Sciencemadness Discussion Board

Glycine Perchlorate

Hey Buddy - 18-12-2022 at 22:33

I began looking into amino acid ligands. Glycine perchlorate is reported to be:
1.89 g/cc
+13.67% (CO) OB
Vd 8470 m/s
32.26 GPa
>60 J IS
>360 N FS
mp 103 C
Td 263 C
("Insensitive Ionic bio-energetic materials derived from amino acids" Zhang, "Scientific Reports" 06 Oct 2017)

This got my attention.
If that information is accurate, this would be good.

I wanted to double displace with glycine ammonium perchlorate and HCl, it didnt happen, here's why...
The first thing I did was heat up 50ml H2O to around 90 C then added .083 mol NH4ClO4 with a matching molar of glycine. At some point during boiling, I detected ammonia with my sniffer. The next thing I knew I was looking at a thick white paste. I put it on a hot plate, it started melting weakly around 140 C or so. I put some under a propane torch, it seemed to melt and let off higher energy perchlorate response with the occasional flash and blue white light.

I then repeated with .485 mol equivalents. This time I refluxed in an open beaker. I first heated the NH4ClO4 in water to around 80 C and had no detection of ammonia. Glycine was added, the temp dropped a little then around 85 C bubbling began and the smell of ammonia was detectable. Litmus paper was hung over the beaker and it gave an alkaline color change ~7-8 pH. Ammonia is being evolved from NH4ClO4 after glycine is added to a boiling solution. I refluxed this, adding water to reduce foaming until I couldnt detect a positive ammonia smell over the beaker, around an hour, fifteen minutes of boiling. Then it was poured into a few hundred ml isopropanol and a precipitate separated to the bottom of the beaker. It melts on a hot plate much lower temp... Probably around 103 C, it has a wide melt temp shelf, I took it up to 145 C and it melted easily, no decomp.

Glycine decomp is 233 C, NH4ClO4 is 200 C. Neither materials melt.
I think this may be glycine perchlorate. It's drying right now.-- It's possible glycine perchlorate can be made by refluxing glycine and ammonium perchlorate until ammonia is lost. If that is in fact what is happening, and if the specs on glycine perchlorate are correct, it's the easiest 8400m/s 32 GPa 103 mp material that I know of. Ive found threads on glycine nitrate. There is nothing on glycine perchlorate. It blows away most amino acid salts in performance, the closest follow up is iso-leucine perchlorate at 7900 m/s and aspartic acid nitrate at 7500 m/s 22 GPa. BTW ASP.NO3 has an mp of 98 C and Td of 183 C. TNT is 6800 m/s 19 GPa mp 80 Td 295.

[Edited on 19-12-2022 by Hey Buddy]

[Edited on 19-12-2022 by Hey Buddy]

Hey Buddy - 18-12-2022 at 23:09



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Hey Buddy - 18-12-2022 at 23:29

I got some aspartic acid. Obviously I'm going to test feasibility of boiling displacement of ammonium nitrate/aspartic acid in the morning.

Perhaps guanidium nitrate ASP or Glycine... I believe glycine might condense as a cyclic.

[Edited on 19-12-2022 by Hey Buddy]

Hey Buddy - 19-12-2022 at 11:18

Aspartic acid in NH4NO3 does not have the same effect as the perchlorate. There is no detectable liberation of ammonia and no change of litmus paper.

It definitely looks like the addition of glycine to ammonium perchlorate is displacing the ammonia. During the repeat test with glycine, I dipped a litmus paper into the solution and it gave a slight acidic response, this would suggest free perchloric acid is in the solution.
The only thing that is unclear to me is if this is making proper glycine perchlorate. The reason is the dried product is not very reactive to flame. In the referenced literature there is a picture of GlyClO4 combusting with a clear 10 cm flame. When I hit this produced material with a torch it lets of sparks and decomposes into black residue with melting at surface. There is no big flame. Perhaps it could be crystal structure? Possibly not dried well enough?

I also wonder if the simple displacement is only attributed to glycine alone or if it is possible with other larger carbon amino acids.
I suppose a test of glycine in NH4NO3 would be good and a test of aspartic acid in NH4ClO4. That could give a better idea of what is generally going on.

Im stumped on flame size not being the same as the referenced test. The GlyClO4 in picture is clearly more vigorous burning than controls of TNT RDX TNP and HMX. In the tested displacement phenomenon, there is only NH4, ClO4 and Gly present. If ammonia is liberated, which it is, then there can only be glycine and perchlorate both of which have much higher bp than water. It should be producing GlyClO4. I don't know why the reactivity appears much lower than it should.

Here is a copy of the referenced paper on amino acid ionic explosives.

[Edited on 19-12-2022 by Hey Buddy]

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[Edited on 19-12-2022 by Hey Buddy]

I also realized tonight there is an Ammonium Glycinate. Glycine can act as acid or base. Seems unlikely as the favored reaction due to free emission of NH3, could be a subtle contaminate.

[Edited on 20-12-2022 by Hey Buddy]

Hey Buddy - 20-12-2022 at 12:39

I found a report of glycine perchlorate embedded in a thread here:
https://www.sciencemadness.org/whisper/viewthread.php?tid=36...

Quote: Originally posted by enthalpy  

Now to the new stuff: Glycine perchlorate

I found absolutely no information about it. PATR 2700 only mentions the nitrate salt and the nitramine (nitroglycine). But the nitrate salt is said to be as powerful as picric acid.
I started as for HDPC. Dissolved the glycine in a bit of destilled water and adding perchloric acid slowly. Afer addition of acid was complete there was no trace of crystalisation. So the beaker was put in the fridge and cooled to 0°C. Still there was no single crystal. I remembered that urea perchlorate has similar properties (in 100ml water over 900g of urea perchlorate can be dissolved). It is also very hygroscopic and crystals are very hard to obtain. But anyway I gave GP another try. This time with success:

14,4g of perchloric acid (70%; 0,1 mole) was cooled to 5°C and stirred electrically. 7,5g of aminoacetic acid (0,1 mole) was added slowly. The slow addition and stirring is important because there could form hot spots (you know…..perchloric acid and organics aren’t that good). The temeprature of the mix rose a bit. After addition was complete all of the glycine dissolved. The mixture was a viscous and clear liquid. Next step was a bit crazy. The beaker was put in a water-bath and heated to 80°C and held there for 20min. Still it was a liquid. This was crazy because boiling down a solution of an unknown organic perchlorate isn’t harmless. The beaker was put into the fridge. Crystalisation occurred. The crystals were scraped out of the beaker and instantly packed airtight. Tests were performed with the following results:

Hygroscopicity: GP is definitive hygroscopic. If exposed to the air it “melts”.
Solubility: GP is very soluble in water, soluble in ethyl alcohol and acetone. It . is however insoluble in non polar solvents such as naphta.

It builds colorless crystals which melts easy without decomposition. If stored airtight there was no trace of decomposition. When crystals of GP get in contact with flame they first melt (fast and easy) and then burn down with a hissing noise. It looks quite energetic. GP can also be detonated by a hammer blow.
I thought about the existence of salts of GP. So I made a solution of GP in water/ethanol (1:1) and slowly added potassium carbonate. Carbon dioxide was evolved and the solution turned milkey. I put it in a waterbath and evaporated as much water/ethanol as possible. Put in in fridge and got a white powder. Upon ignition it melts and then flashes like potassium picrate or calcium nitronate. I don’t know whether this is a real salt of GP or simply a mixture of glycine and potassium perchlorate (the proton in the reaction could also be from the protonated amine group). Just out of curiosity the lead (or other heavymetal salts should be tested).

[Edited on 12-3-2008 by enthalpy]


Based on his description his material sounds close to what Im seeing in this material.
I now strongly suspect GP can be produced by the refluxing of NH4ClO4 and Glycine.
If this is GP, then the Zhang article may not be accurate. Their GlyClO4 stats might not be correct either. Im going to have to make a new personal rule to disregard chinese researchers because I have been served so much confusion and misdirection over the years taking their reports at any literal interpretation. Their flame color in the photo isn't really even consistent with the appearance of flames from the many perchlorates and perchlorate compositions that are known.



[Edited on 20-12-2022 by Hey Buddy]

[Edited on 20-12-2022 by Hey Buddy]

Microtek - 20-12-2022 at 23:14

Yes, it is a very unfortunate trend that papers from chinese universities can't really be taken at face value. On the other hand it means that the work we do here, attempting to reproduce their results, has actual value beyond satisfying our own curiosity.

Laboratory of Liptakov - 22-12-2022 at 14:55

There are many dissertations where math errors appear like elementary school students.
For this reason, basic research here on science madness is often more valuable. Than anything else.

specialactivitieSK - 25-12-2022 at 13:00

How about a double reaction. Glycine hydrochloride and sodium perchlorate.

Microtek - 26-12-2022 at 07:50

Well, that will give you a mix of the four ions. GlyP is very, very soluble in water, but it might be possible to use alcohol solutions to precipitate the NaCl. I still think it would be easier to just make the perchloric acid and use that. IMO, the biggest problem is the hygroscopicity, just like with UZP. I came across a paper recently about the use of co-crystallization with nitrogen heterocycles to improve some of the prperties of energetic salts. In particular, cyclic ureas worked well, so I'm going to try urazine and maybe ethylene urea to try to improve GlyP and also UZP. I will just have to try with a range of molar ratios since I don't have any way to predict the hydrogen bonds that are most likely to contribute.

Etanol - 27-12-2022 at 04:04

Quote: Originally posted by Hey Buddy  
I began looking into amino acid ligands. Glycine perchlorate is reported to be:
1.89 g/cc
+13.67% (CO) OB
Vd 8470 m/s
32.26 GPa
>60 J IS
>360 N FS
mp 103 C
Td 263 C
("Insensitive Ionic bio-energetic materials derived from amino acids" Zhang, "Scientific Reports" 06 Oct 2017)

[Edited on 19-12-2022 by Hey Buddy]


How was estimadet VoD and detonation pressure?
It is very much for these compound at 1.89g/cc. May be c.a. 8000 m/s 25 GPa?

Hey Buddy - 27-12-2022 at 08:49

Etanol, this is exactly what I mean. The paper uses photos of burn tests suggesting the materials burn vigorously more so than RDX control sample. The photo line up and charts in combination are convincing enough, although they seem exaggerated. I'd assume their numbers are calculated not measured. I dont think they faked the photos, because that would be a lot of effort and wouldnt make sense. But I'm not yet convinced that the results are reproduceable nor accurate. My intent was to show how glycine was displacing ammonia from its perchlorate. I do think the amino acid materials need a lot more investigation, they definitely melt, so that makes it worthwhile. I havent had time nor weather to do much experimenting lately. Id like to test some glycine perchlorate from HCLO4 to compare and see if their burn tests are repeatable that way.

Etanol - 27-12-2022 at 11:20

Quote: Originally posted by Hey Buddy  


Yes, I read this article now.
I do not dispute the photo results. Salts of chlorine acid burn very briskly really. But burning does not determine the VoD. Therefore, the calculation method or software is interesting.

Methylinam and ethylendiamine perchlorates have a greater heat of the explosion, but generate no more than 7600 m/s at 1.68 g/cm3. Guanidine perchlorate is only 7150 m/s at 1.67 g/cm3 because It has a lower heat of the explosion. However, with a maximum density of 1.743, its speed is similar.
Glycine perchlorate has even less heat of the explosion than guanidine.

[Edited on 27-12-2022 by Etanol]

Hey Buddy - 27-12-2022 at 12:32

Sorry, didnt mean to suggest you disputed photos, I just meant that I thought they were unexpected, color and shape of burn unexpected to me compared to other perchlorates and size. I doubted reproducibility and their calculated values. The data they determined is probably best-case in *theory. I would prefer it if the data were accurate, because then I could stock up on glycine perchlorate. :).

I have found that relative ratio CHO and the percent of N and organic/inorganic links can somewhat predict behavior profile of explosives, but only generally. The theoretical high density seems realistic from molecule shape. It seems like a glycine ionic compound could be brisant. Its a small amino acid, it would make sense if the other amino acids were more sluggish. That seems to be the general rule they also calculated. Most of their compounds calculated were in the 6-7km/s range. The glycine perchlorate is an outlier.

I assume that displacing ammonia out of its perchlorate using glycine is giving a contaminated product. I would like to test it in detonation because of its simplicity. Experiment with maybe a much longer reflux or alkaline/acidic reflux condition. Even if refluxed material were detonating in modest performance, it would be nice. At the cost of glycine and the lack of other critical materials, no acid etc. if it were detonatable say in 6km/s velocity or higher, then it would be a meltable explosive that could be mass produced inexpensively. That would be worthwhile. If it could somehow achieve their claimed performance it would be incredible, but I doubt.

Samples made from ammonium displacement are burning nothing at all like their claimed burn profile, but they do melt and do react to heat. That would suggest glycine perchlorate is produced but maybe it has contamination of unconverted NH4ClO4 or Ammonium Glycinate. If it can be determined how to push reaction to GlyClO4 with that method, it would really qualify as a high yielding inexpensive OTC explosive preparation. IMO to produce it using HClO4 is fine in small quantity, but it is a bit laborious to produce for a lot of material. So displacement is preferable. If it were possible via displacement, you could buy glycine and make a perchlorate cell for your salt, then drop it out as ammonium cation. It would be a magnitude simpler route to achieve 8km+ melt cast explosive, rather than say K-6/RDX. Also insensitive. Not sure what critical diameter would be but I dont see why it would be large. If critical diameter were low, and high performance were realistic, GlyClO4 would have a lot going for it. You can find glycine ~$10-20/lb but it doesnt have to come from limited pyrotechnic stores. If the ammonium displacement method could be worked out, no acid would be necessary, which is a considerable savings. The perchlorate can be had at the cost of NaCl and NH4 and kW/hr/$.

Doing a control run with HClO4 to see what the pure product does is the first thing I'll do and if it is different in behavior then I will know what to work towards in displacement and if there were any hope in that route.

MineMan - 27-12-2022 at 19:56

Maybe co crystallization will work if for example Urazine is used along with the glycine? Would electricity help the displacement? Maybe heat is needed. Sometimes these solutions need to be 70 plus C for the Metathesis to happen. Of course the great PHILZOU would know… perhaps he can be summoned through the spells of old chemistry books.

PHILOU Zrealone - 28-12-2022 at 16:25

Thanks to Mineman for bringing this topic to my attention,
Nice subject.

The acidity data from aminoacetic acid (glycine) and ammonia/ammonium are consistent with the observed evolution of NH3(g) upon mixing and heating of NH4ClO4 and H2N-CH2-CO2H.
NH3 + HClO4 --> NH4(+) + ClO4(-)
H2N-CH2-CO2H --> H3N(+)-CH2-CO2(-) (the proton of the carboxilic part of the molecule can be taken by the basic amino group next by.

NH3/NH4(+) pKa is arround 9,24 vs water
pKa's of H2N-CH2-CO2H are 2,34 vs water for the -CO2H part and 9,6 for the -NH2/-NH3(+) part.
This means the basicity strenght of ammonia/ammonium and amino/aminium are in the same range...and are hungry for HClO4 but NH3 is volatile what amino part of glycine is not... so with a moderate heating (strong heating is not advisable due to perchlorate salt of organic amine are better kept relatively in a safe zone of temperature range).
NH3 will thus leave the system quite fast with good venting and/or vaccuum.
(NH3 is an old war gas keep that in mind for eyes, respiratory tract and nose/nostrils/lungs protection).
So NH4ClO4 is a source of HClO4 in disguise by displacement of the volatile base NH3 thanks to a less volatile equivalents strenght base.
The carboxilic acid part is effectless vs the strong acid HClO4 (at least a million times stronger in acid strenght).

The performances of glycine is of course better than the other members of the usual amino-acids perchlorates because amine perchlorates performances are dictated by:
-Oxygen balance of the salt as CO2 (and not as CO what is informative but less interesting following me)
-Structure of the amine ... what is strongly related to the basicity and salt formation with strong acids like HOClO3 (HClO4).
-Structure of the molecule and presence of energic fuel sub-structure.

Glycine is H2N-CH2-CO2H and you may look at it as CH3-NH2 + CO2
It is the simpliest tiny one and if monoperchlorated near the perfect OB... close to CH3-NH2.HClO4...
CH3-NH2.HClO4 --> CO2 + HCl + 1/2 N2 + 2 H2O + 1/2 H2
HO2C-CH2-NH2.HClO4 --> 2 CO2 + HCl + 1/2 N2 + 2 H2O + 1/2H2
Any other structure brings more fuel but without increasing the amount of perchloric groups linked to it via extra amino groups of strong basicity, it will no be able to burn from the in situ generated oxygen during the detonation process; so density will be lower and extra fuel uncorrectly used.

The interest of amino-acids is evident as readily available start products and OTC ones; but, of course, any good chemist would know how to design artificial new ones of chozen structure that will surpass natural ones with regard to density, number of amine groups, basicity, energy content of the skeleton and displaying better detonic performances.

I think that metathesis with NH4ClO4 is of value if taking time and precautions but indeed the route via HClO4 is probably more straightforward and rapid despite the need for cooling and probable tempering by water that must be taken rid of afterwards.

Hey Buddy - 28-12-2022 at 18:17

Quote: Originally posted by PHILOU Zrealone  

So NH4ClO4 is a source of HClO4 in disguise by displacement of the volatile base NH3 thanks to a less volatile equivalents strenght base.
The carboxilic acid part is effectless vs the strong acid HClO4 (at least a million times stronger in acid strenght).


Interesting. So if you wanted to try this simple displacement on other molecules would you look for target molecules with NH2 see-sawing against a weak acid?

also, the glycine perchlorate made from simple displacement doesnt burn as intensely as an RDX sample. The reference line up burn test of GlyClO4 has a ~5 cm reaction flame, much larger than their rdx control sample. Is there an obvious reason for this? (The GlyClO4 from displacement was made by boiling for an hour. And another time was made by boiling for only ~20min, neither burn with large flame, both melt.)

PHILOU Zrealone - 30-12-2022 at 19:01

Quote: Originally posted by Hey Buddy  
Quote: Originally posted by PHILOU Zrealone  

So NH4ClO4 is a source of HClO4 in disguise by displacement of the volatile base NH3 thanks to a less volatile equivalents strenght base.
The carboxilic acid part is effectless vs the strong acid HClO4 (at least a million times stronger in acid strenght).


Interesting. So if you wanted to try this simple displacement on other molecules would you look for target molecules with NH2 see-sawing against a weak acid?

also, the glycine perchlorate made from simple displacement doesnt burn as intensely as an RDX sample. The reference line up burn test of GlyClO4 has a ~5 cm reaction flame, much larger than their rdx control sample. Is there an obvious reason for this? (The GlyClO4 from displacement was made by boiling for an hour. And another time was made by boiling for only ~20min, neither burn with large flame, both melt.)


What do you mean by "see-sawing against a weak acid?"?

I would rather play with HClO4 dilluted (10-72%) and a pure or dissolved base or putative base containing a NH2 group.
Indeed if NH4ClO4 was under hand I would probably test it by under vaccuum fusion and evolution / trapping of NH3...

While some perchlorate are quite unsoluble and easily recovered cristallized by precipitation; other are hell hygroscopic and would require considerable heating, vaccuum or dehydration (via dehydrator) in close container and protection from air moisture to avoid remoisturization in a short time.

This is the case of N2H5ClO4 (very sensitive (shock, friction, flame, heat and impact) and powerfull but also very hygroscopic compound).
I could dry my hydrazine nitrate into an hermetic box over an ambiance radiator (40°C) holding also hydrazine perchlorate... the HP turned a full liquid leaving my HN very dry solid.

Such hard to solidify and to dry compounds are also hard to detonate because of the last bit of contained water of crystalization (often cought from the air or from other chemicals)... during exposure to heat, they usually melt into their crystallization water, evaporate and decompose or burn at the same time and this tempers a lot the heat of decomposition, burning, explosion or detonation /power.
It needs super drying... but this increases a lot sensitivity to friction, shock, flame or heat.

I have played with H2N-CN (cyanamide what is if you take a close look at it a dehydrated form of urea...)
H2N-CO-NH2 <--> H2N-C#N + H2O
So cyanamide is a hydrolitic source of urea (and then further of ammonium carbonate) into the soil as fertilizer, it is also a good fuel because less water trapped into the structure and more multiple bond as energy stored source... Cyanamide should logicaly display a better combustion heat than urea.
It must be slightly more acidic than urea (this last is neutral vs water but basic vs HClO4) so cyanamide must stil be able to form salts with the amino group against strong acid like HClO4... forming cyanamide perchlorate (CAP). Cyanamide is a weak acid despite the amino group because of the viccinal electron withdrawing cyano group but HClO4 is very strong acid and it will thus turn the weak acid into a weak base in its own perspective and respect.

H2N-CN when trimerized could be seen as melamine (-N=C(-NH2)-)3 (since cyanamide is dehydrated form of urea melamine is also a trimeric form of urea tripplely dehydrated :D)... isn't it fabulous how chemistry is logical :P and consistent with itself...
Cyanamide heat of combustion must be higher than melamine (due to the stabilization induced by the (poly-hetero-aromatic ring formation/polymerization/cyclic trimerization what implies loss of energy content for stabilization by aromaticity).
Melamine perchlorate and diperchlorate (cannot fix a third perchloric acid molecule into a stable melamine tri-salt)... those are already quite good performer vs urea perchlorate (overoxygenated).
N#C-NH2.HClO4 should beat performances of melamine diperchlorate... but it is too rich at oxygen so OB is positive (a problem melamine diperchlorate circumvent by lacking a HClO4 molecule)... Overoxygenated (positive OB) means a loss of energy for full detonic power of CAP.
The extra oxygen become a unused dead weight... it lacks fuel.
This problem is shared by all positive OB explosives.
There must be an optimal mix of melamine diperchlorate and cyanamide perchlorate that display a perfect OB and thus maximum power output.

Cyanamide does form a dimer with itself called di-cyanamide what is in fact cyanoguanidine...
H2N-C#N + H2N-C#N --> H2N-C(=NH)-NH-C#N
A probable intermediary on the way to melamine by trimerization and cyclization.

Cyanoguanidine is a very interesting powerful molecule... it has more energy content than guanidine because one H had become a C#N...
The guanidine part allows good quality as a base and ease of salt formation vs oxidizer carrying acids...
It was tested as an experiment with a friend about 30 years ago and it detonated strongly... it was made from HClO4 and chemically pure bought cyanoguanidine.
My friend had access to chemically pure chemicals thanks to his father water analysis society. Good memories :cool:.
CGP has a good OB (close to 0) but is stil slightly lacking oxygen for a perfect OB.

H2N-C(=NH)-NH-C#N.HClO4 --> 2 N2(g) + HCl(g) + 2 H2O + 2 CO(g)
Would require one mole equivalent of O2 for perfect OB and maximum energy output...
2 CO + O2 --> 2 CO2

RDX is cristallizing relatively dry and burn well... it seems logical that hygroscopic perchlorate of amines catch water from the air (or unperfectly dried product) and are then tempered a lot in their explosive behaviour or burn rate vs a truly dried sample.

The large flame diameter from glycine perchlorate vs RDX is probably linked to its explosive power (sensitivity to flame and initial burning rate in the open or slighly self confided... read probable faster B2D(2D) transition (burning to deflagration to detonation transition) mass from self burning)... it expels itself in the air and arround while burning more vigourously.

That is what I think explains your observations.

Hey Buddy - 30-12-2022 at 19:08

Quote: Originally posted by PHILOU Zrealone  


What do you mean by "see-sawing against a weak acid?"?



Sorry, this term is hillbilly-pre-realiztion of what defines an amino acid.

PHILOU Zrealone - 31-12-2022 at 03:13

Quote: Originally posted by Hey Buddy  
Quote: Originally posted by PHILOU Zrealone  


What do you mean by "see-sawing against a weak acid?"?



Sorry, this term is hillbilly-pre-realiztion of what defines an amino acid.

Thank you for your clarification.
Amino acids are easy because existing relatively-OTC and cheaper...but limited in structure / design.

Artificial amino acids can be done via a Strecker synthesis from a keton or aldehyd and an aminium cyanide...
R-C(=O)-R' + R"-NH2 + H-C#N (R"-NH3-C#N) --> (R-)(R'-)C(-C#N)(-NH-R")
Where R, R' and/or R" can be alkyle, aromatic or H.
The later addition product upon acidic or basic hydrolysis provides an amino acid... but is this important ? (Because a cyanide / nitrile group is more interesting energetically speaking.
This opens the way to un-natural polyamino and polycarboxylic acids (or polycyanido compounds) allowing for denser poly perchlorate salts on a molecular level (better OB/power)

PHILOU Zrealone - 1-1-2023 at 13:30

Of course playing with aminium cyanide must be done with due caution owing to the inherent composition ... soluble cyanide anion and potential free cyanhydric acid upon exposure to the slightest weak acids like H2CO3 (CO2 from air or breath and air moisture) or aminium (NH4(+) or R-NH3(+) are weak acids)...
Thus only for skilled chemist that understand the danger of such procedures.

PHILOU Zrealone - 9-1-2023 at 03:02

Glycine is a good example of desired amino-acid.
Retro-Strecker is pointing into the direction of formaldehyde CH2=O (CH2(-OH)2).

CH2=O + NH4-C#N --> H2N-CH2-C#N (perchlorate of glycine nitrile must be very potent)+ H2O
-H(+)-> H2N-CH2-C(=O)-NH2 (diperchlorate of this glycin-amide must be very strong and performing, also good density)
-+H2O-> H2N-CH2-C(=O)-O-NH4 (ammonium glycinate)

From this observation it would be an excellent idea to test for Strecker synthesis onto dicarbonyl compounds like glyoxal
O=CH-CH=O + 2 NH4CN --> N#C-CH(-NH2)-CH(-NH2)-C#N
This last as a diperchlorate will be outstanding because as a dimeric kind of Glycine nitrile perchlorate, it will be denser; about the same sensitivity/stability...but with a slightly better OB thus more energy output...
2 (H2N-)(N#C-)CH2.HClO4 -theorical dimerization-> H2 + (H2N-)(N#C-)CH-CH(-C#N)(-NH2).2 HClO4 (bis-glycine nitrile diperchlorate)
This should result into a very good hyperperforming energetic material with very good detonic parameters...just like the bis-glycine amide tetraperchlorate or the bis-glycine diperchlorate.

This is only a tiny examplative sample of my ideas onto the subject of synthetic artificial amino-acids...

Fantasma4500 - 10-1-2023 at 16:25

glycine sulfate and sodium perchlorate maybe? ammonium perchlorate is a pain on its own- for safety we should maybe try to produce glycine chlorate as homemade perchlorate can oftenly contain some chlorate

as for getting it out of solution, i would imagine somehow getting the GlyClO4 into maybe- acetone, then adding in an excess of polar solvent, or a mixture of solvents that shifts the polarity and crashes out the salt

https://www.sigmaaldrich.com/deepweb/assets/sigmaaldrich/mar...

this would claim acetone isnt miscible with anything, methanol seems to go into hexane and heptane, this is very easy to get from lighterfluid for zippo, distill out of gasoline, around 70*C fraction, or sold under names such as "washingbenzine" in europe

now, a sodium salt was mentioned- if thats possible, should an ammonium salt also not be possible to be formed? ammonium picrate was used a lot. forming a salt could maybe make it easier to pull out of solution
maybe good ol' DCM can help? the hygroscopicity is a major drawback, but the added difficulty could hopefully hint at it being very powerful

ammonium permanganate can also be made- and may be possible to combine in similar fashion, its a fair bit more unstable than ammonium perchlorate, so it could potentially be some kind of primary

perchlorate salts are very attractive especially if one can make them from chlorate by melting, half an hour at 300+*C didnt seem to do much for sodium chlorate. sodium perchlorate can be extracted using acetone- coming to think of it, glycine sulfate could maybe be combined with sodium perchlorate in acetone? and then simply shift the polarity, or let the acetone evaporate- as it usually does very well due to its high vapor pressure, let this occur at a very slight vacuum to supposedly keep moisture out and you would have a very practical route

EDIT: glycine chlorate is a real thing and its a primary! albeit, in the form of a coppersalt.
https://www.youtube.com/watch?v=K0X0qZF6DeM

[Edited on 11-1-2023 by Antiswat]

Hey Buddy - 12-1-2023 at 10:10

Glycine + Hydrazine + Ni + NH4ClO4 makes a blue nickel crystal. Very energetic. Not sure if it's a suitable primary explosive, drying it out completely, but when wet state the crystals fire gas jets strong enough to extinguish flame.

PHILOU Zrealone - 12-1-2023 at 15:17

Quote: Originally posted by Hey Buddy  
Glycine + Hydrazine + Ni + NH4ClO4 makes a blue nickel crystal. Very energetic. Not sure if it's a suitable primary explosive, drying it out completely, but when wet state the crystals fire gas jets strong enough to extinguish flame.


It can be too many things...

H2N-CH2-CO2H + H2N-CH2-CO2H --> cyclo(-NH-CH2-C(=O)-)2 (diketopiperazine) + 2H2O
For info: Most amino acid do form diketopiperazine while heated/decomposed.
Such molecules are interesting precursor for nitramide formation by concentrated mixed acids nitration with cooling and without water.
Dinitro-N,N'-Diketopiperazine from glycine must be quite interesting...
See cyclo(-N(-NO2)-CH2-C(=O)-)2
or
C4H4N4O6 --> 4 CO + 2H2O + 2 N2 + heat
It lacks 2O2 for complete combustion and full energy output during detonation.
It must be close to keto-RDX for sensitivity to shock/heat and for hydrolysis.
And close to keto-RDX and RDX for density...

What can it be?
H2N-NH2 + H2N-CH2-CO2H --> H2N-NH-CH2-CO2H + NH3(g)
HO2C-CH2-NH2+ H2N-NH-CH2-CO2H --> (-NH-CH2-CO2H)2 + NH3(g)
(-NH-CH2-CO2H)2 -ox-> HO2C-CH2-N=N-CH2-CO2H + H2O

Into the mix you have NH3, N2H4, Ni(ClO4)2 and the above glycine related molecules (amino-glycine, glycine, hydrazino-diglycine, diazodiglycine) that can make a complexating mix of variable and unknown composition... making colorful complexes...

More likely it can be Ni(NH3)x(N2H4)y(ClO4)2
with x=0,1,2,3,4,5,6
and y=1,2,3
and with x+2*y =6
Of course due caution must be applied with such due to the legendary dangerous Ni(N2H4)3(ClO4)2 reputed to detonate into watery solution from friction/shock between spoon and glass recipient while hand swirling..

Hey Buddy - 12-1-2023 at 17:18

--Philou, that is excellent info on the diketopiperazine. I think a nitramide variation is interesting but the diketopiperazine should in itself make its own metal complexes shouldnt it? I think tetrazole lover in the past prepared piperazine extracted from OTC dewormer. IIRC in a comment he stated that piperazine perchlorate complexes were some of his preferred initiation compounds. I can attempt a controlled decomp. I have aspartic acid and glycine on hand.

--If it assists in making it more clear, the preparation I used to come up with the blue crystal was approximately:
Molar equivalents of perchlorate and glycine heated in minimum water, nickel wire was added in excess with stirring, soln turned bright green after an hour or so. Alcoholic hydrazine was added in molar equivalence. Solution was heated/stirred at around 30C overnight. Solution was royal blue next morning and was then gently air dried in an open container until crystals remained. They are still in drying but I may try to get a picture of them tonight and if they seem dry I may try to get a cautious idea of the sensitivity. I have read of some impractically-high-sensitivity Ni/N2H4/ClO4's so I will be careful in handling. It is a small sample and I will be prepared for detonation. I was thinking that complexing the perchlorate with the glycine and nickel before the hydrazine may be the safest way to experiment and it seems like it went through perhaps at least one intermediate complex changing from green to blue. Im not really sure though.

edit:
It is not flame or impact sensitive like a primary explosive. It burns like an angry version of a nitramine where the mass shoots around on foil. It produces a good amount of smoke. Not sure on residue because it burns holes through foil. A burning test can only give little idea of profile but in terms of things I've burned, it seems to have the most violence in burning, not like a ddt substance but more like ANQ or K-6. But with very little flame. And a bit of smoke. Mostly shooting out jets and smoke. Something about it just seems angry though, hard to explain. It seemed like only small spots burned reacting to flame but they burn with a lot of gas pressure and noise so it makes you think it's going to detonate, but it just burns. It seems to be holding water too. It doesnt seem to be totally dry despite drying for ~2 days on low heat. Sensitivity to hammer impact by hand seems fairly low, maybe a little more impact sensitive than ETN. Im not in search of this kind of material right now but it is interesting. The simplicity of Gly/ClO4 is the most intriguing. Maybe I should try nickel with hydrazine and add to GlyClO4 instead... 2,5-Diketopiperazine seems worth a test in complexation. I assume it can be prepared from heating glycine to under the decomp temp of 230 C.

edit 2: also seems like there was a red spot or two on crystals, not sure if this is a contaminant or a different oxidation state. I burned one of the red crystals and it behaved the same as the blue.

[Edited on 13-1-2023 by Hey Buddy]

_MG_9297.jpg - 168kB 2.jpg - 120kB




[Edited on 13-1-2023 by Hey Buddy]

PHILOU Zrealone - 13-1-2023 at 06:29

Quote: Originally posted by Hey Buddy  
--Philou, that is excellent info on the diketopiperazine. I think a nitramide variation is interesting but the diketopiperazine should in itself make its own metal complexes shouldnt it? I think tetrazole lover in the past prepared piperazine extracted from OTC dewormer. IIRC in a comment he stated that piperazine perchlorate complexes were some of his preferred initiation compounds. I can attempt a controlled decomp. I have aspartic acid and glycine on hand.
[Edited on 13-1-2023 by Hey Buddy]

The difference in structure between glycine and di-keto-piperazine explains why glycine (what displays a free primary amine R-NH2) can do complexation and why di-keto-piperazine (what is a cyclic di-amide (R-NH-CO-R')) shouldn't do so easily... urea or other amide (to my knowledge) doesn't complexate well or at all... I never noticed or eard of color change from urea/amides and transition metals salts like Fe(2+), Ni(2+), Co(2+), Cu(2+), Cr(3+), Mn(2+)... :( although to be sure I should have a spectrophotometer to detect any peak variation or shift in absorbance...


[Edited on 13-1-2023 by PHILOU Zrealone]

PHILOU Zrealone - 13-1-2023 at 14:42

Quote: Originally posted by Antiswat  
glycine sulfate and sodium perchlorate maybe? ammonium perchlorate is a pain on its own- for safety we should maybe try to produce glycine chlorate as homemade perchlorate can oftenly contain some chlorate

as for getting it out of solution, i would imagine somehow getting the GlyClO4 into maybe- acetone, then adding in an excess of polar solvent, or a mixture of solvents that shifts the polarity and crashes out the salt

https://www.sigmaaldrich.com/deepweb/assets/sigmaaldrich/mar...

this would claim acetone isnt miscible with anything, methanol seems to go into hexane and heptane, this is very easy to get from lighterfluid for zippo, distill out of gasoline, around 70*C fraction, or sold under names such as "washingbenzine" in europe

now, a sodium salt was mentioned- if thats possible, should an ammonium salt also not be possible to be formed? ammonium picrate was used a lot. forming a salt could maybe make it easier to pull out of solution
maybe good ol' DCM can help? the hygroscopicity is a major drawback, but the added difficulty could hopefully hint at it being very powerful

ammonium permanganate can also be made- and may be possible to combine in similar fashion, its a fair bit more unstable than ammonium perchlorate, so it could potentially be some kind of primary

perchlorate salts are very attractive especially if one can make them from chlorate by melting, half an hour at 300+*C didnt seem to do much for sodium chlorate. sodium perchlorate can be extracted using acetone- coming to think of it, glycine sulfate could maybe be combined with sodium perchlorate in acetone? and then simply shift the polarity, or let the acetone evaporate- as it usually does very well due to its high vapor pressure, let this occur at a very slight vacuum to supposedly keep moisture out and you would have a very practical route

EDIT: glycine chlorate is a real thing and its a primary! albeit, in the form of a coppersalt.
https://www.youtube.com/watch?v=K0X0qZF6DeM

[Edited on 11-1-2023 by Antiswat]

To avoid chlorate into perchlorate batches usually you mix it with a little HCl... HCl sets HOClO2 free and mutual oxidoredox destroys it into Cl2, Cl2O, ClO2, HOCl, HOClO and O2...then swirling and heat-venting makes it chlorate free. I think it was displayed into a Laboratory of Liptakov's YT video. HCl is not acting onto HClO4... only onto HOCl, HOClO and HOClO2.

Usually chlorate salts of amines are not a good idea... such are often very sensitive and on the edge of decomposition... most known salts decompose with time from various stimuli (heat, friction, hydrolysis by slight acidity, shock, and probably even more like spontaneous oxydoredox probably forming chloramines or chloramides related to NF3, -NF2, -NF-, =NF... but based onto chlorine... remember that CH3-NCl2 or Cl2N-CH2-CH2-NCl2 or bromo derivatives are quite powerful energetics about as powerful and sensitive as NG (See Axt tread about those)... the driving force of the explosive decomposition is the formation of HCl or HBr (instead of HF) such explosions generate a big black cloud of carbon sooth.
See chlorates like NH4ClO3, N2H5ClO3 have bad reputation of sensitivity and spontaneous decomposition.
A glycine chlorate will probably be quite powerful and sensitive... but also a serious risk of fire, deflagration or detonation upon storage...better put it into a soft recipient under shielding and away from breakable/fragile stuffs.

Glycine will probably react with aceton since ketons do form imines with amines...
(R-)2C=O + H2N-R' --> (R-)2C(-OH)-HN-R' --> (R-)2C=N-R' + H2O

Aceton is quite miscible with a lot of things including water in all proportions, ethanol, ether, ... but also hydrophilic or lipophilic compounds... it also dissolves some various salts but solubility is not straightforward...
NaCl is unsoluble while NaI is soluble (that is the base of the halide exchange reaction to go from R-Cl to R-I from R-Cl and NaI saturated into aceton and resulting in precipitation of NaCl.

Also NaClO3 is soluble and NaClO4 is even more... a simple Sohxlet extration will leave NaCl behind from a mix of NaCl, NaClO3 and NaClO4 (NaClO4 can be made by melting NaClO3 and leave some NaCl behind... indeed mp NaCl > Tdéc NaClO4> mp NaClO4 > Tdéc NaClO3 > mp NaClO3)...so aceton extraction is interesting into that very specific example (this doesn't work wel for KClO3 and KClO4)...
I have used the thermo-disproportionation technique and it works wel... you just need to heat to melting and keep it at that temperature and max 40-50°C above the MP until the clear liquid starts to leave white crystals in the bottom of the test tube (NaCl and NaClO4).No O2 bubbles... you have made a succesful perchlorate formation from a chlorate salt.
4 NaOClO2 (l) -heat-> 3 NaOClO3(s) + NaCl(s)

The solubility of NaClO3/NaClO4 into aceton is not terrific but sufficient and it works wel under the recirculating solvent extration process of Sohxlet... then you extract NaClO4 and NaClO3 (as a minor amount of impurity)... the remaining is non extractible NaCl.
This also was illustrated into one of Laboratory of Liptakov's YT videos.

NH4 picrate or NH4MnO4 have nothing to do with glycine perchlorate, glycine chlorate or complexes of transition metal oxidizing salts with glycine ...those ammonium salts have totally different stories and properties.

As mentionned earlier glycine and NH3 have like pKa/pKb and as such enters into competition for complexation or acid catching. The advantage of NH3 being its volatility and easier gazeification with low heating and low pressure/vacuum... so it will leave the system on its own if in the open.


[Edited on 14-1-2023 by PHILOU Zrealone]

Fantasma4500 - 14-1-2023 at 14:23

about NH4ClO3 it was tested by Dornier335A and he found it to be a bit disappointing, seemed sort of stable even, ammonium bromate however woelen have videos of, extremely unstable.
ah yes it may oxidize the glycine ... into with some luck nitroethane?

the chlorate salt of copper and glycine is a primary- the bromate would probably be much more so


PHILOU Zrealone - 15-1-2023 at 05:03

Quote: Originally posted by Antiswat  
about NH4ClO3 it was tested by Dornier335A and he found it to be a bit disappointing, seemed sort of stable even, ammonium bromate however woelen have videos of, extremely unstable.
ah yes it may oxidize the glycine ... into with some luck nitroethane?

the chlorate salt of copper and glycine is a primary- the bromate would probably be much more so


Yes NH4ClO3 is isolable but storage is unadvisable and unwise...once I planned to make a few kg batch because a bit disappointed by NaClO3 pyro-mixes and then I thought about NH4ClO4 what is quite good... so maybe NH4ClO3 would be great... but then I soon found about uncompatibility between NH4(+) and ClO3(-) (I was already aware of the uncompatibility between S/SO3/H2SO4 and chlorates)...and this changed my mind (just a few days prior my big batch of reacting large amounts of Ba(ClO3)2 or Ca(ClO3)2 solutions with (NH4)2SO4, then filtrating/centrifugating unsoluble BaSO4/CaSO4, and concentrate/evaporate/crystallize desired NH4ClO3... (I was about 18...now 47...stil 21 fingers).

Bromate and iodate are aswel...energetic and unstable.

Maybe disapointing in low quantities and unconfined but just like NH4NO3...amount/larger quantities may reveal a real danger and power.
I think I should test those in parallel for power and energetic properties...The exotic halide atom may bring some serious density increase (what is usually good for brisance and VOD...but also heavy gases may be a dead-weight and slowering detonation gases and reduce power?)

I think NH4 perbromate must be quite energetic and sensitive vs NH4ClO4.
BrO4(-) will improve density but also electrical oxydation power ( thus electric potential and ease of oxydation of NH4(+)... thus increased speed of reaction and power).

To stick transition metals arround chlorate, bromate, iodate or perchlorate, perbromate and periodate anions of amine complexes as mentionned into a past post into a complex/or exotic primary tread... is like boosting the sensibility and catalysing the sensitivity (ease of D2D by heat, shock or friction) of energetic aminium salts...

I do agree with you Cu(ClO3)2 and Cu(BrO3)2 and Cu(glycinate)2 must be very interesting investigation priorities...for primary field.

I am sure oxydoredox of ClO3(-) or BrO3(-) and HO2C-CH2-NH2 will never lead to CH3-CH2-NO2 (conversion of -CO2H to -CH3 is not possible with a strong oxydant ;)... but maybe (stil in doubt about it) it may lead to nitromethane if -NH2 could be oxydized to -NO2... then it would decarboxylate (like conventional synthesis of nitromethane from O2N-CH2-CO2H made from chloroacetic acid/ chloroacetate via halide exchange with a NO2(-) carier (like AgNO2 or from NaNO2, KNO2, LiNO2 into specific solvents).
Axt had tried to make nitramide and dinitramide from R-NHX and R-NX2 (X= Br or Cl)... with a moderate (but full of hope/promise) transitory success?

I thought more modestly to susbtitution of X(-) with OH(-) to maybe lead to R-N(-OH)2 and then R-N=O + H2O
I never found any reference of that experiment except maybe an obsure old mention in a book about degradation of NCl3 that lead to NO2(-) and NO3(-).
I was hoping converting easy accessible (but dangerous and explosive) NCl3 into valuable nitrite and nitrate anion...and to transpose this to organic R-NX2 with as results nitroso and nitro compounds.

In this case of glycine, I think the result may be diazo-diglycine (via a nitrosoacetic acid)...
HO2C-CH2-NH2 + O=N-CH2-CO2H --> HO2C-CH2-NH-N(-OH)-CH2-CO2H
--> HO2C-CH2-N=N-CH2-CO2H + H2O



[Edited on 15-1-2023 by PHILOU Zrealone]

[Edited on 15-1-2023 by PHILOU Zrealone]

PHILOU Zrealone - 22-1-2023 at 14:11

Quote: Originally posted by Etanol  
Quote: Originally posted by Hey Buddy  
I began looking into amino acid ligands. Glycine perchlorate is reported to be:
1.89 g/cc
+13.67% (CO) OB
Vd 8470 m/s
32.26 GPa
>60 J IS
>360 N FS
mp 103 C
Td 263 C
("Insensitive Ionic bio-energetic materials derived from amino acids" Zhang, "Scientific Reports" 06 Oct 2017)

[Edited on 19-12-2022 by Hey Buddy]


How was estimadet VoD and detonation pressure?
It is very much for these compound at 1.89g/cc. May be c.a. 8000 m/s 25 GPa?

As they explained into their article in page 9-10, they used a Kamlet-Jacobs equations type... but those are usually used into the case of CHNO explosives with some succes but not with other atoms like Cl... although I suppose maybe some adaptations/modifications or inclusions could now be made for those cases(?)
No wonder values are or seem inconsistant or practically off by a lot.

PHILOU Zrealone - 22-1-2023 at 14:42

Sadly I noticed by now that their study was far from complete and that they left aside the most interestings natural occuring amino-acids... the complexing ones and/or basic ones (holding extra amine, guanidine or basic cycloamine into the lateral chain of the amino-acid)...

They exposed Glycine (what is great because the shortest and simpliest amino-acid and thus displaying a good OB (or higher oxydiser/fuel ratio) aside with Alanine, Serine, Asparagine, Valine, isoLeucine, Leucine and Proline as their perchlorate or nitrate... but those are obviously less performing than some forgotten ones...

They stupidly forgot Lysine, Arginine, Histidine, Ornithine, Citruline, Pyrolysine... :mad: and those should have displayed higher densities and OB because able to host 2 or sometimes 3 HClO4(or HNO3) moeities... what a pitty blindness.

[I will edit this soon to detail a bit each of the valuable naturally occuring amino-acid left aside...]

[Edited on 22-1-2023 by PHILOU Zrealone]

Etanol - 23-1-2023 at 18:55

Quote: Originally posted by PHILOU Zrealone  
[rquote=679828&tid=159159&
As they explained into their article in page 9-10, they used a Kamlet-Jacobs equations type... but those are usually used into the case of CHNO explosives with some succes but not with other atoms like Cl... although I suppose maybe some adaptations/modifications or inclusions could now be made for those cases(?)
No wonder values are or seem inconsistant or practically off by a lot.

Oh thanks. I was hoping another method.
The Kamlet-Jacobs equation does not always provide the correct result even for CHNO substances. For example, with a high nitrogen content. The volume of gases from 1 kg of water at normal pressure is 28/18 from 1 kg of nitrogen. But nitrogen gives a greater contribution to pressure and VoD than water.

Hey Buddy - 18-5-2023 at 21:15

I'm back on glycine perchlorate again. The original samples from direct NH4ClO4 displacement have been stored until this last week. The samples appeared to have a slight color change, browning. I attempted to melt cast the samples. They would not melt. Im not sure what to make of that. I attempted a double displacement of glycine and ammonium perchlorate with equivalent HCl. The solution was boiled down to precipitation and then dried over night. A white powder dries out of evaporated solution. This material was put in a pan over 120 C and it melted easily. I have cast a test cylinder for firing. The glycine perchlorate made this way casts very densely and is probably the best material I've casted with. It seems denser than TNT and is very flat and smooth on its surfaces. There are no air bubbles nor off gassing during melting. I tried to burn a piece to see if it's burn flame matched the images from earlier in the thread. It did not behave with a large flame as in the pictures but rather fires off gaseous hisses through out burning and in this limited test the material didnt entirely catch fire and required continuous flame to decompose. I tested some of the first old material by firing against a can, it explodes in small mass and has a low critical diameter. I have fired it as low as 50 mg mass in confinement. I will churn out some more glycine perchlorate and continue testing but it's a pretty useful material simply from the castability alone.

UPDATE:

apparently glyClO4 melt cast detonates from a cap of NAP directly with no booster. I loaded a 1"x1.5" cylinder. couldn't find anything remaining in the dirt.
I only made one sample as a test, so now I will replicate

[Edited on 19-5-2023 by Hey Buddy]

MineMan - 19-5-2023 at 15:53

Update?

How does the power compare to ETN? If it is detonating from NAP is it sensitive?

At max density 8kms should be more impressive than RDX, as being a powder is never compressed enough.

Hey Buddy - 19-5-2023 at 16:51

Quote: Originally posted by MineMan  
Update?

How does the power compare to ETN? If it is detonating from NAP is it sensitive?

At max density 8kms should be more impressive than RDX, as being a powder is never compressed enough.


Here is a sitrep:
It looks good, Im really pleased. but it's not settled at all. First, there are some issues with the production methods and their products. I'm not entirely sure that only glycine perchlorate is being produced. Or how much of the material is being converted to glycine perchlorate. Is it 100%, 90%, 80%? This I dont know. Obviously the way around that is to use HClO4. In my opinion, HClO4 is a last resort because it adds a magnitude of effort to an otherwise effortless preparation. The two preparations Ive used so far at small <20 g samples:
1) Reflux NH4ClO4 + Glycine in a beaker, several hours, evaporate, dry.
2) Reflux NH4ClO4 + HCl + Glycine in a beaker, several hours, evaporate and dry.

Method 1 produces a powder which appears to melt above 100 C and less than 140 C. I did not try casting with the material, only tested if it melted in correct range. This material detonates in small masses ~50 mg+. This material undergoes some browning over months of storage in air tight container. This material after long storage lost its ability to melt at the same temperature range as before.

Method 2 produces a white powder that melts between 100-120 C. It melts very easily and homogenous pour that isnt too thick or thin. I casted this material into a 1x1.5" PEX line, buried it in dirt. Primed it with an NAP cap of stainless steel. There is a hole in the ground wide enough for my hand and ~8" deep. With pulverized dirt on the edges. I found no remaining plastic in the hole, no shreds, no powder or melt cast material. I went back out to the hole again and dug out the pulverized dirt and recovered 2 strips of flat stainless steel from the blasting cap. The hole was impressive for the size of the charge. It was a small charge so when it detonated in dirt the report wasnt impressive to the ear.

The sensitivity of GlyClO4 is supposed to be very low. I will hammer test for impact on the next batch to verify insensitivity. Overall, it is capable of doing work. It's hard to say from only one small charge shot, but it seemed less powerful than Comp B but more powerful than TNT. The hole was more than I would expect from TNT. Overall it just needs a lot more testing. I also think maybe some of the amino acids not from the original paper would be worth trying because if they can hold a positive OB with the oxidizer addition and melt at low temp, it could be the perfect cast carrier. I think glycine perchlorate for the price and availability and ease of preparation is really good, already. TNT and even TNP is way more effort and time in production compared to this. Even the NQ eutectic melts are more time/effort.
I need to distill some nitric and try the AspNO3, it should be boiling water bath meltable. Glycine is about twice as cheap as aspartic acid...

And it melts well, the glyClO4. It is very workable, pourable. dries so flat. Hardens like a thermo plastic. I may try a couple with Al to see if they thermobaric...

I think a high energy material like ANQN or K-6 would be well within the safe temp of cast and would probably be pretty high performance for cast comps. I wonder if ANQN would be protected and stabilized further by the melt cast?

[Edited on 20-5-2023 by Hey Buddy]

UPDATE:
I just went out to measure the actual hole and Im glad I did because my assumption of 8" was way overblown. It was really about ~5". Diameter was around ~4".
Still, GlyClO4 is looking pretty good in my book.

IMG_0818.jpg - 838kB IMG_0819.jpg - 784kB



[Edited on 20-5-2023 by Hey Buddy]

MineMan - 20-5-2023 at 01:28

Okay

To be an honest man I am comparing this to DAUN with 9000ms VOD and melt cast below 100C I can’t say I see advantages But I would like to be convinced

underground - 20-5-2023 at 03:09

I tried a mixture af DU and AP at 1:1 molar ratio and boiled down. DU is a weak base so no NH4 come off, or very little. Most likely it was a mixture of DUPer DU and AP. The thing did not want to crystalize like DUNitrate. After adding a bit of Cuo and heating NH4 come out and a light violet powder formed. Most likely a Cu complex of DUPerch. It did not seemed energetic, it did not burned even with a flame but continuous heating left almost nothing. It is not a primary for sure. I will probably try the nickel salt but i dont expect much. Maybe a chlorate salt would do something. I will probably made some aminonitro urea from DUnitrate and H2SO4 and test its properties. It seems that you can not do much with DU. Aminnitrourea could probably be far better than DU

In my opinion DU does not worth since i bought it at the same price as Aminoguanidine from Alibaba. AmGu is much more useful than DU.

[Edited on 20-5-2023 by underground]

Hey Buddy - 20-5-2023 at 08:19

Quote: Originally posted by MineMan  
Okay

To be an honest man I am comparing this to DAUN with 9000ms VOD and melt cast below 100C I can’t say I see advantages But I would like to be convinced


I've never made DAU so I cant compare the two characters. In terms of preparation, DAU is a lot harder to prepare than buying glycine. I think DAU would probably have to be nitrated and would have problems displacing. Is it even verified that it is melt cast and useable? I've read some about it on SM but it all seems to be theoretical. I havent read about case use. I can tell you for sure that a pound of glyClO4 is a lot easier to prepare than a pound of DAUN. For sure. The hardest part is waiting for it to dry. I made 300 g last night and the reaction only took 1.5 hours.

underground - 20-5-2023 at 12:18

Hey Buddy, in theory you could know how much of your producs is converted to GlPerc by measuring the final product. 1 mole of Glyc is 75,07g. 1 mole of AP is 117,49g. 1 mole of GlycPec is 173.51g. So in theory if you reflux 75,07g of Gly with 117,49g of AP you should take 173,51g as final product if 100% of material is being converted. Now if your final product weights more then ofcourse not all of your product is being converted. By seeing how much of your end product weights you could actually calculate how much of GlyPer is being converted. You could even capture the ammonia that escapes and weight it out to find out how much 100% of material is being converted.


[Edited on 20-5-2023 by underground]

Microtek - 20-5-2023 at 13:41


Quote:

1) Reflux NH4ClO4 + Glycine in a beaker, several hours, evaporate, dry. 2) Reflux NH4ClO4 + HCl + Glycine in a beaker, several hours, evaporate and dry.


This is already more time than preparing HClO4 from HCl (aq) and NaClO4.

Method number 2 will produce some mixture of NH4Cl, NH4ClO4, Gly*HClO4, Gly*HCl. It's difficult to say which proportions. I'm also not convinced enough of the ammonia will be driven off by boling glycine with NH4ClO4.

If you add ANQN to a melt consisting of an ionic perchlorate such as GlyP, some of it will be conerted to ANQP which is much more sensitive (1 J impact sensitivity IIRC). It might sensitize such a charge to an unsafe level.

underground - 20-5-2023 at 14:07

You can actually make Hclo4 from Nh4Clo4 with nitric acid and hydrocloric acid. LL have a very good video about it.

https://www.youtube.com/watch?v=KXpGlgj9_uw&t=16s

Hey Buddy - 20-5-2023 at 18:25

Quote: Originally posted by Microtek  


This is already more time than preparing HClO4 from HCl (aq) and NaClO4.


Method number 2 will produce some mixture of NH4Cl, NH4ClO4, Gly*HClO4, Gly*HCl. It's difficult to say which proportions. I'm also not convinced enough of the ammonia will be driven off by boling glycine with NH4ClO4.

If you add ANQN to a melt consisting of an ionic perchlorate such as GlyP, some of it will be conerted to ANQP which is much more sensitive (1 J impact sensitivity IIRC). It might sensitize such a charge to an unsafe level.


-Glycine/NH4ClO4/HCl was only tried because the original two salt method was not melting after some time of storage. The original method is preferrable because it is more correct, in theory, but if it doesnt melt there is no point. So out of curiosity, it was attempted with HCl just in case there was some unforeseen precipitation or possibility of separation. There was no precipitation, so it was boiled down. There are certainly mixed products. I don't know what the melting temps of all of those are, but many of them are high. NH4Cl is over 300 C. Glyicine and NH4ClO4 are 230+ and 200 C decomp. The product of this evaporated mixed product is melting just over 100 C. GlyClO4 is claimed to be 103 C. I would guess due its responsiveness to what amounts to a medium powered cap and the low melt temp, it is likely a high concentration of GlyClO4.

In my opinion, refluxing everything together and drying is fewer steps than preparing HClO4 and then protonating the glycine as a second step and washing/drying. Of course it may be more beneficial to just take the extra step and churn out HClO4.

I agree that in both methods of preparation, the NH3 isn't getting entirely boiled off. It appears to have a diminishing exponent curve in displacement. A lot of it is driven off at first and then it tapers and can be refluxed basically forever with faintly detectable NH3. In the end, there is a degree of mixed product.
The mixed product probably explains why it fits many of the characteristics from the paper, but doesnt respond the same way to flame. There is likely a diminished performance due to mixed product.

The overall question is how well does it perform. This is what needs qualification. If the end product achieves ends then it is worth while. I thought from a small test it seemed to perform a little better than TNT, but its only one impromptu. I didnt even think it would actually fire during the test. So I was surprised and unprepared. My judgement could be off. It could be not really performing that well, whereas perhaps the proper attempt from HClO4 would be high-performance. --The exciting aspect to me is that it melts and pours well, and responds to a blasting cap.

Im finding glycine at ~$14 USD per pound, (lysine is $10/lb). so for a melt cast substrate easier to prepare than TNT, melting under 130 C, this might be the cheapest, next to perhaps some other Amino acid nitrates/perchlorates. Perhaps this method produces an underpowered mixed product, but it appears to still fill a role as a cast carrier. In that case the HClO4 derived GlyClO4 may prove to be even higher performance. Point is, there are not a lot of melt cast explosives. Most of them are unrealistic to produce in anything greater than novelty quantities. TNT production, in any real quantity is a PITA. It is messy and has a lot of waste liquor. There really just arent a lot of melt cast substrates. Eutectics there are more of, emulsions are a dime a dozen, but melt substrates are needed to carry mixtures at high density in useable forms.

Thats a good point about ANQN. Nitrimines and Nitrate esters are likely more compatible with a melt perchlorate loading. I suppose the ANQN could be used with a AspNO3 or other nitrate amino acid melt which may be pretty simple prep after all.

All this stuff needs testing. So while im pleased, it's far from settled. Im just trying to give mineman an update. I made 300 g batch last night which is drying, Im trying to repeat the process for validation. I plan to compare it to a HClO4 glycine in the future. I want to know how different the two are, and if the large flame signature from the paper is repeatable from HClO4/Glycine.

Untitled.jpg - 113kB lysine.jpg - 128kB

[Edited on 21-5-2023 by Hey Buddy]

Microtek, what do you think is a good test of performance for a secondary? The small scale steel perforations on ~2.5mm steel? Or aluminum block witness crater? I think I still have both of those from earlier last year..

[Edited on 21-5-2023 by Hey Buddy]

Hey Buddy - 20-5-2023 at 18:27

Quote: Originally posted by underground  
You can actually make Hclo4 from Nh4Clo4 with nitric acid and hydrocloric acid. LL have a very good video about it.

https://www.youtube.com/watch?v=KXpGlgj9_uw&t=16s


Anyone is welcome to pick up some common glycine and make some perchloric acid at any time. It wont bother me the slightest. : )

Hey Buddy - 20-5-2023 at 21:14

Quote: Originally posted by underground  
Hey Buddy, in theory you could know how much of your producs is converted to GlPerc by measuring the final product. 1 mole of Glyc is 75,07g. 1 mole of AP is 117,49g. 1 mole of GlycPec is 173.51g. So in theory if you reflux 75,07g of Gly with 117,49g of AP you should take 173,51g as final product if 100% of material is being converted. Now if your final product weights more then ofcourse not all of your product is being converted. By seeing how much of your end product weights you could actually calculate how much of GlyPer is being converted. You could even capture the ammonia that escapes and weight it out to find out how much 100% of material is being converted.


[Edited on 20-5-2023 by underground]


This is a good point but I think to save effort, simply compare HClO4/Glycine product-work with NH4Clo4/Glycine product-work. There is no point to the theoretics if the actual is "good enough", in my opinion.

Microtek - 21-5-2023 at 01:51

I would suggest the aluminum block crater if you can make the GlyP fire in "small" charges (otherwise you'll need large aluminum blocks). Alternatively, envision the application of the substance (is it for loading shaped charges, for shattering stone, for excavating holes or maybe for deforming metal?) and then devise a suite of tests that examines these abilities at an appropriate scale. This will tend to give more useable results than more generic tests. For instance, since I'm only working at the ca. 1 g scale, things like NTO which has good theoretical performance, is simply not practical because of critical diameter effects.

About GlyP from glycine and HClO4, you just add them together, then heat to evaporate the water and pour into whatever mold you want. There is no washing or separate drying step (indeed GlyP is much too soluble in water to wash; youu'd simply redissolve it).

Hey Buddy - 21-5-2023 at 08:47

disappointing update:
Well, Im still drying out the 2nd batch of glyP to validate the first test. I was mowing the field today and found the section of PEX from the test about 25 meters from the test site. It is expanded but barely damaged, not even ripped apart. Assuming it is the casing from glyP test, it must have fired out of the hole like a rocket. Somehow, despite not destroying the casing, it managed to blow a hole in the ground. Im not sure what exactly to make of that... I found blasting cap segments in the hole at time of test but no casing fragments, so I assumed it was practically destroyed. It's possible it could be a casing from an entirely different test at another time, but I think it is the glyP test. If it is, then glyP made from the salt methods cant be as powerful as TNT. TNT shreds this stuff.

The modified update is: glyP from HClO4 needs to be tested. Mixed salt glyClO4 dodesnt look "as good" as it did. It still melts and fires, but it's certainly no 8km/s. Maybe glyP from salts is a good rocket fuel if it is launching pipes like that?

[Edited on 21-5-2023 by Hey Buddy]

Hey Buddy - 21-5-2023 at 08:53

Quote: Originally posted by Microtek  


About GlyP from glycine and HClO4, you just add them together, then heat to evaporate the water and pour into whatever mold you want. There is no washing or separate drying step (indeed GlyP is much too soluble in water to wash; youu'd simply redissolve it).


Okay this is the next step. I will get around to this when I can. I am still evaporating the mixed salt batch and will test sme of its properties maybe for propulsion.

MineMan - 22-5-2023 at 02:01

Even high VOD explosives, plastic seems pretty resilient to, especially thick plastic. I am still excited. I think this is a good find!!

specialactivitieSK - 1-6-2023 at 08:01

Has anyone tried to make it by double replacing glycine hydrochloride and sodium (ammonium) perchlorate in water or another medium.

Hey Buddy - 1-6-2023 at 11:36

I havent tried HCl of glycine. I did get some of the cheap Lysine HCl that may hold 2 nitrates. Havent tried it yet though. If you could find a good solvent for dropping out NH4Cl or glyClO4, displacement from an HCl would be beneficial.

specialactivitieSK - 5-6-2023 at 01:36

By guanidine perchlorate, methanol is used.

Consolidated update

Hey Buddy - 22-6-2023 at 12:09

I've not been working on this as much as i'd like. I am still at the exploration of the simple displacement methods. I wanted to sum up findings:

-A dirty version of GlyClO4 can be prepared via reflux of stoich NH4ClO4 and glycine, or with added HCl.
-I haven't compared yields between the two. its unknown if any advantage is had by HCl.

-The product of the HCl route can be easily melted at low temp. I melted it at around 120 C which seemed like a good working temp. The original text version of this material, prepared via HClO4, is reported to melt at 103 C.

-Both methods of producing the dirty version of this material result in a strange behavior: The material readily melts into a clear opaque castable substrate that cures flat. BUT... If the material is left un-melted such as in a drying plate, it develops brown spots and the smell of caramelized sugar. A sample made via HCl was left in the drying cabinet @ 60 C for two weeks and it developed this character. Another sample, prepared without HCl, was stored in a sealed plastic container for several months and when it was opened, it exhibited both the sweet sugar smell and some browning.
The brown-tainted material does not melt at any useful temp up to 180 C. The material after browning is still hot water soluble, and the brown color comes out into hot water and a solid material can be recovered leaving a brown water and white material. In the instance where I tried this to purify it, I refluxed it again after separating the brown water, and ammonia did not evolve from reflux. Then I accidentally burned the sample and wasnt able to continue recovery for checking explosive character.



Regarding explosive character of the dirty version of GlyClO4:

I used NAP to test all detonations of the material.
The brown version from the bottle (mentioned before, prepared without HCl), could be detonated but not melted. It can be detonated in small masses like a primary explosive (>50 mg). I believe this is only possible due to the power of NAP.

--A fresh sample made with HCl was cast within 2 days of drying in a 1" diameter x 1.5" length. It was not hygroscopic.
That sample detonated entirely and I believe it is detonating at reduced velocity. I couldn't say for sure, but suspect it's detonating around 5-6km/s. That test's results are in the photos posted earlier.

I attempted to prepare a sample using Isopropanol solvent. Neither glycine nor ammonium perchlorate appeared to dissolve into boiling IPA. the IPA sample was dried then refluxed again in water. Ammonia was evolved.
Reflux lasted 1 hour. The sample was cooled to room temperature and stayed dissolved in the water. While in liquid phase, and at RT, 90% IPA was added to the sample.
White material precipitated. The beaker was left out overnight and resulted in two crystals. A long needle crystal which consolidated over the ptfe stir bar, and large blocky square crystals which formed on the bottom of the beaker. The crystals were decanted and separated on a hot pan. The crystals would not melt at 120 C.

Im not sure what any of this means, but I thought I would just describe this and maybe someone would get value out of it. I have no idea why the material seems to behave unpredictably. My only guess is there are variable proportions of impurities at play here.

The next interest in this exploration is a pure HClO4 sample. Which probably should have been attempted first as control, but I was too fascinated at the prospect of a material produced from OTC salts.
Currently building up HNO3 towards that.
Regardless, I think there is value to the dirty version because of its simple utility. It really casts nicely and would be an excellent cast substrate for anything in that temp range. I regard its explosive character comparable to dinitrotoluene.

Does anyone know if nitrate esters can be safely carried in a perchlorate melt cast? I would like to try nitro guanidine and PETN in the dirty version.

[Edited on 22-6-2023 by Hey Buddy]

MineMan - 23-6-2023 at 03:13

I can’t answer your other questions. I wish PHILOU was here too.

As for the melt cast. Can you try incorporating a few percent glass microballoons and or aluminum, should allow full VOD.

The displacement reaction from AP is obviously most interesting. Any other amino acids that might work as well? Citrulline?

Was really hoping this synth would be as easy as NAP? Is it possible to add aminoguanidine and use glycine as the ligand… such as glycine aminoguanidine perchlorate. Probably not, as you need a heavy metal with a positive charge?

Hey Buddy - 23-6-2023 at 07:27

Quote: Originally posted by MineMan  


The displacement reaction from AP is obviously most interesting. Any other amino acids that might work as well? Citrulline?

Was really hoping this synth would be as easy as NAP? Is it possible to add aminoguanidine and use glycine as the ligand… such as glycine aminoguanidine perchlorate. Probably not, as you need a heavy metal with a positive charge?


practically all the amino acids have ~decent explosive performance. There are several that are liquids that perhaps could be used as energetic plasticizer in PBX. Of course that is out of scope for me for now. I am mostly focused around finding alternatives to TNT due to waste liquor of aromatics, and finding a high performance filler to experiment with that would approximate or exceed RDX. Aspartic acid NO3 is 7.5km/s 22 GPa with an mp of 98 C, but it has half the heat of formation as TNT, so it would probably be approximate to TNT in experimental performance. Still it is a nitrate that could potentially overcome shortcomings of TNT and be compatible with nitrimine and nitrate fillers like carbohydrazide nitrate or ANQN. IsoLeucine perchlorate would also be interesting because it has approximate heat of formation to TNT, but 25%+ GPa and an extra km/s. Its also mrlting at mid 70 C. The biggest problem with that is availability of isoleucine. Aspartic acid is also somewhat more expensive as well. Glycine and lysine are very inexpensive and easily available where as the others ive found are twice in cost.

I think the dirty version of GlyClO4 is almost as easy as NAP. It has to be cast right away after drying. It isnt tested if it is stable long term or if it degrades in the cast state. the browning may be degradation of impurities. The actual HClO4 version may be more stable
.--For detonation, An energetic filler like PETN would definitely bump up the numbers quite a bit. ETN melt phase sensitivity is too bad, because it would be ideal for this sort of purpose if it were safe.
--Regarding complexes, you can definitely make glycine perchlorate metal complexes. I have not experimented with aminoguanidine with glycine, but I have done a little bit of guanidine/glycine. I have experimented with a Cu 1 variant and I moved on because I was looking for sensitive primary explosives rather than secondary character explosives. That copper/clo4 complex from guanidine standalone was very simple, in my memory i think i used sulphate as the copper source. It produced a green copper 1 complex that was insoluble and detonated on hammer stike a little less sensitive than PETN. I was not looking for that kind of material at the time, but it is probably worth revisiting and also checking melt properties. It was a metal complex of secondary explosive character. There are certainly possibilities in that realm of glycine, its just so many variables, it is a difficult thing to decide which direction to explore. Once I have more experience with casting, I can begin doing a lot more comparison of actual work of secondaries.

yobbo II - 23-6-2023 at 15:11


This sounds too easy to be usable.

Glycine Sulphate (which seems to exist) + Barium Perchlorate (or chlorate).
Barium Sulphate is totally insoluble. You are left with Glycine Perk. in solution.

Yob

Amino acid anecdote

Hey Buddy - 24-6-2023 at 07:23

I found this paper on the interaction of amino acids with ammonium nitrate. The purpose of the paper is phase stabilization of AN using amino acids. It concludes that amino acids do stabilize AN. The relevent part is they determined that amino acids like glycine form GlyNO3 and Gly/AN complex under heat and water. Other amino acids only form complexes without release of NH3.

There is really a lot of much deeper exploration warranted for amino acid energetics. I wonder if amino acid stabilized AN is still hygroscopic?

Attachment: amino acid NH4NO3 stabilization.pdf (1MB)
This file has been downloaded 163 times


Amino acid anecdote

Hey Buddy - 24-6-2023 at 07:24

I found this paper on the interaction of amino acids with ammonium nitrate. The purpose of the paper is phase stabilization of AN using amino acids. It concludes that amino acids do stabilize AN. The relavent part is they determined that amino acids like glycine form GlyNO3 and Gly/AN complex under heat and water. Other amino acids only form complexes without release of NH3.

There is really a lot of much deeper exploration warranted for amino acid energetics. I wonder if amino acid stabilized AN is still hygroscopic?

Attachment: amino acid NH4NO3 stabilization.pdf (1MB)
This file has been downloaded 144 times

Not sure why this posted twice?





[Edited on 24-6-2023 by Hey Buddy]

Microtek - 24-6-2023 at 08:49


Quote:

The next interest in this exploration is a pure HClO4 sample. Which probably should have been attempted first as control, but I was too fascinated at the prospect of a material produced from OTC salts. Currently building up HNO3 towards that.


What is the purpose of HNO3 in the context of making HClO4?

Hey Buddy - 24-6-2023 at 12:05

Quote: Originally posted by Microtek  


What is the purpose of HNO3 in the context of making HClO4?




I was going to try this method
https://www.youtube.com/watch?v=rUFsvlsi08E

What do you recommend?

[Edited on 24-6-2023 by Hey Buddy]

Aspartic Acid Nitrate 151.11 g/mol

Hey Buddy - 25-6-2023 at 11:04

1.6g/cm3
-8.16 OB (CO)
98 C mp
22.9 GPa
7508 m/s
[insensitive bio energetics, zhang 2017]

This is the highest performing nitrate currently known of amino acids. It outperforms TNT theoretically and outperforms TNP in velocity, though not in pressure. This material is reported to melt between the temp of TNT and TNP. This is the initial procedure I used in preparation. I'm just going to dump all ionic amino acid experiments into this thread to keep them all together since they are somewhat similar.

43.4 g (29 ml) HNO3 (75%-99%)
70.6 g L-Aspartic Acid (.53 mol @ 133.103 g/mol)
60 ml dH2O

60 ml dH2O was added to a beaker (@ rt ~30 C), water was stirred as 70.6 g Aspartic Acid was added.
Asp conglomerates in a somewhat insoluble, self-clinging, white mass at the bottom of beaker. It can be stirred into the slurry but it quickly settles back to the bottom as a thick mass.
Nitric was added slowly. At 10ml addition of HNO3, the temperature of reaction increased 7 C and the mass concentration of aspartic acid changed as it was converted to nitrate, dissolving into solution.
*60 ml H2O was probably too much H2O. two-thirds or even half is probably suitable, despite the insolubility of aspartic acid at first addition.
On complete addition of HNO3, temperature was 40 C. The reaction changed from thick and opaque to thin and clear like water within around 10 minutes.
The reaction was stirred ~15 minutes after complete addition of HNO3.
The viscosity of the finished nitrate product in this volume of water is a syrup, similar to mineral oil.
The finished product was poured out onto a pyrex pan and dried at 75 C.

I plan to test mp, castability, hygroscopicity, and perhaps some blasting in 1x1.5" pex as standalone and perhaps with some PETN and NQ. It is drying now.
Please let me know if there is something youd be interested in testing in this material, and I will accomodate if in my ability. I originally planned to compare to TNT, but I have run out and found I also have no toluene so if the material is good, I will direct compare to TNT and TNP later. This is a small validation batch, so its limited to however much nitrate is made from 70 g Aspartic.

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[Edited on 26-6-2023 by Hey Buddy]

[Edited on 26-6-2023 by Hey Buddy]

Hey Buddy - 26-6-2023 at 04:42

It's now the next morning. Drying appears to have plateaued. It is now the consistency of melted hot glue. It is around 80-85 C, I'm hesitant to go higher because I dont want to melt it. Any suggestions?

will try desiccator

[Edited on 26-6-2023 by Hey Buddy]

underground - 26-6-2023 at 08:22

Vacume desiccator would be ideal. Could you also give a try the perchlorate salt?

Hey Buddy - 26-6-2023 at 09:54

Quote: Originally posted by underground  
Vacume desiccator would be ideal. Could you also give a try the perchlorate salt?


I guess i should probably build a vacuum desiccator. I put it in a trashbag with a half pound of NaOH, hopefully that will work. I believe from the paper, the perchlorate salt of aspartic acid is a liquid phase material with lower power than the nitrate. I will however attempt some perchloric acid and treat the glycine. hopefully today. I fear if the AspNO3 cant be dried by heat, it may be hygroscopic? I was looking through the paper and I didnt see anything about hygroscopicity. Maybe its some technical measurement reading in the paper that I'm unfamiliar with?.. they do use water evaporation then vacuum desiccator though it says, so maybe its not hygroscopic and requires desiccation to dry?

[Edited on 26-6-2023 by Hey Buddy]

I found a vacuum pump and a vacuum desiccator in garage but i cant transfer the material from the pan because its too gummy. Pan is too big to fit. I will just leave it in NaOH for now.

[Edited on 26-6-2023 by Hey Buddy]

underground - 26-6-2023 at 13:29

It reminds me the diaminourea nitrate. It was a PITA to crystalize out and it was very hydroscopic. You could try to add a solvent that it is not soluble in to force it to crystalize out.

Hey Buddy - 26-6-2023 at 23:15

Quote: Originally posted by underground  
You could try to add a solvent that it is not soluble in to force it to crystalize out.


Good idea. That's a good thing to test anyways. I will scrape some and put it in desicator, try some in solvents and if nothing else, try to melt it to release water. If all that failed it may just detonate anyways regardless of water. Then move on back to glycine.
I ordered some isoleucine which should make decent NO3 and ClO4 salts. Have yet to test lysine which is a complete unkown. Dont know if it will be solid phase or not.

Microtek - 26-6-2023 at 23:53

Regarding the perchloric acid, I have advocated the NaClO4 + concentrated HCl several times in the past here on SM:


Quote:

An easier way to perchloric acid is to use highly concentrated HCl (37-40 %) and NaClO4. In the mix, NaCl is practically insoluble (common ion effect), so filtering off the NaCl will give you a mix of hydrochloric and perchloric acids. This can then be heated (or distilled) to drive off the HCl. By heating the liquid to 135 C, the perchloric acid will be pure enough to not give a precipitate with AgNO3.

Problems with this method are:
- You need a acid resistant filter, preferably a fritted glass Büchner (or you can settle for decanting, but you will lose some acid)
- You really need a very highly concentrated hydrochloric acid or the solubility of NaCl will be appreciable

Advantages:
- If your NaClO4 contains some chlorate it will be destroyed
- You avoid high temperature distillation of HClO4 and all the dangers associated with that


I'm attaching the paper with the method I used. If you only have NH4ClO4, you can easily convert it to NaClO4 by reacting with the stoichiometric amount of NaOH, and heating to drive off the ammonia.

Attachment: HClO4 from NaClO4.pdf (377kB)
This file has been downloaded 173 times


Hey Buddy - 27-6-2023 at 05:19

Quote: Originally posted by Microtek  
Regarding the perchloric acid, I have advocated the NaClO4 + concentrated HCl several times in the past here on SM:


That looks like a good route

Hey Buddy - 27-6-2023 at 06:08

I've been playing with AspNO3 for the past day. Here are some findings...

Regarding AspNO3 itself:
This material is hygroscopic and water soluble. When dried, it is a semi-solid similar to a glassed soft-polymer like melted sucrose. It melts below 100 C as referenced in paper. In melt phase, it is thicker towards 100 C, perhaps like a melted sugar. It becomes thinner at higher temperatures like melted butter.
I mistakenly used too much nitric acid because the concentration was unknown. During melt phase, a lot of what (I'm assuming) was excess HNO3/H2O was vaporized into the air.

AspNO3 casts as a clear semi hard flat cast, similar to a soft epoxy. It is hygroscopic on the surface.

It is soluble in acetone, MeOH and IPA
Insoluble in nitromethane
It forms a milky solution and in acetone, falls out of solvent as a powder and when removed, quickly returns to goo. It possibly reacts with the solvents changing its properties, like melting point and opacity.



Now the interesting part:

Melted AspNO3 plasticizes nitroguanidine. I cant tell you what the rate is, because I learned this in haphazard experimentation, not expecting it to melt NQ. Not only does it melt NQ, it does so with impressive proportions of NQ. It seems endless. I stopped adding NQ because I simply didn't want to use that much nitroguanidine stock.

The NQ is dissolving in AspNO3 presumably at or near max density. It is certainly the easiest way to achieve max density of NQ. Plasticized NQ is very sticky while hot but cools in a few minutes to consistency remarkably similar to comp C4. It shapes and forms practically identically to C4 warmed to body temperature. It has greater adhesive properties than C4, and easily bonds its surface to concrete, wood, metal and plastic. It can be molded into shapes and can mold into thin sheets.

The NQ plastique has two components, the AspNO3 and the NQ plastique itself. The AspNO3 component appears to retain hygroscopicity at surface of material and cast shape but the inner volume of material is unaffected. The NQ plastique can be exposed to water where the ASPNO3 in exposure to water is dissolved, leaving the NQ at ultra high density which cures to a hard plastic like PVC. The plasticity of the NQ plastique (without additional hydrophobic plasticizer) is moldable on exposure to atmospheric air for around 6 Hours. At 6 hours the plastic begins to set hard. I haven't tested if it can be remelted yet.

FYI: Nitroguanidine has been underutilized due t its low density crystal form which really cant be overcome easily. High bulk density techniques are used but are under performing. propyl nitroguanidine is another way to melt NQ but its not really feasible and I believe it loses some of the benefit of NQ. The performance of NQ at high density is reported to be 8344 m/s Vd, 29GPa pressure @ 1.759 g/cc according to Koch.

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[Edited on 27-6-2023 by Hey Buddy]


It's now been 9 hours since experimenting with the NQ plastique. It remelts after being rock hard like PVC. I would consider this material to be a reversible thermo-curing NQ plastic. A sample was left in water over night. At first, the sample cured solid like a marble. Overnight the sample broke apart and left presumably NQ at high density in the water. This may be a low-effort method of achieving high density NQ.


[Edited on 27-6-2023 by Hey Buddy]

AspNO3 continued

Hey Buddy - 27-6-2023 at 20:48

The AspNO3 cast into a 1" body began to leak out of the bottom today as temperatures got into 90 F in garage. In my mind, there was no reason therefore to attempt a detonation of that straight sample because anything that leaks at ambient temps isnt really a suitable material in stand alone casting. I attempted to fire the unknown qty NQ/AspNO3 mix. It did not detonate on a 1g NAP cap. Thats business as usual for nitroguanidine. It projected the material all over in small pieces.

I then attempted a PETN pbx and recorded numbers this time. 13.44 g AspNO3 were melted at 110 C on a glass dish. 13.46 g PETN were slowly added and carefully kneaded into melt. The entire mass appeared to melt in with the aspNO3. By the end of addition, consistency was like a dense dough. The material stuck to the watch glass and a ball of 23.95 g was recovered from the melt. This is a plastique 50:50 w/w AspNO3/PETN. The material is very much like C4 again, but you can feel it is less dense. Its pliability and rigidity attributes are quite similar to C4. It sets into hardening slower than the NQ mix. I rolled it into a ball as well as I could and calipered the diameter (31.92 mm) and came to the density of 1.406 g/cc which is somewhat low, presumably entrapped air and water. No degassing. C4 is at ~1.72 g/cc, for comparison. PETN should be 1.77 g/cc and the AspNO3 should be 1.60 g/cc. This PETN/AspNO3 should fire with less fuss than the NQ analogue.

Last image is high density NQ separated from water solution of the NQ plastic from earlier. This technique, melting NQ into a water soluble substrate, then dissolving substrate, may be handy for high NQ density. More testing needed, but looks promising.

Aside from hygroscopicity, the quality of these plastics is quite good. The PETN version seems less attracting to water, but the NQ version wasn't maxed out on w/w NQ, so it may actually work better. I made a sample of the NQ version and added a small amount of PETN as sensitizer to test as well.

If a low temp melting amino acid were found, without hygroscopicity, it could be very useful in a simple 2 part mix alone. Additives could improve these I'd imagine, but for two simple components, energetic melt carrier and filler, they are quite good. I'm familiar with government contract produced C4, and these two materials are pretty similar in handling. Which is interesting to me because they are so simple with no inerts, and were randomly learned of.

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[Edited on 28-6-2023 by Hey Buddy]

UPDATE:
These two comps have good handling properties for a few hours, but the hygroscopicity makes them practically unusable. The high density benefit effect for nitroguanidine is interesting and the prospect of a two part energetic PBX is interesting. A non-hygroscopic amino acid salt would be much more practical. Maybe even one that is lower performance but has the same material properties. I could not get either the 50% PETN nor the NQ/PETN to fire on a cap. Or if they did it was partial and so-low power it was uneventful. Unsure if this is an effect of water absorption or the effect of insensitivity of AspNO3. Will move on to proper attempt of glyClO4 now.

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[Edited on 28-6-2023 by Hey Buddy]

High Density Nitroguanidine

Hey Buddy - 29-6-2023 at 19:46

report for anyone interested:
I recovered NQ from one of the NQ/AspNO3 charges by simply soaking it overnight in water, then rinsing with water and drying on heat for 24 hours. I believe all of the AspNO3 is dissolved in water. NQ is left behind. The density measured was 1.4 g/cc - 1.5 g/cc on the sample recovered. There could be something unseen at play responsible for that reading, such as an unkown chemical reaction of the molecule, but assuming it is actually NQ, it's higher than industry standard high bulk density NQ, which is .97 g/cc in strict cases. In broad application, high bulk density NQ is considered >.81 g/cc. I give the range of 1.4 -1.5 g/cc to cover error. 1.4 g/cc is certainly attained by this material recovered out of AspNO3/NQ melt.

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[Edited on 30-6-2023 by Hey Buddy]

Update on amino acid research:
I have still managed to somehow avoid preparing HClO4 again, things have been busy and hot. Ive ordered some isoleucine, will probably also attempt citrulline and arginine. The Isoleucine is reported to make decent nitrate and perchlorate. Others are unkonwn. Goal is to find a <150 C mp, melt cast with solid state performance higher than TNT, nonhygroscopic. Glycine nitrate makes a reported low-power explosive with a 150 C mp, which is high. Since glycine is already at hands and glycine is common, I will knock out glycine next for hygroscopicity and mp check. Isoleucine, lysine, arginine will all be checked for NO3 and ClO4. Im waiting on a storage bottle for HClO4...





[Edited on 1-7-2023 by Hey Buddy]

Microtek - 30-6-2023 at 01:46

I can report that, from my own experiments, glycine perchlorate is quite hygroscopic. It does melt at a useable temp though. It would be very nice indeed if we could find a cheap, ionic compound that could function as a carrier for melt cast formulations. In general, I think performance should be tested on pressed powder charges rather than melt cast ones. Otherwise, it will be difficult to achieve full detonations of the highest velocity.

In my experience the number one obstacle is hygroscopicity. Practically all of the perchlorate salts of nitrogen containing bases I have tried have shown a high degree of it.

Hey Buddy - 30-6-2023 at 05:55

Quote: Originally posted by Microtek  
I can report that, from my own experiments, glycine perchlorate is quite hygroscopic.


I thought so too, but was hoping a direct HClO4 would be less. Dang. Truth hurts.

Quote: Originally posted by Microtek  

It does melt at a useable temp though. It would be very nice indeed if we could find a cheap, ionic compound that could function as a carrier for melt cast formulations.


IMO, more melt casts are crucial because a given explosive is always practically used in a carrier substrate or body of some sort. PBX, Cast, or det cord etc. Powder is really only used in early rockets or detonators. Shock tube and det cord use powder but it's an isolated application, the tubing itself lends its plasticity quality to the function of the powder. TNT has virtually no real alternative other than perhaps TNP if you discount its >100 C mp.

Quote: Originally posted by Microtek  

In general, I think performance should be tested on pressed powder charges rather than melt cast ones. Otherwise, it will be difficult to achieve full detonations of the highest velocity.


I agree with this, a melt cast only gets in the way comparing secondaries head to head. I have tried some melt casting of secondaries in the AspNO3, but really its because one shot is enough to spot check the melt cast alone. After that, if it does/does not fire, it becomes a question of: "how insensitive of a filler can this fire with?" / "How sensitive of a filler is needed to make it fire at all?" Those two questions were in my head when filling with NQ / PETN.
In the AspNO3 case, it's practically unusable, so it doesn't really matter. Doesn't fire well at all. The only good resolution out of it was learning of its plasticization ability, eliminating Aspartic acid from amino acid list, and the route to high density material. Not disappointing per se, but I wasn't writing home about it.

Quote: Originally posted by Microtek  

In my experience the number one obstacle is hygroscopicity. Practically all of the perchlorate salts of nitrogen containing bases I have tried have shown a high degree of it.


Agreed.-- Hygroscopicity is a show-stopper for secondaries. Water solubility is a much lesser detriment than hygroscopicity.
--What is it about a molecule or a complex, like for example, NAP. What makes it non-hygroscopic? Is it the metal? is it the guanidium group? Is guanidium perchlorate hygroscopic? The amino acids seem like they are flexible enough to easily modify with complexation, if necessary. That is a lot more time consuming in testing, so hopefully avoided. There are also several amino acids that contain guanidine groups, that might prospect better, if that aspect is favorable to a non-hygroscopic NO3/ClO4. Arginine comes to mind. Citrulline has carbonyl which seems more likely to be hygroscopic. I was disappointed by aspartic acid nitrate because I had hoped the nitrate would be less hygroscopic, but it was opposite.

underground - 30-6-2023 at 09:11

In my opinion a relatively cheap secondary with good performance is sentisized nitromethane. The main disadvantage obviously is that it is a liquid and it has to be prepared few minutes before.

[Edited on 30-6-2023 by underground]

MineMan - 30-6-2023 at 10:38

Quote: Originally posted by underground  
It reminds me the diaminourea nitrate. It was a PITA to crystalize out and it was very hydroscopic. You could try to add a solvent that it is not soluble in to force it to crystalize out.


Is that a solvable problem with the right equipment? I still can’t find an energetic as attractive?

Hey Buddy - 30-6-2023 at 17:31

It appears glycine nitrate is hygroscopic as well. I've been drying a sample for 24 hours on heat...

Glycine is so inexpensive its probably the most realistic for the cast purpose. Maybe a complex is the way to go...so many combinations. endless... I got the isoleucine but it has added sugars making it useless. I got lysine but they sent the HCl by mistake. Perhaps its a sign its time to take the ANQN/TNT pill and get off these fancy fly by night amino acids.

IMG_9773.jpg - 186kB

GlyNO3 melts technically at reported mp but is workable around 170-180 C. It dissolves NQ but its composite isn't very dense. I'm melting in NQ to these amino acids to inspect their melt character.



[Edited on 1-7-2023 by Hey Buddy]

It's now the next day, the NQ/GlyNO3 and straight GlyNO3 are definitely less hygroscopic than aspNO3 or NQ/NH4NO3 eutectic. Unfortunately, the mp of glyNO3 makes it only useful for high temp explosives and it's also low power. If there is great variation in hygroscopicity in amino acid nitrates, perhaps there is a low melt non hygroscopic amino acid ionic compound.

[Edited on 1-7-2023 by Hey Buddy]

MineMan - 1-7-2023 at 01:05

ANQN ans TNT. I don’t see the point. You’re taking a beyond military explosive and dumbing it down. Even if your 80 percent mix. You would have better performance using 10 percent water and 90 percent ANQN. Water fills the goods quite nice and represents almost near max densities. Even ETN 90 percent and 10 percent water will approach performance near cast. Better yet add 5 percent Al ans use the water as an oxidizer. This will cast into any container. It won’t harden by if it’s sealed who cares.

[Edited on 1-7-2023 by MineMan]

Hey Buddy - 1-7-2023 at 06:10

Quote: Originally posted by MineMan  
ANQN ans TNT. I don’t see the point. You’re taking a beyond military explosive and dumbing it down. Even if your 80 percent mix. You would have better performance using 10 percent water and 90 percent ANQN. Water fills the goods quite nice and represents almost near max densities. Even ETN 90 percent and 10 percent water will approach performance near cast. Better yet add 5 percent Al ans use the water as an oxidizer. This will cast into any container. It won’t harden by if it’s sealed who cares.

[Edited on 1-7-2023 by MineMan]


If the topic is military application, ie. Devices:
Explosives aren't used in powder form except in limited application. It isn't practical or ideal, realistically. If one is loading detonators, it isn't apparent how necessary a cast or pbx is. When the vessel becomes something other than small diameter cylinder, then the need of casts and pbx becomes obvious. When an explosive is moved or carried or subjected to higher temperatures, casts and pbxs become needed. Powder isn't suitable. Same goes for water or liquid explosives. Present state of art is casts/pbx. Water should be kept out of explosives in general unless it's for some purpose and going to be used without storage. Water in explosives is part of their natural decomposition as they experience in ambient environment in the ground.

MineMan - 1-7-2023 at 11:06

I suppose, but water does fill the voids and increase VOD.

As For PBX. Lots of new developments such as the chitosan nitrate I mentioned.

Hey Buddy - 1-7-2023 at 12:16

I'm not familiar with that but I'm always learning new stuff and like contrarian science, so I like the claim. I know you are aware of effects of water with explosives, I only meant as a generality in explosives. Obviously lots of exceptions like immediate emulsion blasting etc

Honestly, with how big of a pool the amino acids are, and after the pronounced dissolving effect of aspNO3, I'm thinking about the possibility of non hygroscopic ionic liquid as an energetic binder in pbx. For example, proline and leucine perchlorates are liquid at room temp and don't decompose until mid 200C. that's a 200 C range of heating that could absorb powdered energetics making a pbx. The aspartic acid plastics were really quite nice for the first hour or so.

[Edited on 1-7-2023 by Hey Buddy]

MineMan - 2-7-2023 at 00:40

Quote: Originally posted by Hey Buddy  
I'm not familiar with that but I'm always learning new stuff and like contrarian science, so I like the claim. I know you are aware of effects of water with explosives, I only meant as a generality in explosives. Obviously lots of exceptions like immediate emulsion blasting etc

Honestly, with how big of a pool the amino acids are, and after the pronounced dissolving effect of aspNO3, I'm thinking about the possibility of non hygroscopic ionic liquid as an energetic binder in pbx. For example, proline and leucine perchlorates are liquid at room temp and don't decompose until mid 200C. that's a 200 C range of heating that could absorb powdered energetics making a pbx. The aspartic acid plastics were really quite nice for the first hour or so.

[Edited on 1-7-2023 by Hey Buddy]


I am down. Sounds promising. I think ANQN is promising as the main filler as well. Or even better the melem N oxides. You seem to have knowledge of what is actually practical for industry and military. The advantages of an active ionic liquid are vast. Could also make a very good propellant being pumped into a simple liquid engine/nozzle.

MineMan - 2-7-2023 at 00:40

Quote: Originally posted by Hey Buddy  
I'm not familiar with that but I'm always learning new stuff and like contrarian science, so I like the claim. I know you are aware of effects of water with explosives, I only meant as a generality in explosives. Obviously lots of exceptions like immediate emulsion blasting etc

Honestly, with how big of a pool the amino acids are, and after the pronounced dissolving effect of aspNO3, I'm thinking about the possibility of non hygroscopic ionic liquid as an energetic binder in pbx. For example, proline and leucine perchlorates are liquid at room temp and don't decompose until mid 200C. that's a 200 C range of heating that could absorb powdered energetics making a pbx. The aspartic acid plastics were really quite nice for the first hour or so.

[Edited on 1-7-2023 by Hey Buddy]


I am down. Sounds promising. I think ANQN is promising as the main filler as well. Or even better the melem N oxides. You seem to have knowledge of what is actually practical for industry and military. The advantages of an active ionic liquid are vast. Could also make a very good propellant being pumped into a simple liquid engine/nozzle.

Hey Buddy - 2-7-2023 at 04:39

Does anyone know if it is possible for something like pentaerythritol to exchange nitros with perchlorates in its Ester? I mean, if hot melting a nitrate ester into a perchlorate carrier, can a perchlorate ester be a possible unintended reaction? I suppose perchlorate esters must be possible theoretically?

I was thinking ideally for an ionic liquid carrier pbx, erythritol tetranitrate would be ideal. Already common, and over oxygenated, lend some oxygen to a deficient ionic liquid and if it plasticizes, is non hygroscopic, you have a two part all-active pbx from cheap stuff. If it cures too hard, keep it soft with a small qty polyurea grease, which is still nitrogen heavy enough to participate in the detonation redox.

[Edited on 2-7-2023 by Hey Buddy]

underground - 2-7-2023 at 06:55

It is not possible

Hey Buddy - 2-7-2023 at 20:29

Glycine complexes with nickel and ammonium perchlorate resulting in cyan/blue hard crystal that has no melt shelf. appears to decompose at around 150 C. Judging from unreacted nickel carbonate, I would guess the complex is 1x Ni, 2x Gly, 2x NH4ClO4. I suspect the ammonia stays in the complex because it isn't smelled during reaction, or at least I couldn't smell it. Complex appears to contain some energy from combustion test but otherwise seems to not be overly sensitive.

Microtek - 3-7-2023 at 00:07

Molten ETN is not an ionic liquid (since it is not an ionic compound), but of course that is mostly semantics. ETN would be a great carrier if the melting point was a little higher and, most importantly, it was a lot less sensitive. You could look into the PTX formulations (Picatinny Ternary eXplosive). They are detailed in PATR2700 IIRC.

Hey Buddy - 3-7-2023 at 18:19

Quote: Originally posted by Microtek  
Molten ETN is not an ionic liquid (since it is not an ionic compound), but of course that is mostly semantics. ETN would be a great carrier if the melting point was a little higher and, most importantly, it was a lot less sensitive. You could look into the PTX formulations (Picatinny Ternary eXplosive). They are detailed in PATR2700 IIRC.


Sorry For confusion, I meant ETN in an ionic liquid carrier, as a filler. Not ETN melted as the carrier itself. I composed my thoughts into writing carelessly.

I hope anyone reading this in the future understands that ETN changes sensitivity in the melt phase. People do handle it in melt phase but molten ETN approaches fulminate primary explosives in sensitivity. Personally, I only melt ETN for specific purposes like cheap detonator fills. IMO it's not safe to handle in molten phase in large masses like a secondary.

To be more clear, there are several amino acid nitrates and perchlorates which are liquids at room temperature. For example, Proline is one they report, liquid in both anions. One of these room temp insensitive ionic liquids could act as the other amino acids do, absorbing large amounts of other energetic fillers, and plasticizing. Because the amino acid ionic explosives in question are liquid at room temp, there is a possibility they could plasticize ETN in its solid phase without any application of heat, or perhaps very little heat, under ETN mp, where its more insensitive. In theory, if possible, it should form an insensitive pbx because of the amino acid's insensitivity. The ETN itself lending oxygen to the ionic carrier as a possible benefit over something like penthrite. If the pbx became too stiff after settling, as is seen in other amino acid ionic pbx, it could be softened with a small amount of polyurea grease which has urea chains higher than 30% nitrogen content, thus capable of contributing energy to the overall redox. A pbx with entirely active components from the local fitness nutrition and hardware store. In theory...

There is definitely huge character variability to be found in the amino acids and their potential complexes as well. For instance, GlyNO3 is significantly less hygroscopic than the perchlorate. NiGlyClO4 is entirely non-hygroscopic and also does not melt, unlike glyClO4. So radically different characteristics can be introduced into these materials. Exactly what complex gives which qualities is a shot in the dark however.





[Edited on 4-7-2023 by Hey Buddy]

Microtek - 3-7-2023 at 22:59

Ah, ok. Good to know we are on the same page regarding molten ETN. I think the application of ionic liquids as solvents/carriers for more energetic fillers has a lot of potential. We still need to find some that aren't hygroscopic, but if the solvent action of the ionic liquid is high enough (so it can dissolve a lot of high quality secondary), it may not have to be very energetic itself. This must broaden the field, hopefully enough that a good material can be found that isn't hygroscopic.
IIRC, Roscoe posted about a mix of ETN and PETN that was pourable in the molten state and was surprisingly difficult to initiate. Maybe the mechanical sensitivity was also lower than the constituents, but AFAIK, it was never properly investigated.

MineMan - 5-7-2023 at 18:27

There are energetic UV cure resins

Hey Buddy - 9-7-2023 at 06:30

I tested some other amino acid nitrates. In general the nitrates are more soluble and have lower decomposition temperatures. Isoleucine nitrate is hygroscopic but slightly less than than AspNO3. Its crystal is "harder" than ASpNO3. Its melting point is around 100 C. It melts as a clear yellow tint liquid, very pourable. Proline nitrate is a liquid, it decomposes around 110 C which is lower than reported. It isn't really useable with such a low decomp. There are still several amino acid nitrates that are not reported that could show promise. The perchlorates I will do after I finish nitrates screening for hygroscopicity. Many of the perchlorates have a much wider temp range and are more suitable as candidates for melt casting due to much higher decomposition Temps. Proline is also a liquid as a perchlorate, so I will revisit that as a possible ionic liquid for pbx. It seems there may be chance of eliminating hygroscopicity via metal complexation. Of the metals, Cu Ni Mg seem to be most accessible, not sure if it would be worth it to screen Fe but I will probably try it in form of ferrous carbonate because obviously Fe is the most accessible metal. Usually Fe complexes are more sensitive and less stable than other metals but the amino acids are so stable, they may not present that same trend. Ca and K may also be worthwhile to screen in complexing because I believe tetrazole lover checked a calcium glycine compound that he found nonhygroscpic. If non hygroscopics can be found from calcium complexes, then they seem worth screening for due to easy access to Ca, along with K.

Of everything tested so far, glyClO4 via perchlorate salt is the best melt cast candidate. It's Hygroscopicity is medium, its complex with nickel is entirely non hygroscopic but that complex loses ability to melt which defeats its purpose as melt cast carrier. aspartic acid was unusable as nitrate due to high hygroscopicity but a nitrate metal complex may make it more suitable.

underground - 9-7-2023 at 08:25

Iron could be very useful as a metal complex cause it can take 3 anions like trinitrate or triperchlorate meaning you can add more oxygen for better OB

dettoo456 - 10-7-2023 at 11:01

Iron complexes are usually pretty hygroscopic and generally have underwhelming properties as compared to accessible metals like Cu and Ni or even Mn and Zn. You might also run into issues of reducing and oxidizing between Fe ii and iii under heating, chem conditions, etc.

@Hey Buddy If hygroscopicity and sensitivity aren’t a concern, why even mess with the more expensive amino acid esters and look through MeNH3+, Me2NH2+, and Me3NH+ nitrate and perchlorate salts. TOVEX has been used for decades as a cheap and reliable agent, and if you just use its prime content (MeAN) as a relatively pure compound, it’ll outperform even TNT and PA with no contest. It is hygroscopic (but I’m sure it’s much less than Gly salts) and nitrate salts would be more chemically stable than those of b-amino acids. Both MeAP and MeAN are cheap, safe, and easy to produce as well. The only drawback is that they’d need to be used in a container since they form eutectic-like mixes with water.

Hey Buddy - 10-7-2023 at 14:34

Quote: Originally posted by dettoo456  

@Hey Buddy If hygroscopicity and sensitivity aren’t a concern, why even mess with the more expensive amino acid esters and look through MeNH3+, Me2NH2+, and Me3NH+ nitrate and perchlorate salts. TOVEX has been used for decades as a cheap and reliable agent, and if you just use its prime content (MeAN) as a relatively pure compound, it’ll outperform even TNT and PA with no contest. It is hygroscopic (but I’m sure it’s much less than Gly salts) and nitrate salts would be more chemically stable than those of b-amino acids. Both MeAP and MeAN are cheap, safe, and easy to produce as well. The only drawback is that they’d need to be used in a container since they form eutectic-like mixes with water.


That had never crossed my mind but it seems like something worth trying. IMO the hygroscopicity is a problem in this application (casting or plasticizing) . The glyClO4/NO3 is hygroscopic, yes, but their complexes are not. So far, none of them melt, which defeats the purpose. The KGlyClO4 is also not melting... Overall, they arent looking like they are going to deliver anything spectacular, but Im committed to look a little deeper into common amino acids. Dont want to overlook something from attrition when there is a near-potential there.