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dettoo456
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I don’t know if it’s been mentioned already, but here’s an interesting paper from LMU: 4 AgNTZ molecules are able to complex to NH3 (one of the
Ag’s itself actually does) to produce a comparably safer primary. I know some here have tried to recrystallize AgNTZ from aq NH3, they might
inadvertently form this in the process.
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dettoo456
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I’m not able to edit the previous post for some reason, so here’s the link to the article:
https://onlinelibrary.wiley.com/doi/epdf/10.1002/prep.12013
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Etanol
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Quote: Originally posted by Etanol  |
Co(ClO4)2+NH4ClO4+NH3(excess)+H2O2=>[Co(NH3)6](ClO4)3 red solution
[Co(NH3)6](ClO4)3+3 (4-ATrz)=(boiling?)=>[Co(4-ATRz)3](ClO4)3
The subs is a dark-red resin or red-brown grains that easily melt into red resin. When cooling, the resin turns into a red vitreous mass. The
substance is poorly soluble in cold water and insoluble in isopropyl alcohol.
It is difficult to ignite. Unconfined, it melts first, then burns with flashes and burns out. The melting temperature is lower than the decomposition
temperature.
Unconfined, being heated on a metal foil, it melts, then burns with a flash.
Approximately 20-30 mg, confined into aluminum foil, strong detonate when heated.
In my opinion, this is powerful, but unsuitable subs. |
I apologize. My failure was caused by the fact that I could not correctly oxidize cobalt(II) in cobalt(III), because I used a false manual without a
catalyst. The properties of the substance will be double-checked.
The cobalt(III) complexes are very very stable really. If you received it, then it is almost impossible to destroy it either with boiling or acid.
However, it is important to prepare them correctly and clean in front of the next stages.
[Edited on 2-5-2025 by Etanol]
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Axt
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I neutralised formic acid with a slight excess of hydrazine then heated the hydrazine formate to 180-190C for 5hrs in an oil bath. After cooling the
solid was recrystalised from ethanol/ether gave what I'm assuming to be 4-aminotriazole as a white crystalline precipitate, the melting point of about
80C seems correct.
I mixed the stoichiometric quantities of basic copper carbonate, perchloric acid and 4-aminotriazole to give {[Cu(C2H4N4)3](ClO4)2}n. A light blue
precipitate forms immediately, it was stirred for an hour and filtered.
CuCO₃·Cu(OH)₂ 0.553 g
70% HClO₄ 1.435 g
4-Aminotriazole 1.262 g
Now actually reading the literature (main discussion on pg. 28) they use a considerable excess of copper perchlorate to give the tris-ligand instead
of the tetrakis-ligand. I presumably have Cu(C2H4N4)4(ClO4)2. It flares off like blackpowder on ignition but only as a powder, if the caked lumps are
ignited it flashes in a blue jet of flame, scoots away and deflagration does not propagate.
Does anyone have experience with Cu(C2H4N4)3(ClO4)2 or Cu(C2H4N4)4(ClO4)2? What are their "vehemic" properties?
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Etanol
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| Quote: Originally posted by Axt |
Does anyone have experience with Cu(C2H4N4)3(ClO4)2 or Cu(C2H4N4)4(ClO4)2? What are their "vehemic" properties? |
I prepared Cu(C2H4N4)2(ClO4)2, Cu(C2H4N4)3(ClO4)2 and Cu(C2H4N4)4(ClO4)2 but I have not used it in detonators so far.
If you use an excess of copper perchlorate, you will get a hygroscopic Cu(C2H4N4)2(ClO4)2*nH2O.
Apparently, to prepare Cu(C2H4N4)3(ClO4)2, it is important not only to mix reagents 1:3, but to get a hot saturated solution without solid sediment.
It is not necessary to stirring it for an hour. Only then can you cool it in a mixture of the ice and water to 0C. At the same time, the entire subs
is crystallized. The substance is very poorly soluble in ice water.
Try to enclose 20-30mg in aluminum foil and heat. It will be very loud.
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Axt
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I see.
So, there is two reported procedures, one used stoichiometric quantities (3:1) https://www.sciencemadness.org/whisper/files.php?pid=698661&... . The other used an excess of copper perchlorate (1:1) https://www.sciencemadness.org/whisper/files.php?pid=698664&... . I notice these are the same authors and the 3:1 is the later published.
I guess I was after a correlation between the deflagratory properties I gave with others experience. I'm not sure if "unconfined blackpowder" is where
this stuff maxes out when ignited in the open.
I'll probably try the 1:1 and see if its properties change. I made a bit more 4-aminotriazole, isopropanol is the better recrystallisation solvent.
For 0.3mol formic acid used you'll need about 18g boiling isopropanol to dissolve then cool to 5C and vacuum filter (it's a solid mush).
[Edited on 20-5-2025 by Axt]
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Axt
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Ok, I tried it again.
CuCO₃·Cu(OH)₂ 2.63 g
70% HClO₄ 6.82 g
4-Aminotriazole 5.00 g
This is a 1:2.5 ratio, which wasn't really done on purpose rather I just overestimated how much 4-aminotriazole I had. The basic copper carbonate and
perchloric acid were mixed in 100mL of water and brought up to 90C. The 4-aminotriazole was dissolved into 50mL water and poured in in one go turning
the solution darker blue. The hotplate and stirrer were turned off and it was allowed to slowly return to room temperature. I was aiming for large
crystals here, but it still dropped out quite fine, in quite a desirable free flowing crystalline needle powder.
It may just be the morphology, but this batch was significantly more vehemic than the prior. It thumps off in half-pinch sized quantities reminiscent
of NHN. I can see how this would act as an initiatory primary.
[Edited on 20-5-2025 by Axt]
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Axt
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The filtrate dropped out slightly more which I filtered and dried, hand pressed in copper det and fired on a thin steel channel. It was about 400mg,
no base charge just the Cu(C2H4N4)3(ClO4)2. The matchhead didn't even reach the charge there was an air gap.
This isn't meant to prove much, but I'm confident it is a detonation. 400mg of PETN will do more to that channel but not dramatically more, and its
pure detonation not having to DDT.
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Axt
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Attaching the hypochlorite oxidation of 4-aminotriazole to 4,4′-azo-1,2,4-triazole. The complexes of zinc perchlorate and copper nitrate given
probably have no practical interest being hydrates but other experimentation may be interesting, being that 4,4′-azobis(1,2,4-triazole) is itself an
explosive.
The other which may be more convenient is with sodium dichloroisocyanurate.
Qi, C., Li, S.-H., Li, Y.-C., Wang, Y., Chen, X.-K., & Pang, S.-P. (2011). A novel stable high-nitrogen energetic material:
4,4′-azobis(1,2,4-triazole). Journal of Materials Chemistry, 21(9), 3221. doi:10.1039/c0jm02970j gives explosive props of
4,4′-azo-1,2,4-triazole. (file size too large to attach)
Density = 1.62 g/cm3
VOD = 7520 m/s
Det. pres. = 23.5 GPa
Impact sens. = 14J (about half sensitivity of RDX)
Friction sens. = Slightly more sensitive than RDX
Low static sensitivity.
I have no iodate salts but this is interesting, from the supporting info of J. Phys. Chem. C 2024, 128, 5, 2240–2246.
1.1 Preparation of [M(atrz)(IO3)2]n (M =Mn, Fe, Co, Ni, Cu, and Zn)The preparation of [M(atrz)(IO3)2]n (M = Mn, Fe, Co, Ni, Cu, and Zn)
are similar. M(NO3)2 (M = Mn, Fe, Co, Ni, Cu, and Zn), atrz and KIO3 were dissolved by adding appropriate amount of water
according to the molar ratio of 1:1:2, and heated to 80 °C for stirring reaction for 6h. After cooling to room temperature, they
were filtered and dried to obtain [M(atrz)(IO3)2]n (M =Mn, Fe, Co, Ni, Cu, and Zn) powder sample, yield of 62-84%
[Edited on 21-5-2025 by Axt]
Attachment: 4-aminotriazole oxidation to azo.pdf (639kB)
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Axt
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Just a bit more info. These are recent so it's again a copy and paste from the supporting info.
The iodate complexes seem rather insensitive, probably not primaries. If I was to do this I'd try swapping iodate with bromate.
The impact and friction sensitivities of three EMOFs dried samples were determined by BAM standards. The IS and FS for [Co(atrz)(IO3)2]n is 18 J and
120 N, for [Zn(atrz)(IO3)2]n is 11 J and 80 N, for [Cu(atrz)(IO3)2]n is 18 J and 60 N, respectively.
J. Phys. Chem. C 2024, 128, 5, 2240–2246
A different prep. using sodium dichloroisocyanurate, the hypochlorite still seems the easiest.
Synthesis of 4,4'-azo-1,2,4-triazole (ATRZ): Sodium dichloroisocyanurate (20.12 g, 96 mmol) was dissolved in 200 mL of deionized water at room
temperature with stirring until complete dissolution. Subsequently, 10 mL of acetic acid was added, and the mixture was vigorously stirred at room
temperature for 4 hours, maintaining the reaction temperature below 10 °C
using an ice bath. Separately, 4-amino-1,2,4-triazole (10.1 g, 120 mmol) was dissolved in 10 mL of water and added to the reaction mixture. Stirring
was continued for an additional 5 hours to ensure completion of the reaction. The reaction mixture was then filtered, and the solid obtained was
dissolved in 300 mL of deionized water by boiling. After cooling for 3 hours, the solution was filtered again to isolate needle-shaped crystals of
ATRZ. Yield: 5.12 g, 52%.
And the azide complex, interestingly has the same structure as the iodates ie. one ATRZ ligand per two counterions. Looks to be a primary although I'm
not super interested in more inorganic azides.
Leveraging its distinctive structural attributes of encapsulated confinement, CA-ATRZ is substantially improved in terms of safety compared to CA,
while maintaining its superior detonation performance.
Synthesis of [Cu(ATRZ)3(NO3)2]n: ATRZ (15 mmol, 2.5 g) was added to 200 mL of boiling deionized water and added into a 200 mL boiling aqueous
solution of Cu(NO3)2·3H2O (4.5 mmol, 1.1 g). The resulting mixture was stirred for 1 hour, followed by filtration. Blue single crystals were obtained
through slow evaporation filtrate over several days. Yield: 2.1 g, 70 %.
Synthesis of [Cu(ATRZ)(N3)2]n: Add [Cu(ATRZ)3(NO3)2]n (2 g, 3 mmol) to 120 mL of aqueous sodium azide solution (0.5 mol L-1). After 3 days, brown
crystals suitable for X-ray diffraction are obtained, which are then filtered, washed, and dried to obtain final product. Yield: 0.79 g, 85 %. Td
(onset) 209 °C. IR (KBr) ν = 3090(w), 2044(s), 1493(m), 1382(w), 1341(w), 1313(w), 1220(w), 1180(m), 1044(m), 880(m), 700(m), 616(s), 555(m) cm-1.
Anal. calcd for C4H4CuN14 (311.72 g mol-1): C 15.41, H 1.29, N 62.91; found: C 15.38, H 1.30, N 62.93.
Inorg. Chem. Front., 2024,11, 8235-8245
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Microtek
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I have experimented with ATRZ from SDIC and 4-amino-1,2,4-triazole. In my experience the large amount of cyanuric acid that is produced (and which has
quite low solubility) complicates the isolation of the product. I haven't tried it with hypochlorite.
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Axt
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I don't think I'm going to make any more 4-aminotriazole but it's probably something worth buying if you can, with the wide utility of it. I assume
you've also tried the melt cast nitrates/perchlorates?
Just to remove any doubt, below is a compound det. with 800mg PETN and 300mg CATP. At least that's the weight i was aiming for but I think the scale
was playing tricks on me. Regardless the black marks show where the column of each sit. PETN lightly arbor pressed, CATP hand pressed.
[Edited on 23-5-2025 by Axt]
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MineMan
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A insensitive Urazine metal polymer capable of DDT.
Microtek and Axt. Curious, this seems to have potential. I can’t grab the paper to see what the synth is like. It’s also unaffected by moisture
and has an impressive det pressure (31GPa)
https://pubs.rsc.org/en/content/articlelanding/2022/ce/d2ce0...
[Edited on 24-5-2025 by MineMan]
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MineMan
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| Quote: Originally posted by Axt | Ok, I tried it again.
CuCO₃·Cu(OH)₂ 2.63 g
70% HClO₄ 6.82 g
4-Aminotriazole 5.00 g
This is a 1:2.5 ratio, which wasn't really done on purpose rather I just overestimated how much 4-aminotriazole I had. The basic copper carbonate and
perchloric acid were mixed in 100mL of water and brought up to 90C. The 4-aminotriazole was dissolved into 50mL water and poured in in one go turning
the solution darker blue. The hotplate and stirrer were turned off and it was allowed to slowly return to room temperature. I was aiming for large
crystals here, but it still dropped out quite fine, in quite a desirable free flowing crystalline needle powder.
It may just be the morphology, but this batch was significantly more vehemic than the prior. It thumps off in half-pinch sized quantities reminiscent
of NHN. I can see how this would act as an initiatory primary.
Any sensitivity figures? Seems with the fast DDT it could be a stand alone detonator.
[Edited on 20-5-2025 by Axt] |
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Axt
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You can generally open the supporting information and view the experimental details without buying the article. https://www.rsc.org/suppdata/d2/ce/d2ce00182a/d2ce00182a1.pd...
It presents an inconvenient route to urazine. The AgNO3 complex seems to readily drop out of aqueous solution. It'd be an interesting one to try, the
negatives being the easiest route takes you through carbohydrazide and the expense of silver nitrate. It would be interesting to see another nitrate
complex capable of initiation though.
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Axt
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There was a ResearchGate link into full pdf.
Attachment: Silver Urazine Nitrate.pdf (2.9MB)
This file has been downloaded 49 times
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MineMan
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| Quote: Originally posted by Axt |
You can generally open the supporting information and view the experimental details without buying the article. https://www.rsc.org/suppdata/d2/ce/d2ce00182a/d2ce00182a1.pd...
It presents an inconvenient route to urazine. The AgNO3 complex seems to readily drop out of aqueous solution. It'd be an interesting one to try, the
negatives being the easiest route takes you through carbohydrazide and the expense of silver nitrate. It would be interesting to see another nitrate
complex capable of initiation though. |
Thank you! That is a great tip about the supporting materials! Great to know in the future!
Why is the route inconvenient? If I recall to make Urazine requires extremely high temperatures for a few hours done the standard way from
diaminourea?
Yes silver nitrate is expensive but, SADS was a common primary used on this forum for a while. If the compound is insensitive and can DDT confined in
small amounts it seems to offset the cost. Other metal nitrates would be interesting, the benefit of silver being low toxicity… although I don’t
know if the final product is toxic.
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dettoo456
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The starting compound, the hydrazodicarboxylate diester, is just a little harder to procure compared to carbohydrazide.
And the interest in metal-free, or at the least, transition and heavy metal-free, stems from the metals' reactivity with cap materials and other
energetics it may come in contact with, environmental safety, and especially in the case of silver compounds; air and light instability.
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MineMan
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| Quote: Originally posted by dettoo456 | The starting compound, the hydrazodicarboxylate diester, is just a little harder to procure compared to carbohydrazide.
And the interest in metal-free, or at the least, transition and heavy metal-free, stems from the metals' reactivity with cap materials and other
energetics it may come in contact with, environmental safety, and especially in the case of silver compounds; air and light instability.
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The paper states no incompatibility with metal shells or any light or air sensitivity.
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dettoo456
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That may be the case as is reported by them, but I personally would not trust this compound(s), simply due to my own paranoia, unless I or someone
else without grant funding examined its properties. Chinese & Indian publications are hit & miss, so excuse my cynisim.
[Edited on 25-5-2025 by dettoo456]
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Microtek
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I will certainly test the properties of this compound. It seems very easy if you have access to urazine, which I do through the carbohydrazide route.
I am very doubtful of the merits of the coumpound as a primary though; as I read the paper it seems to deflagrate in the hot needle test which I find
not so promising.
Regardless, the experiments will reveal the truth.
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MineMan
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| Quote: Originally posted by Microtek | I will certainly test the properties of this compound. It seems very easy if you have access to urazine, which I do through the carbohydrazide route.
I am very doubtful of the merits of the coumpound as a primary though; as I read the paper it seems to deflagrate in the hot needle test which I find
not so promising.
Regardless, the experiments will reveal the truth. |
I look forward to it Microtek! CuAGdiperchlorate also deflagrates out in the open up to and beyond one gram according to reports. But posters have
noted here that properly confined it detonates in as little as 20mg with more initiating power than its nickel counterpart; would still like you to
re-investigate that one! There was a post on it that was apparently deleted where a proper sand crusher and sensitivity test was preformed comparing
it to the nickel compound and it performed better. I can’t find that post using the search engine.
A few things with this paper. They use the KJ equation to predict detonation velocity which does not work with metal ligands. They also mention a
cadmium compound with a det velocity of over 10kms, but it has a lower density than the silver compound but less oxygen balance. But if I recall the
paper indicates the molecule has less partially oxidized molecules.
The silver compound does have a density of 2.6g/cc and good OB, which makes me think it’s actual performance is much higher?
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Microtek
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I did examine the copper analogue to NAP (I usually refer to it as CAP) and found it to be fine, though it requires more confinement to DDT compared
to NAP. IIRC, Etanol had some misgivings regarding the long term stability. For this reason I prepared a small batch some months (I think it was in
october or november) ago to see if it deteriorates on storing. So far it hasn't changed noticably in appearance or performance.
I just did the synthesis of the Ag(H2Ur)NO3 complex as described in the paper. An extremely dense white powder is produced. It settles to the bottom
of the beaker in seconds once stirring is stopped, and filters very well. On drying, I did the usual flame tests on foil, and found it to be
completely non-energetic. On looking through the paper a second time, I found that most of the results were on substance 5, the powder form slowly
recrystallized from nitric acid.
I added 1.00 g of the white powder to 8.5 ml distilled water at 85 C. It was difficult to get it suspended due to the aforementioned density. Then
about 2 ml HNO3, 62% was added. This caused most of the powder to dissolve, leaving a slightly turbid solution which was filtered hot. The filtrate is
evaporating at ambient conditions at time of writing. I find it likely that the initially precipitated white powder does not in fact contain the
nitrate ion, but we will see what is left when the solution has evaporated, and which properties it has.
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MineMan
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| Quote: Originally posted by Microtek | I did examine the copper analogue to NAP (I usually refer to it as CAP) and found it to be fine, though it requires more confinement to DDT compared
to NAP. IIRC, Etanol had some misgivings regarding the long term stability. For this reason I prepared a small batch some months (I think it was in
october or november) ago to see if it deteriorates on storing. So far it hasn't changed noticably in appearance or performance.
I just did the synthesis of the Ag(H2Ur)NO3 complex as described in the paper. An extremely dense white powder is produced. It settles to the bottom
of the beaker in seconds once stirring is stopped, and filters very well. On drying, I did the usual flame tests on foil, and found it to be
completely non-energetic. On looking through the paper a second time, I found that most of the results were on substance 5, the powder form slowly
recrystallized from nitric acid.
I added 1.00 g of the white powder to 8.5 ml distilled water at 85 C. It was difficult to get it suspended due to the aforementioned density. Then
about 2 ml HNO3, 62% was added. This caused most of the powder to dissolve, leaving a slightly turbid solution which was filtered hot. The filtrate is
evaporating at ambient conditions at time of writing. I find it likely that the initially precipitated white powder does not in fact contain the
nitrate ion, but we will see what is left when the solution has evaporated, and which properties it has.
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Thank you for the update! I am excited for the results! How would you compare the sensitivity (mechanical and impact) of CAP to uNAP or iNAP? Do you
think there is a way to get uCAP as I recall users saying the crystals are about 100um cubic?
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Microtek
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The sensitivity of CAP is a little higher than that of NAP IIRC, possibly because of the larger crystals. I did do an experiment with ultrasonication
of the mix during CAP synthesis and it did reduce the crystal size. I never got around to systematically testing the sensitivity of the uCAP though.
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