol hexanitrate will be more powerfull than nitrocellulose but inositol hexanitrate(*) will be less poweful than the polymer H-(CH(ONO2)-)n-H with n=near infinite whose density is in the viccinity of 1,90 g/ccm (+/- 0,05 g/ccm).

(*)By the way what are the datas of IHN? VOD, LBT, d, Pcj?



[Edited on 17-3-2014 by PHILOU Zrealone]




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[*] posted on 17-3-2014 at 15:19


PHILOU,

thanks for the compliment…Now for the serious part. You didn’t convinced me that polymers or the Van der Waals weak inetractions are the best ways for increasing the density. You are saying that you have a lot of proof and you didn’t find any exception. Well, one of these “exceptions” (I don’t consider it an exception) is the example of glucose and cellulose. Glucose (the monomer of cellulose) has a density of 1.54 g/cm3 (taken from Wikipedia, Wikipedia cited Lange's handbook of chemistry for the density of glucose. I consider this handbook a reliable reference). Cellulose (α-cellulose) on the other hand has a density of 1.48 g/cm3 [1]. Special form of cellulose (e.g., Avicel® PH-101) can reach density of 1.60 g/cm3. A difference of 0.06 g/cm3 between simple glucose molecule and Avicel® PH-101 is small and cannot be consider a big achievement…
Also you mentioned that most people (including me) think that Van der Waals weak interactions are not an efficient mean for improving the density. In fact, this is what I saw during the last decade while reading on energetic materials. To my knowledge, nobody mention the Van der Waals interaction as a potential method for improving the density. However, if you have reference that tell us the opposite post them here.
As we are concerned with energetic materials here I will prove to you by calculation that the big size of the molecule is not the important factor for making powerful explosive. In an interesting study entitled “A Trigonometric Approach to a Limiting Law on Detonation Velocity’’, Dr. Lemi TURKER concluded the following [2]:

The present trigonometric model enables one to understand some obscure facts involved behind the velocity of detonation. The most important of them is the ”limiting law of detonation velocity” which states that for a series of explosives, after a certain optimum value of the total energy (E), detonation velocity decreases asymptotically to a constant value. This statement, as a mathematical conjecture, should also hold for the size of an explosive (because E is an implicit function of molecular weight) and indeed the case. Therefore, instead of increasing the size of the explosive molecule by adding more explosophoric groups to a base structure, it is better to design more energetic base structures keeping the molecular weight small but having high maximum density. The survey of the literature implies that this line of research has been intuitively (or by trial and error) followed by some groups in the absence of any theoretical analysis as deep as the present one

I invite you to read this paper that I attached below. For the detonation performance of inositol hexanitrate, the Preparatory Manual of Explosives for Jared Ledgard estimated a 7800 m/s for detonation velocity (he didn’t mention at what density he made the estimate). The trauzle block power relative to TNT is 1.34 (TNT= 1) taken form The Power of High Explosives in Theory and Practice for Dave Everest. Personally, I didn’t hear about Dave Everest before in detonation science…
Anyway, this what I found on inositol hexanitrate.

References

[1] Azubuike, C. and Odulaja, J.O. and Okhamafe, A.O. (2012) Physicochemical, spectroscopic and thermal properties of powdered cellulose and microcrystalline cellulose derived from groundnut shells. Journal of Excipients and Food Chemicals, 3 (3). pp. 106-115.

[2] Lemi Türker, A Trigonometric Approach to a Limiting Law on Detonation Velocity, MATCH Commun. Math. Comput. Chem. 67 (2012) 127-146.

Dany.



[Edited on 17-3-2014 by Dany]

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[*] posted on 18-3-2014 at 04:15


Hey Dany,

You scared me, you almost got me on this with glucose and cellulose.

The rule is simple but you have to watch closely to the structure to be able to compare "apples with polyappels" and of course when there are a lot of H bonding groups into the molecule each increment has a very powerful effect as is seen here in the comparison between cellulose and glucose. To be "comparable" you should cut the cellulose into pieces (kind of monomeric units).
To simplify:
Cellulose is a polymer of the type -Glu-O-Glu-O- with beta 1-4 ether (hemiacetal) linkages... so the monomeric unit would be Glu-O what can't exist on its own except if you were able to bend the molecule sothat the two positions 1 and 4 could be joined by an ether linkage...but it would change the structure a lot...so the closest molecule that would keep the same structure and not add extra H bondings would be the 1,4-dimethyl ether of glucose (CH3-O-Glu-O-CH3) or a derivated molecule H-Glu-O-CH3 or H-Glu-H... and the later will be below the density of 1,54 g/ccm from glucose, because you loose two hydroxyl groups (strong H bonders) on five.

You get the same effect If you compare.
-Pentaerythritol
(HOCH2-C(CH2OH)2-CH2OH)
d= 1,396
-Dipentaerythritol
(HOCH2-C(CH2OH)2-CH2-O-CH2-C(CH2OH)2-CH2OH)
d= 1,373
-Tripentaerythritol
(HOCH2-C(CH2OH)2-CH2-O-CH2-C(CH2OH)2-CH2-O-CH2-C(CH2OH)2-CH2OH)
d= 1,30

Then the rule doesn't seems to hold...but it is only the reduction of the number of OH groups per unit that induces the density decrease (4/u goes to 3/u then to 2,666/u)
To be "comparable" you would have to leave two OH groups in PE via methoxylation or reduction of OH to H (methyl group).
Thus the initial comparison product would be dimethoxyPE (d = ?) or 2,2-dimethyl-1,3-propandiol (neopentylglycol d= 1,06 g/ccm).

Another example maybe more speaking to you is Polyethylene glycol (-CH2-CH2-O-)n: the monomer is not ethylene glycol (although it can be prepared by multistep dehydration of it into diethyleneglycol, triethyleneglycol,etc. ) but ethylene oxyde (epoxyde).
The closest "monomer like" would be glycol dimethyl ether (CH3-O-CH2-CH2-O-CH3).
There is a clear difference in density between epoxyde or DMGE and ethylene glycol; the later displaying two strong H bronding groups has a higher density.
If you compare the densities of PEG and DMGE (or Epoxyde) my rule is 100% accurate.

All this will be clear as water source once I have written the specific tread.

[Edited on 18-3-2014 by PHILOU Zrealone]




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[*] posted on 18-3-2014 at 12:00


I have a big smile on my face after reading your last reply, PHILOU

in all your reply you didn't mention the Van der Waals interaction even once. You explained the increase in density via the hydrogen bonding which you mentioned 3 time in the text...So, after the conclusion of Dr. TURKER (that the size of molecule is not the important factor for powerful HEDM) and the explanation giving by you in the last post i consider that what you told in the first reply:

Linear polymeric materials ensure better densities by increase of the Van der Waals intermolecular forces so the longer the chain, the better the explosive performances will be!

is simply wrong...

btw, you mentioned that you are working on a theorem rule about polymeric being the best to improve density for almost two decades...well, if this is true (working for 20 year on a theorem) you should submit this work to Nature or Science journal, before posting it on a amateur website.

Dany.
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[*] posted on 19-3-2014 at 03:10


:D If I made you smile, then you make my day too :)

Your criticism is of value to me, true that I forgot to mention the other intermolecular forces while discretely implying those into my theory. It comes from the fact I have started the study with purely linear hydrocarbons and monomers/polymers that don't show H-bondings...but after the theory was extended to polyols, to polyamines and to polynitramines (the poly-primary-nitramines display very strong acidic H-bondings, while the poly-secondary-nitramines doesn't because there is no H left free on the Nitrogen core R2N-NO2). The theory fitted all and all the intermolecular forces effects are simply additive but all go into the same direction and reinforce the theory.

I should rephrase my sentence:
Linear polymeric materials ensure better densities than monomeric (or monomeric-like) materials by increase of all the intermolecular forces (dipolar interactions (dipole-dipole, ion-dipole, ion-induced dipole, H bondings (for H-O, H-N and H-F) and Van der Waals); so, in the specific field of explosives, to enhance and to acheive the best explosive performances in a given array of molecules derived from a monomer (or monomeric-like) molecule the longest polymeric chain is wished!




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