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Hey Buddy
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Quote: Originally posted by pdb  |
Does anyone know how to properly prepare NiCO3 from Ni nitrate? Otherwise, I just need to double the amount of my suspect nickel carbonate in the
synthesis.
[Edited on 20-11-24 by pdb] |
I know a guy who prepares it through NiCl2 metathesis which worked well, and changes color between the two Ni salts for visual confirmation.
Just for reference, NiCO3 is available widely as a glaze component from any ceramic supply shop across the world. In the US, it is around $18-25/lb.
[Edited on 20-11-2024 by Hey Buddy]
[Edited on 20-11-2024 by Hey Buddy]
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Axt
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I you are desperate enough, you could extract the nickel hydroxide from dead NiMh batteries.
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pdb
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This time, I followed example 2.3 from the patent and Microtek's advice:
Synthesis of Hexaammine Nickel(II) Perchlorate Ni(NH3)6(ClO4)2
Ni(NO3)2·6H2O + 6 NH3 (aq) → Ni(NH3)6(NO3)2 + 6 H2O
Ni(NH3)6(NO3)2 + 2 HClO4 → Ni(NH3)6(ClO4)2 + 2 HNO3
- 2 g of Ni(NO3)2·6H2O in 5 ml of H2O
- add 1.86 g of NH3 (aq)
- add 1.57 g of 70% HClO4
Instead of attempting to isolate Ni(NH3)6(ClO4)2, the synthesis continues according to the patent:
- add 55 ml of H2O
- add 4.08 g of 70% HClO4
- add 3.81 g of aminoguanidine hydrogen carbonate
- after effervescence, fast heating until boiling, kept for 5 mn: the solution turns gray.
- ultrasonicating 4x5 mn: no precipitation occurs until the temperature drops to around 30°C.
The filtrate continues to deposit some NAP over the following hours.
However, the yield is only 32%, far from the 89% claimed in the patent
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Laboratory of Liptakov
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water solution: Ni(NO3)2 - anhydride 10g + NaHCO3 9,2g = 6,5g NiCO3 (insoluble) + 9,3g NaNO3 (hi soluble) + 2,4g CO2 + 0,1 H2O
water solution: NiCl2 (anhydride brown) 10g + 13g NaHCO3 = 14g Ni(HCO3)2 (insoluble in water) + NaCl
water solution: NiSO4 (anhydride) 10g + 10.9 NaHCO3 = 7.7g NiCO3 (insoluble) + Na2SO4 9.2g + CO2 2.8g + H2O 1.1g
Procedure from Ni(NO3)2: 2g Ni(NO3)2 hexahydrate insert as crystalls into glass + 2g NaHCO3 as dry powder added. Add 40g dH2O and temperaure
increase on 80 C on waterbath. Partially open cap was used. After 60 min. at 80 C is solution decantated, added 100g normal water, washing and
decantated or separated on Buchner device. After drying you have fine and pure powder of NiCO3...
 
[Edited on 22-11-2024 by Laboratory of Liptakov]
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Etanol
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| Quote: Originally posted by pdb |
Instead of attempting to isolate Ni(NH3)6(ClO4)2, the synthesis continues according to the patent:
- add 55 ml of H2O
- add 4.08 g of 70% HClO4
- add 3.81 g of aminoguanidine hydrogen carbonate
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Bad idea. Ni(AGu)2(ClO4)2 and Ni(AGu)2(NO3)2 mix formed.
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Microtek
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Yes, the advantage of isolating the Ni(NH3)6(ClO4)2 is the absence of any ions that might interfere with the reaction, ensuring that whatever you get
really must be NAP. Also, I would suggest heating the AQ*HClO4 solution close to boiling before adding the Ni(NH3)6(ClO4)2.
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pdb
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| Quote: Originally posted by Laboratory of Liptakov |
Procedure from Ni(NO3)2: 2g Ni(NO3)2 hexahydrate insert as crystalls into glass + 2g NaHCO3 as dry powder added. Add 40g dH2O and temperaure
increase on 80 C on waterbath. Partially open cap was used. After 60 min. at 80 C is solution decantated, added 100g normal water, washing and
decantated or separated on Buchner device. After drying you have fine and pure powder of NiCO3 |
Thank you LL. There is a typo I guess... you mean 4 g (or more precisely 3.46 g) of Ni(NO3)2.6H2O
Heating the solution like this allows the decomposition of NiCO3 hydrates or hydroxides?
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Laboratory of Liptakov
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In short, such proportions that the baking soda is in excess over the reacting nickel nitrate. For example, by 10% by weight. Because baking soda is
much cheaper than nitrate, which needs to be used as much as possible in the production of NiCO3.
Decompositions on hydrates and hydroxides was not examinated at heating....
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pdb
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| Quote: Originally posted by Axt |
Solution 1
Displacing AG bicarbonate with hydrochloride
2CH7N4.HCO3 + 2HCl --> 2CH7N4.Cl + 2H2O + 2CO2
Freebasing aminoguanidine
2CH7N4.Cl + 2NaOH --> 2CH6N4 + 2NaCl + 2H2O
Solution 2
Dissolution of nickel perchlorate
NiO + 2HClO4 --> Ni(ClO4)2 + H2O
Combine 1 & 2
Complexing aminoguanidine to nickel perchlorate
Ni(ClO4)2 + 2CH6N4 --> Ni(CH6N4)2(ClO4)2
Replace the HCl with HClO4 if the chloride complex has too low of a solubility. I feel like nickel oxide is more readily available than the carbonate
or nickel metal itself. |
I attempted this protocol with strictly stoichiometric proportions. Solution 1 was brought to a boil under magnetic stirring. Upon adding solution 2,
the solution turned gray-brown immediatly, and a greenish deposit appeared—CH7N4.Cl or what? After 5 minutes of boiling, the beaker was placed in an
ultrasonic bath, which produced nothing until the temperature dropped to around 30°C. At that point, a brick-red precipitate appeared along with red
needles on the surface.
In all my experiments with uNAP, I noticed that ultrasonication was ineffective as long as the solution temperature had not dropped to around 30°C.
Can everyone confirm this?
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Hey Buddy
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| Quote: Originally posted by pdb | | Quote: Originally posted by Axt |
Solution 1
Displacing AG bicarbonate with hydrochloride
2CH7N4.HCO3 + 2HCl --> 2CH7N4.Cl + 2H2O + 2CO2
Freebasing aminoguanidine
2CH7N4.Cl + 2NaOH --> 2CH6N4 + 2NaCl + 2H2O
Solution 2
Dissolution of nickel perchlorate
NiO + 2HClO4 --> Ni(ClO4)2 + H2O
Combine 1 & 2
Complexing aminoguanidine to nickel perchlorate
Ni(ClO4)2 + 2CH6N4 --> Ni(CH6N4)2(ClO4)2
Replace the HCl with HClO4 if the chloride complex has too low of a solubility. I feel like nickel oxide is more readily available than the carbonate
or nickel metal itself. |
I attempted this protocol with strictly stoichiometric proportions. Solution 1 was brought to a boil under magnetic stirring. Upon adding solution 2,
the solution turned gray-brown immediatly, and a greenish deposit appeared—CH7N4.Cl or what? After 5 minutes of boiling, the beaker was placed in an
ultrasonic bath, which produced nothing until the temperature dropped to around 30°C. At that point, a brick-red precipitate appeared along with red
needles on the surface.
In all my experiments with uNAP, I noticed that ultrasonication was ineffective as long as the solution temperature had not dropped to around 30°C.
Can everyone confirm this?
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Yes, it is supposed to be 20 C. It also is disrupted if the temp is really low, like when an ice bath is used. The target temp is 20 C and there
shouldnt be any needle crystals. The appearance of needle crystals probably means the transmission of sonication is not effective. Needle crystals
should be unable to form.
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Axt
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I would think the initial "green/brown" would be something more akin to a basic nickel perchlorate precipitating (not knowing anything of the
properties of Ni(OH)ClO4). Did it redissolve?
How did you make the Nickel perchlorate solution? using NiO + HClO4? I've never done this, but it will go through a basic nickel perchlorate
intermediate if it works.
Are the successful ultrasonicated precipitates using the bare solution or immersing a beaker in the ultrasonic bath? That may be your issue.
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pjig
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Is this axt that helped developing water gels?
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Axt
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Offtopic Watergel http://www.sciencemadness.org/talk/viewthread.php?tid=3214
| Quote: Originally posted by pdb | | Quote: Originally posted by Axt |
Solution 1
Displacing AG bicarbonate with hydrochloride
2CH7N4.HCO3 + 2HCl --> 2CH7N4.Cl + 2H2O + 2CO2
Freebasing aminoguanidine
2CH7N4.Cl + 2NaOH --> 2CH6N4 + 2NaCl + 2H2O
Solution 2
Dissolution of nickel perchlorate
NiO + 2HClO4 --> Ni(ClO4)2 + H2O
Combine 1 & 2
Complexing aminoguanidine to nickel perchlorate
Ni(ClO4)2 + 2CH6N4 --> Ni(CH6N4)2(ClO4)2
Replace the HCl with HClO4 if the chloride complex has too low of a solubility. I feel like nickel oxide is more readily available than the carbonate
or nickel metal itself. |
I attempted this protocol with strictly stoichiometric proportions. Solution 1 was brought to a boil under magnetic stirring. Upon adding solution 2,
the solution turned gray-brown immediatly, and a greenish deposit appeared—CH7N4.Cl or what? After 5 minutes of boiling, the beaker was placed in an
ultrasonic bath, which produced nothing until the temperature dropped to around 30°C. At that point, a brick-red precipitate appeared along with red
needles on the surface.
In all my experiments with uNAP, I noticed that ultrasonication was ineffective as long as the solution temperature had not dropped to around 30°C.
Can everyone confirm this?
|
Ok, curiosity got the better of me this is what works and what doesn't.
The method as posted works, but the problem is you cannot use the stoichiometric quantity to dissolve the NiO, it's just too hard to get in solution
even when run hot and concentrated. I was left with a lot of NiO unreacted. Taking the prep to the end, pouring in the NaOH resulted in an immediate
dump of the brick red precipitate but heavily contaminated with oxide.
Here's the better way,
Use the total acids needed to dissolve the NiO, this provides the excess needed to get the NiO into solution.
1.5g (0.02mol) nickel oxide and 11.5g (0.08mol) 70% perchloric acid in 20ml water.
Heat with stirring on 150 degree hotplate (solution temp 75 rising to 90) until a slurry with no black oxide left. Dilute and redissolve with 50ml
water for a clear emerald green.
Add 5.44g (0.04mol) aminoguanidine bicarbonate in 50ml, this will neutralise with the excess acid, you've now a dirty green solution of Ni(ClO4)2 and
2CH6N4.HClO4 in 100ml water.
A slight excess 3.74g (0.05mol) 25% ammonia is added, it turns dark purplish blue.
If left stand Ni(CH6N4)2(ClO4)2 precipitates out as brick coloured needles. This takes maybe 10 minutes. Use NaOH instead and its instant and less
controllable. Mixing was all done at room temp.
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pdb
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This time, the precipitation of uNAP took only 5-6 minutes with ultrasound. After filtration, I observed something I’ve noticed before: if the
washing with water is prolonged too much, the precipitate develops a gray film within a few minutes. I suppose this is the decomposition by water
mentioned by others? I don't have any IPA on hand; I need to get some.
[Edited on 28-11-24 by pdb]
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Hey Buddy
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| Quote: Originally posted by pdb | This time, the precipitation of uNAP took only 5-6 minutes with ultrasound. After filtration, I observed something I’ve noticed before: if the
washing with water is prolonged too much, the precipitate develops a gray film within a few minutes. I suppose this is the decomposition by water
mentioned by others? I don't have any IPA on hand; I need to get some.
[Edited on 28-11-24 by pdb] |
Yes
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pdb
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Comparison of uNAP with other primary explosives
First of all, I must say that so far I have not been able to observe DDT with samples of a few milligrams (< 5 mg): all I get is a "noisy
deflagration," with no mechanical effect on the aluminum foil. DDT requires slight confinement or a dose of around ten milligrams.
Next, I conducted my usual comparison test with two other primaries: a rubber tube 5-6 mm in length is glued to the surface of a 1 mm thick aluminum
sheet, then filled with 40 mg of primary compacted by hand. A small pellet of NC is used to seal the tube and transmit the flame.
The last three pictures show the result: on the left, AgN3; in the middle, uNAP; on the right, nitrobenzenediazonium perchlorate. It seems fair to say
that the first two produced similar results, which means a new, perhaps different, test will be needed to distinguish between them. And as usual,
nitrobenzenediazonium perchlorate takes the crown.
Based on this test (which would need to be repeated for confirmation), uNAP could be an interesting alternative to AgN3 because it has similar power
but reportedly lower sensitivity according to comments in this thread (I have not personally tested its sensitivity). However, AgN3 has the advantage
of high bulk density.
  
 
  
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Laboratory of Liptakov
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I see a lot of work done in the field of primary perchlorates. Of course, a weak aluminum foil is a meaningless test. Because, for example, an
activated mixture of Pb(NO3)2 + Pb(H2PO2)2 (1:1) can tear the foil to pieces with just one small grain of 1 mg or less. But the initiation effect of
this mixture in a detonator does not work even at 100 mg.
For this reason, your test on a 1 mm aluminum sheet + 40 mg of primary substance is important. The results look relevant. If your
nitrobenzenediazonium perchlorate (NBDP?) had an easier preparation (and availability of precursors) than uNAP, it would be a miracle in the field of
primary perchlorates.....Hats off once again for the work done.......
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pdb
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In fact, its preparation (diazotization using NaNO2) is easier than that of NAP; the real difference lies in the difficulty of obtaining or
synthesizing the precursors HClO4 and 3-nitroaniline. By the way, when I first mentioned it in 2003 on RS, I named it DPNA after its french name
(diazoperchlorate de méta-nitroaniline). At least it's a bit easier to pronounce than NBDP ;-)
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Hey Buddy
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| Quote: Originally posted by pdb | First of all, I must say that so far I have not been able to observe DDT with samples of a few milligrams (< 5 mg): all I get is a "noisy
deflagration," with no mechanical effect on the aluminum foil. DDT requires slight confinement or a dose of around ten milligrams.
Next, I conducted my usual comparison test with two other primaries: a rubber tube 5-6 mm in length is glued to the surface of a 1 mm thick aluminum
sheet, then filled with 40 mg of primary compacted by hand. A small pellet of NC is used to seal the tube and transmit the flame.
The last three pictures show the result: on the left, AgN3; in the middle, uNAP; on the right, nitrobenzenediazonium perchlorate. It seems fair to say
that the first two produced similar results, which means a new, perhaps different, test will be needed to distinguish between them. And as usual,
nitrobenzenediazonium perchlorate takes the crown.
Based on this test (which would need to be repeated for confirmation), uNAP could be an interesting alternative to AgN3 because it has similar power
but reportedly lower sensitivity according to comments in this thread (I have not personally tested its sensitivity). However, AgN3 has the advantage
of high bulk density.
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I haven't experienced any of the problems or difficulties you have experienced in prep or use of NAP. I don't know what the differences are due to.
There must be some difference. I have been making the material regularly for more than a year. I participate in a group, it is popular there. I know
maybe 5 or so people that use NAP variants in that group. They don't have any differences in their product. There is no instance of deflagration in my
experience. I think there is something different in your product that is drastically changing results. There shouldn't be any deflagration at all. It
detonates aggressively on the slightest touch above 270 C. It repeatedly transfers detonation in only a few hundred micrograms. I produce small 1 g
batches regularly. They are always the same.
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Axt
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I'm guessing pdb is referring to a loud POP as "loud deflagration"? as that's what I get if it's directly ignited. There is very few things more
vehemic than the diazonium perchlorates to direct ignition.
Lab is correct though, there is no test that I know of that predicts initiating efficiency short of hitting it with the spit of a fuse in a detonator.
Cyanuric triazide shown is a potent initiator but the feeblest when just ignited (although generally it melts a bit before ignition causing detontion,
not in this case), and I trust the reports about NAP.
Here's a couple vids, the sound on the digital cam is muffled it's much louder in person but you can tell the difference between a fffp a pop and a
snap, these were all 5mg. The diazonium salts were recorded 20 years ago on an old analogue tape recorder it had much better sound.
[Edited on 7-12-2024 by Axt]
Attachment: CTA DPPE NAP compress.mp4 (6.4MB)
This file has been downloaded 88 times
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Axt
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Diazonium salts as comparison.
Attachment: diazonium-salts_704x576.mp4 (3.6MB)
This file has been downloaded 42 times
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Hey Buddy
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| Quote: Originally posted by Axt | I'm guessing pdb is referring to a loud POP as "loud deflagration"? as that's what I get if it's directly ignited. There is very few things more
vehemic than the diazonium perchlorates to direct ignition.
Lab is correct though, there is no test that I know of that predicts initiating efficiency short of hitting it with the spit of a fuse in a detonator.
Cyanuric triazide shown is a potent initiator but the feeblest when just ignited (although generally it melts a bit before ignition causing detontion,
not in this case), and I trust the reports about NAP.
Here's a couple vids, the sound on the digital cam is muffled it's much louder in person but you can tell the difference between a fffp a pop and a
snap, these were all 5mg. The diazonium salts were recorded 20 years ago on an old analogue tape recorder it had much better sound.
[Edited on 7-12-2024 by Axt] |
I've tried to explain the crystal size makes a large difference in performance of NAP. Using standard crystal NAP will always give a lower
performance, it isnt the ideal morphology. This is the purpose of the use of the ultrasonicator. It precipitates nano crystals. They have entirely
different performance and sensitivity than standard NAP. They are practically different materials.
Attachment: NAP vs uNAP.mp4 (7.3MB)
This file has been downloaded 44 times
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pdb
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@Hey Buddy: the initial difficulties came from the fact that NiCO3 is not common in my country, whereas NiO is readily available. So, I ordered oxide,
and while waiting for delivery, I conducted tests using impure NiCO3 because the synthesis from Ni(NO3)2 and NaHCO3 apparently produces a mixture with
hydroxide and basic carbonate. I also wanted to use NH4OH, as others in this thread have done, instead of HClO4.
From now on, I use the cold method with NiO, HClO4, and NaOH to neutralize the acid and induce precipitation under ultrasound. The yield is around
55%.
The product obtained, which seems to have the characteristics of the uNAP described by other members (first pic -length of pic is about1.5 mm), does
not exhibit DDT for quantities of at least up to 5 mg. This is demonstrated in the attached video.
10 mg are weighed on aluminum foil (with a 5 g tare for better balance precision). Then, the material is divided into 3 charges by hand and eye
estimation: each pile should weigh between 2.5 and 3.5 mg. They are then ignited one by one. The photo shows that after unfolding, the aluminum foil
is not pierced anywhere.
The last sequence in the video shows the same test with a DPNA charge, estimated to be between 0.5 and 1 mg.
I don’t see an explanation for the absence of DDT. In your video, do you get the same effect with direct flame contact?
   
Attachment: 3 x uNAP + 1 x DPNA.mp4 (5.7MB)
This file has been downloaded 40 times
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Hey Buddy
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| Quote: Originally posted by pdb |
I don’t see an explanation for the absence of DDT. In your video, do you get the same effect with direct flame contact?
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It is common for primary explosives to not detonate from open top heat. I think bottom heating is a higher resolution examination of a material in
minimum mass DDT capability. Closer to as it would be when confined in a device during actual use. There are tetrazoles that wont detonate on open top
heat. Bottom heating reveals the minimum mass necessary to cause a detonation transition. Some materials are incapable of detonating by bottom heat in
low mass, and so it is a useful comparison. The Al foil is useful as a witness medium because it is resilient to perforation unless a detonation takes
place at such small mass.
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pdb
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OK, so the explanation lies in the testing method. Although the bottom heating test is widely used on this forum, in my opinion, it is biased for
evaluating DDT. Heating samples of different energetic materials to their explosion temperatures will result in detonation much more often than if
they were exposed to a flame.
I’m not saying this test should be abandoned, but there should at least be a distinction between h(eat)DDT and f(lame)DDT. In this case, uNAP
exhibits hDDT but not fDDT, unlike some other primaries. However, these differences no longer matter when the charge is confined, as in a detonator.
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