Glycine Perchlorate

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]

Attachment: insens_bio_energetics.pdf (3.4MB)
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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]

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]

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]

Quote: Originally posted by Hey Buddy

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.

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).

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 )... isn't it fabulous how chemistry is logical 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 .
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.

Quote: Originally posted by PHILOU Zrealone

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

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.

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.

--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]






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

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]

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]

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]

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?

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... 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]

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.

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.





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

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

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.



[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]

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

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]

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).

Consolidated update

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?

Amino acid anecdote

Amino acid anecdote

Quote: Originally posted by Microtek

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

Aspartic Acid Nitrate 151.11 g/mol

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.






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

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

Quote: Originally posted by underground

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

Quote: Originally posted by underground

You could try to add a solvent that it is not soluble in to force it to crystalize out.

Quote: Originally posted by Microtek

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

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.



[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

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.



[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.





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

High Density Nitroguanidine

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.


[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]

Quote: Originally posted by Microtek

I can report that, from my own experiments, glycine perchlorate is quite hygroscopic.

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.

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.

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.

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.

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.



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]

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]

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]

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]

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.

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.