KonkreteRocketry
Hazard to Others
Posts: 165
Registered: 12-11-2012
Location: Dubai
Member Is Offline
Mood: No Mood
|
|
Lithium Perchlorate LiClO4
Lithium Perchlorate aka LiClO4 is a strong oxidizer.
I just checked now, LiClO4 have a higher percentage in weight, molecules, everything, higher than the modern rocket propellant APCP's oxidizer
NH4ClO4.
This means you can put less oxidizer with more fuel.
I read a report where LiClO4 or LPCP, reached a peak Specific impulse of 280+
Is this real ? I tried to find some reports or info about LiClO4 propellant related stuff but almost nothing, any one can help me please, thank you.
|
|
|
KonkreteRocketry
Hazard to Others
Posts: 165
Registered: 12-11-2012
Location: Dubai
Member Is Offline
Mood: No Mood
|
|
I saw that Asphalt was used with KClO4 in missles before, does Asphalt work good with nitrates ?
I heard there are some tries, but how was it, can some one help me out
Also, does KClO4 often burn more hotter than KNO3 even if with same fuel ?
Thank you guys, sorry for asking too much !
|
|
|
PHILOU Zrealone
International Hazard
Posts: 2893
Registered: 20-5-2002
Location: Brussel
Member Is Offline
Mood: Bis-diazo-dinitro-hydroquinonic
|
|
Be(ClO4)2 should be even better. Even less oxydiser vs fuel...
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
|
|
|
woelen
Super Administrator
Posts: 8012
Registered: 20-8-2005
Location: Netherlands
Member Is Offline
Mood: interested
|
|
That would be an awesome oxidizer, only very sad that Be is incredibly toxic and most likely Be(ClO4)2 will also be very hygroscopic. LiClO4 also is
very hygroscopic.
LiClO4 sometimes can be obtained commercially. Some time ago, I saw hydrated LiClO4 for sale on Keten's website, but they don't have it on their
website anymore. Probably they have sold all of it, it was not one of their standard items.
|
|
|
KonkreteRocketry
Hazard to Others
Posts: 165
Registered: 12-11-2012
Location: Dubai
Member Is Offline
Mood: No Mood
|
|
Yes true, but i can buy LiClO4 easily and cheaply, but i can not find
Be(ClO4)2 ...
Also, they both are almost the same, do they give more efficiency ?
|
|
|
PHILOU Zrealone
International Hazard
Posts: 2893
Registered: 20-5-2002
Location: Brussel
Member Is Offline
Mood: Bis-diazo-dinitro-hydroquinonic
|
|
Another idea would be, if possible, to make lewis adduct of anhydrous NH4ClO4 and anhydrous Al(ClO4)3...
NH4ClO4 + Al(ClO4)3 --?--> NH4Al(ClO4)4
It works for AlCl3
PH Z (PHILOU Zrealone)
"Physic is all what never works; Chemistry is all what stinks and explodes!"-"Life that deadly disease, sexually transmitted."(W.Allen)
|
|
|
simply RED
Hazard to Others
Posts: 209
Registered: 18-8-2005
Location: noitacoL
Member Is Offline
Mood: booM
|
|
It does work but with slightly changed experimental conditions:
http://www.dtic.mil/cgi-bin/GetTRDoc?AD=AD0634105
"Studies of Complex Perchlorates"
Sadly, NH4Al(ClO4)4 is unstable at water boiling temperature...
When logic and proportion have fallen sloppy dead...
|
|
|
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
Posts: 1986
Registered: 2-3-2011
Member Is Offline
Mood: No Mood
|
|
But it seems that the complex salt (NH4)3Al(ClO4)6 is stable.
(NO2)3Al(ClO4)6 was made by reacting NO2ClO4 and AlCl3 in liquid SO2 at -10 °C, reaction time 4 hours.
What I found interesting was that anhydrous aluminum nitrate can be prepared from AlCl3 in N2O4 at 0 °C.
[Edited on 23-12-2012 by AndersHoveland]
I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
|
|
|
simply RED
Hazard to Others
Posts: 209
Registered: 18-8-2005
Location: noitacoL
Member Is Offline
Mood: booM
|
|
From the same document:
"One sample (NH4)3Al(ClO4)6 exploded at 100 C."
When logic and proportion have fallen sloppy dead...
|
|
|
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
Posts: 1986
Registered: 2-3-2011
Member Is Offline
Mood: No Mood
|
|
I would be especially interested in NH4B(NO3)4, the paper mentioned that the B(NO3)4- ion shows surprising stability.
It might make a good solid rocket fuel oxidizer.
I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
|
|
|
jock88
National Hazard
Posts: 505
Registered: 13-12-2012
Member Is Offline
Mood: No Mood
|
|
Hi All,
It became more and more clear for me that I have inherent fancy for making
exotic propellants. One of ideas that never leave me in peace is to make
homogeneous solid propellant with oxidizer and fuel completely solvable in
each other. I tried to dissolve AP in various potential fuels, such as
sucrose, sorbitol, polyethyleneglicol, triazole, benzotriazole,
dimethylsulfoxide, etc. at ambient temperature and up to 120°C. (to my
surprise, AP is stable at that temperature) Neither of these mixtures was
homogeneous or at least pourable.
BUT LiClO4 !
The first attempt was successful. I mix 70% LiClO4 / 30%
epoxy+curative(maleic anhydride - for high temperature processing), heat to
150°C and mixture became clear liquid (well, brown liquid), all bubbles
readily released. After heating 2 hours at 150°C mixture was still liquid
and after cooling I had hard plastic-like mass.
Summary of some test results:
Thermal stability
I put small piece (~0.1g) on the top of hot plate (black iron surface) and
turn on power. At 130°C propellant melted, at 180°C began to bubble, at
230°C became dark-brown solid porous mass. I heat it up to 290°C, but it
don't ignited. I concluded that preparation of propellant at 150°C is
reasonably safe.
Burn test
I poured hot propellant in paper tube (ID=9mm) and lit it after cooling. It
burned vigorously, ambient pressure regression was 2 mm/s. It is comparable
to what I have with uncatalised AP/epoxy 80/20 (2.7 mm/s). Flame color was
not as red as I expected.
Performance prediction
PROPEP gives maximum Isp=233 for LiClO4/ SHELL EPON 815 78%/22%. (D=
0.06993 LB/CU-IN OR 1.9358 GM/CC).
70/30 mix has Isp=221. (D= 0.06534 LB/CU-IN OR 1.8087 GM/CC)
For AP/ SHELL EPON 815 maximum Isp=249 (87%/13%). (D= 0.06422 LB/CU-IN OR
1.7777 GM/CC).
80/20 mixture has Isp=238. (D= 0.06152 LB/CU-IN OR 1.7030 GM/CC).
Does anyone have thoughts about possible pressure exponent for this
propellant?
Thereby, LiClO4/epoxy propellant has advantages:
- very simple preparation. Finished grain may be prepared during 3 hours.
- high performance (possible).
- high density.
It is expensive, however.
Serge Pipko
Anthony Colette wrote:
>
> Be very careful with homogenous mixtures of fuels and oxidizers. They
> can detonate high order. And just because it was apparently stable at
> 290' C doesn't mean it will be indefinitely. Neither will it
> necessarily be indefinitely stable at 150' C either. Such mixtures
> can be very impact sensitive and have high burn rate exponents. Be
> careful.
See also Patent No. GB 1047474
|
|
|
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
Posts: 1986
Registered: 2-3-2011
Member Is Offline
Mood: No Mood
|
|
Dissolving the oxidizer and fuel together in the same phase will very much increase the sensitivity to detonation, especially when it contains
perchlorate. These soluble propellants are generally not suitable for large rockets, because of the danger of detonation, or if this is compensated
for, the inferior specific impulse. There are, however, some interesting mixes used for, or being investigated for, mono-propellants when the thrust
needs to be precisely controlled or easily turned on/off in space.
Lithium and beryllium (both metals and compounds), because of their low atomic weights, are ideal for rocket fuel and oxidizer, but their high cost is
prohibitive. An economic argument could still be made for incorporating them into the upper stage of a rocket, however.
The lithium ion in LiClO4 is actually slightly acidic, this explains its unique solubility in ethers.
[Edited on 29-12-2012 by AndersHoveland]
|
|
|
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
Posts: 1986
Registered: 2-3-2011
Member Is Offline
Mood: No Mood
|
|
Something else interesting:
"The tetranitratoborate anion, [B(NO3)4]-, ... Surprisingly the anion is not hydrolyzed by water, it is soluble in hot water, methanol, acetonitrile,
and may be recovered unchanged."
C.C. Addison and D. Sutton
Progress in Inorganic Chemistry, Volume 8, p216
I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
|
|
|
KonkreteRocketry
Hazard to Others
Posts: 165
Registered: 12-11-2012
Location: Dubai
Member Is Offline
Mood: No Mood
|
|
Quote: Originally posted by jock88  | Hi All,
It became more and more clear for me that I have inherent fancy for making
exotic propellants. One of ideas that never leave me in peace is to make
homogeneous solid propellant with oxidizer and fuel completely solvable in
each other. I tried to dissolve AP in various potential fuels, such as
sucrose, sorbitol, polyethyleneglicol, triazole, benzotriazole,
dimethylsulfoxide, etc. at ambient temperature and up to 120°C. (to my
surprise, AP is stable at that temperature) Neither of these mixtures was
homogeneous or at least pourable.
BUT LiClO4 !
The first attempt was successful. I mix 70% LiClO4 / 30%
epoxy+curative(maleic anhydride - for high temperature processing), heat to
150°C and mixture became clear liquid (well, brown liquid), all bubbles
readily released. After heating 2 hours at 150°C mixture was still liquid
and after cooling I had hard plastic-like mass.
Summary of some test results:
Thermal stability
I put small piece (~0.1g) on the top of hot plate (black iron surface) and
turn on power. At 130°C propellant melted, at 180°C began to bubble, at
230°C became dark-brown solid porous mass. I heat it up to 290°C, but it
don't ignited. I concluded that preparation of propellant at 150°C is
reasonably safe.
Burn test
I poured hot propellant in paper tube (ID=9mm) and lit it after cooling. It
burned vigorously, ambient pressure regression was 2 mm/s. It is comparable
to what I have with uncatalised AP/epoxy 80/20 (2.7 mm/s). Flame color was
not as red as I expected.
Performance prediction
PROPEP gives maximum Isp=233 for LiClO4/ SHELL EPON 815 78%/22%. (D=
0.06993 LB/CU-IN OR 1.9358 GM/CC).
70/30 mix has Isp=221. (D= 0.06534 LB/CU-IN OR 1.8087 GM/CC)
For AP/ SHELL EPON 815 maximum Isp=249 (87%/13%). (D= 0.06422 LB/CU-IN OR
1.7777 GM/CC).
80/20 mixture has Isp=238. (D= 0.06152 LB/CU-IN OR 1.7030 GM/CC).
Does anyone have thoughts about possible pressure exponent for this
propellant?
Thereby, LiClO4/epoxy propellant has advantages:
- very simple preparation. Finished grain may be prepared during 3 hours.
- high performance (possible).
- high density.
It is expensive, however.
Serge Pipko
Anthony Colette wrote:
>
> Be very careful with homogenous mixtures of fuels and oxidizers. They
> can detonate high order. And just because it was apparently stable at
> 290' C doesn't mean it will be indefinitely. Neither will it
> necessarily be indefinitely stable at 150' C either. Such mixtures
> can be very impact sensitive and have high burn rate exponents. Be
> careful.
See also Patent No. GB 1047474
|
Amazing ! I think some aluminium powder can push it specific impulse to 260+
|
|
|
KonkreteRocketry
Hazard to Others
Posts: 165
Registered: 12-11-2012
Location: Dubai
Member Is Offline
Mood: No Mood
|
|
| Quote: Originally posted by AndersHoveland | Something else interesting:
"The tetranitratoborate anion, [B(NO3)4]-, ... Surprisingly the anion is not hydrolyzed by water, it is soluble in hot water, methanol, acetonitrile,
and may be recovered unchanged."
C.C. Addison and D. Sutton
Progress in Inorganic Chemistry, Volume 8, p216 |
umm interesting, any info i can find about that ?
|
|
|
franklyn
International Hazard
Posts: 3026
Registered: 30-5-2006
Location: Da Big Apple
Member Is Offline
Mood: No Mood
|
|
Inorganic Nitrate Hydrogen Peroxide Adducts & Methods for Their Preparation
US patent 20080190525 => Attachment: H2O2 Nitrate adducts US20080190525.pdf (1.1MB)
This file has been downloaded 799 times
A possibility of a peroxidate of LiClO4 is not addressed , but it is notable that
the ClO4- ion is not reactive at any pH with H2O2 and Mg(ClO4)2 is used as
a drying agent when concentrating H2O2. Following the procedure described ,
it is a simple matter to determine if an LiClO4 • H2O2 adduct can be made.
Testing Mg(ClO4)2 is of interest also , possibly yielding Mg(ClO4)2 • 2H2O2
.
|
|
|
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
Posts: 1986
Registered: 2-3-2011
Member Is Offline
Mood: No Mood
|
|
Tetramethylammonium chloride can be reacted with BCl3 to form (CH3)4BCl4. This can then be reacted with N2O4 to form the tetranitratoborate complex,
(CH3)4N[B(NO3)4]. The byproducts, NO2Cl / NO2 and Cl2, are easily volatized off. Although the tetranitratoborate complex is perfectly stable at room
temperature, the reaction is best performed at reduced to temperature (liquid SO2 as solvent -20 °C) to prevent the undesirable formation of oxyboron
nitrates.
N-methyl pyridinium tetranitratoborate is a liquid at room temperature, being an example of an ionic liquid.
I wonder whether a hydroxylamine tetranitratoborate salt is possible, whether tetranitratoborate shows any oxidizing behaviour, or if hydroxylamine
would reduce the complex. I suspect not, but am not sure.
On the subject of complex perchlorate salts, I found this:
"Boron triperchlorate did not form an adduct with trimethylamine but did form a somewhat stable adduct with nitronium perchlorate. The compound is
thermally unstable, B(ClO4)3 decomposing with evolution of chlorine heptoxide"
THE STUDY OF BORON PERCHLORATE AND RELATED SYSTEMS, R. A. Mosher, E. K. Ives, E. F. Morello
I think this adduct they are describing is probably NO2B(ClO4)4
[Edited on 2-1-2013 by AndersHoveland]
I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
|
|
|
Fantasma4500
International Hazard
Posts: 1681
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline
Mood: dangerously practical
|
|
[/rquote]
What I found interesting was that anhydrous aluminum nitrate can be prepared from AlCl3 in N2O4 at 0 °C.
[Edited on 23-12-2012 by AndersHoveland][/rquote]
A bit off topic, but when ive made Pb(NO3)2 by HNO3 + Pb i have covered my flask with 10 layers of aluminium foil, and apparently the NO2 formed can
and WILL react with the aluminium foil to make aluminium nitrate, infact this reaction is probably taking place right now, just thought its weird that
aluminium wont react with HNO3 but NO2 reacts with aluminium
|
|
|
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
Posts: 1986
Registered: 2-3-2011
Member Is Offline
Mood: No Mood
|
|
| Quote: Originally posted by Antiswat |
when ive made Pb(NO3)2 by HNO3 + Pb i have covered my flask with 10 layers of aluminium foil, and apparently the NO2 formed can and WILL react with
the aluminium foil to make aluminium nitrate, just thought its weird that aluminium wont react with HNO3 but NO2 reacts with aluminium
|
I am not sure exactly what is happening, this might help:
Aluminum is resistant to nitric acid if the acid concentration is over 95%, but if the concentration is below 80%, or if the nitric acid is heated
above 40 °C, the corrosion rate is much faster. Handbook of corrosion data. Bruce D. Craig, David S. Anderson, ASM International
I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
|
|
|
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
Posts: 1986
Registered: 2-3-2011
Member Is Offline
Mood: No Mood
|
|
Anhydrous Aluminum triperchlorate
Some russian investigators did report a successful preparation of anhydrous aluminum perchlorate:
| Quote: |
"...we obtained for the first time anhydrous Al(ClO4)3 from AlCl3 and Cl2O6 in liquid ClO2."
|
They had to use cryogenically liquified ClO2 in their procedure?! Seems like a very bad idea...
| Quote: |
"It was found that Al(ClO4)3 does not dissolve in noncoordinating organic solvents - saturated hydrocarbons and their derivitives - but reacts with
them. ...
Treatment of Al(ClO4)3 with THF leads to formation of a poorly soluble solvate of the composition Al(ClO4)3 • 3C4H8O; its IR spectrum does not
display bands of the ClO4- ion, but it has bands of the ClO4 coordinated group: 920, 1040,and 1200 cm-1. Aluminum perchlorate dissolves in
considerable amounts in CH3NO2; removal of the solvent leaves the poorly crystallizing complex Al(ClO4) • 3CH3NO2.
The inorganic solvents investigated were liquid SO2, N2O4, NOCl, and anhydrous HClO4. ... In NOCl and N2O4 we observe complete solvolysis of Al(ClO4)3
to nitrosyl perchlorate and aluminum chlorido or nitrato complex."
"Solvation, Solvolysis, and Complexing of Anhydrous Aluminum Perchlorate in Anhydrous Media", Z.K. Nikirina, V. Ya. Rosolovskii, Izvestiya
Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1223–1227, June, 1980.
|
Apparently anhydrous aluminum perchlorate is a fairly reactive oxidizer:
| Quote: |
"Addition of solid Al(ClO4)3 to CH3OH at [around] 20 °C leads to a flash."
|
In another paper by the same researchers, the enthalpy of formation of anhydrous aluminum perchlorate was experimentally determined to be −136.5
±0.5 kcal/mole.
There was a very old book about various perchlorates, which I do not have a link to, including an entry for aluminum perchlorate (almost always
encountered as the hydrate). Despite devoting several paragraphs to this compound, they did not mention anything about it being explosive. This source
did make mention to the anhydrous form, although another article I later read somewhere else cast doubt on these early reports.
Anhydrous titanium perchlorate also exists:
| Quote: |
Nonsolvated titanium perchlorate was produced by the action of TiCl4 on anhydrous perchloric acid (containing up to 2% Cl2O7). Titanium perchlorate
possesses an appreciable intrinsic vapor pressure and can be repeatedly sublimed at 70 °C under vacuum. The properties of sublimed Ti(ClO4)4 differ
from the properties of the starting material.
It was established by the method of differential thermal analysis that Ti(ClO4)4 melts with partial decomposition at 85–95 °C, and above 110°C
under vacuum it decomposes to TiO2, O2, and oxides of chlorine. The heating of Ti(ClO4)4 at atmospheric pressure ends in explosive decomposition at
∼130 °C.
Ti(ClO4)4 dissolves vigorously in water, it dissolves with decomposition in nitromethane and acetonitrile - the solution turns yellow. It is insoluble
in CCl4 but above 25 °C it reacts, forming a yellow solution.
Titanium perchlorate is a colorless hygroscopic crystalline substance. ... The density of Ti(ClO4)4 ... is equal to 2.35 g/cm3.
"Volatile titanium perchlorate", V. P. Babaeva, V. Ya. Rosolovskii,
Bulletin of the Academy of Sciences of the USSR, Division of chemical science, November 1974, Volume 23, Issue 11, pp 2330-2334
|
[Edited on 9-3-2013 by AndersHoveland]
I'm not saying let's go kill all the stupid people...I'm just saying lets remove all the warning labels and let the problem sort itself out.
|
|
|
Fantasma4500
International Hazard
Posts: 1681
Registered: 12-12-2012
Location: Dysrope (aka europe)
Member Is Offline
Mood: dangerously practical
|
|
well i remember still very clearly that nurdrage explained that HNO3 as 99% makes a protective layer around copper metal, but as soon as you add a
drop of water you got a reaction, nearly immediately.. (:
i have 62% HNO3 tho, and i use aluminium tubes (but they have a really thick Al2O3 coating on
on one end where ive broken the tube off i sometimes use it as a top sometimes not, the times i dont use it as top, so to say, i put it in the HNO3
and cover the top with my finger and then drags up the HNO3 without problems..
so.. aluminium isnt attacked by HNO3, as far as i know
but NO2 sure does a job.. perhaps its because of the presence of the water?
also.. about perchlorates...
as i understand you can form NH4ClO3 and NH4ClO4 by the addition of KClO3 / KClO4 to ammonium tartrate, giving insoluble potassium tartrate and the
corresponding ammonium salt..
not only is this useful for making NH4ClO4 cheaply (or well relatively cheaply, ammonium tartrate can be made with NH4OH + tartrate acid anyways) but
also for making other exotic perchlorates (wee)
i have Pb(ClO4)2 in my mind, as Pb(ClO2)2 will explosively decompose when heated
if Pb(ClO4)2 isnt explosive by itself, then it would be an insane oxidizer..
i know that Pb(NO3)2 is a really reactive nitrate, mixed with magnesium in the correct amounts i got a mixture that ignited by contact quite
powerfully for just a nitrate and magnesium powder..
and if Pb(ClO4)2 isnt interesting, i could expect Pb(MnO4)2 to be even more interesting, as NH4ClO4 is already quite reactive, and NH4MnO4 is by
itself explosive and can be detonated with less force than ETN, that should make a reason for that Pb(MnO4)2 should be even better than Pb(ClO4)2
|
|
|
AndersHoveland
Hazard to Other Members, due to repeated speculation and posting of untested highly dangerous procedures!
Posts: 1986
Registered: 2-3-2011
Member Is Offline
Mood: No Mood
|
|
I do not think either of these behave unusually. These two compounds are ionic salts and are not reactive oxidizers at room temperature.
The reason they work better in thermite mixtures is because the Pb+2 is easily reduced to metallic lead. Lead can also be fairly easily oxidized
during combustion to PbO2·2PbO
Lead may be a less electropositive, fairly inert metal, but because it is lower down on the periodic table it still prefers to form ionic bonds rather
than covalent. Usually metals higher up on the periodic table and in higher oxidation states tend to form more covalent bonds. It is these covalent
bonds with nitrate or perchlorate groups which lead to oxidizing properties. Perchlorate groups become much less stable when they do not have an extra
electron resonating around.
[Edited on 10-3-2013 by AndersHoveland]
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
