From: glhurst@onr.com (Gerald L. Hurst)
Newsgroups: rec.pyrotechnics,alt.engr.explosives
Subject: Re: Hydrazine was: Bomb recipe GUARANTEED to work!
Date: 2 Sep 1995 03:29:13 GMT
Organization: Consulting Chemist
Lines: 109

In article <427eg2$ede@sulawesi.lerc.nasa.gov>, TPDMT@lims01.lerc.nasa.gov 
(DeeTee) says:

>  You're right, very dangerous stuff. I worked with it here at NASA as
>a single component rocket fuel. Simply feed it under pressure into the
>rocket motor and ignite it by passing it over a palladium (platinum?)
>catalyst. It was suppossed to break down into nitrogen and hydrogen,
>and then the hydrogen burned in a secondary reaction. We fired in a
>vacuum chamber at high altitude conditions, however, and there was
>always a strong ammonia smell when we opened the chamber.

When I was Chief Scientist of EXCOA (Explosives Company of America), 
the parent company, Rocket Research Corporation (RRC) was in the 
business of manufacturing gas generators for use as attitude control 
rockets and as aircraft escape slide inflators (Boeing 747). The 
catalytic decomposition of hydrazine in these units procedes partly
according to the reaction 2N2H4 -> 2NH3 + N2 + H2 so some ammonia 
is to be expected.

>  We attended a 3 day safety couse before handling it. We wore
>pressurized "moon suits" at all times while working with the stuff. The
>rooms which contained the fuel tanks were kept flooded several feet
>deep with water in case of a hydrazine leak. Overhead water spray bars
>would go off if hydrazine was detected. We had hydrazine monitors in
>all rooms, and small ones on each person. If we had to open a fuel
>line, a pan of dilute bleach was held under the fitting. Hydrazine was
>allowed to run into the pan, and the fittings were dropped in also.

NASA goes all out for safety and could afford it. We used to 
literally blend the liquid with wooden paddles in 20 l 
polyethylene jugs. Our source of water was a 55 gal drum
located on the roof of our remote lab and our fume hood was
the an open window or the great outdoors when it wasn't
raining in Seattle..

>  We were told that it explosively reacted with iron oxide (rust) above 20 
>degrees F (not sure about the temp, its been a while). 

Hydrazine is a reducing agent so one needs to keep it away from
metal salts, especially copper alloys to avoid potential fires.

>Also, our literature 
>said (QUOTE!) "A single drop on the skin of a laboratory animal will cause 
>death within hours" Believe me, we remembered that quote!

It would have to be a very small animal as is indicated by my own
survival of many, many splashes and lots of eye-watering fumes.

>  As I had it explained to me in the safety course, if hydrazine is
>restrained, it explodes in small diamond-shaped "cells" less than 1/4
>inch across. Pressure increase in a cell was about 20 (40?) times the
>ambient pressure. Each cell than raised the pressure of adjacent
>hydrazine, then detonated it by propagation. This multiplying action
>continued. We were told that the explosive power was extreme
>(infinite?) because of this mechanism. It could keep developing
>pressure until any container burst.
>
>  The demonstration we saw (filmed, not live) had a thick walled steel
>tube maybe 6" long by 1/4" diameter fitted to very heavy 6" or 8"
>diameter flanges.  Flanges were bolted together with standard bolts,
>1/2" or 5/8" I recall. The tube was filled with hydrazine and a
>diaphragm between the flanges was popped by pressure from the other
>side, setting off the hydrazine. The 1/4" tube nearly vaporized, and
>all the flange bolts failed in tension, while the heavy flanges were
>dished by the internal force of the blast. VERY impressive. By the way,
>we were taught by a chemist who had spent decades studying hydrazine.

I'm not quite sure about the mechanism of this experiment, but
it is unlikely that pure hydrazine detonated. We developed a
ternary N2H4/AN/H2O graph on which we were able to shade in
the area of composition which was detonable, and it did not
include any compositions near that of pure hydrazine. Of course
these experiments might not be valid at higher temperatures.
If there were some sort of catalyst present then, of course,
no flange would be able to hold the pressure of the liberated
nitrogen and any hydrogen not removed by the formation of 
ammonia. However this mechanism should destroy either the 
flange bolts or the tubing, but not both. If it did detonate,
I would suggest that either there was another reactant 
present or that the material was heated. I would certainly
like to know more details about this demonstration.

I've taken hydrazine/oxidizer combinations up to 12,000 psi
in stainless steel without incident until I fired the 
seismic cap in the liquid. The mixtures do shoot at such
pressures where other liquids like PLX may fail.

Jerry

Newsgroups: rec.pyrotechnics
From: tip@mercury.aichem.arizona.edu (Tom Perigrin)
Subject: Re: Hydrazine was: Bomb recipe GUARANTEED to work!
Followup-To: rec.pyrotechnics,alt.engr.explosives
Date: Fri, 1 Sep 1995 21:50:55 GMT

In article <pas16.229.30471E3D@psu.edu>, pas16@psu.edu (Noodle) wrote:
> 
> In article <426dls$s3@odo.PEAK.ORG> billn@PEAK.ORG (Bill Nelson) writes:
> > : Hydrazine has recently been "discovered" by survivor types as an 
> incredibly > : high-explosive, when mixed with another element. Hydrazine is 
> also near > : impossible to ship, dissolves steel, very expensive (though 
> available) and one > : whiff will kill you instantly. I wouldn't recommend it.
> 
> >Wrong again. You really should research your subjects before posting such
> >nonsense.
> 
> >Hydrazine is easy to ship, does NOT dissolve steel, and is toxic - but NOT
> >instantly lethal.
> 
> >Still, I do not recommend messing with it. It IS a rather nasty chemical.
> 
> >Bill
> 
> We're talking about _anhydrous_ hydrazine, right? The hydrazine that,
> when two parts are mixed with one part NH4NO3, creates the most
> powerful chemical explosive in existence? And the same hydrazine that
> manufacturers use moon suits and respirators to handle, and costs $146
> for 500g? The hydrazine that DOES eat through any metal? The hydrazine
> that will blister an animals' lungs with one diluted whiff? That
> hydrazine, right? Well I did my research and it looks like I'm not the
> one peddling the nonsense.

Having worked with anhydrous hydrazine many years ago in the lab, I
remember it as a foul liquid that required some caution in handling.  At
that time, they didn't know about the carcinogenicity.

According to the Merck Index, Tenth Edition, entry 4669, Anhydrous
Hydrazine has a pentrating odor resembling ammonia.   LD50 in mice, 59
mg/Kg orally, about the same IV.  (LD50 of potassium cyanide in mice is 10
mg/Kg, so this is about 1/6'th as toxic as NaCN).  

The NIOSH Toxic Substances List, Vol 39, lists the LC50 for inhalation in
rats as 570 ppm/4 Hours.  For comparison, the value for HCN is 544 ppm/5
minutes.  Hydrazines value is closer to substances which we consider less
toxic, such as the gas from burning sulfur (SO2) which has a LC50 inhl rat
611 ppm/5 Hour.

Houben Weyl, Vol XI, Stickstoff Dopple Verbindungen, states that hydrazine
may be handled with nickel, chromium, vanadium and platinum vessels. 
However, the use of stainless steel, copper, iron, or similar metals is
advised against due to the possibility that the metal may catalyze a highly
exothermic decomposition of the hydrazine, leading to explosion.  Merck
also warns against the use of molybdenum containing alloys.

However, hydrazine is listed as having a strong caustic action on skin due
to the high heat of hydration.  Anhydrous hydrazine strips out the water,
and liberates heat, much as H2SO4 does.  That would help explain why
manufacturers handling ton quantities would want to utilize the same
confinement and containment protocols as they do for many other highly
nasty compounds.  

I'd say you are both right, but from different aspects.  In ton quantities
the stuff is very very nasty. On the other hand, I'd hate to have to deal
with a spilled ton of bleach!   But given a few dozen grams, I'd say that
apart from the carcinogenicity it is no worse than many chemicals that we
are sometimes exposed to.  (H2S, SO2, HCN, con H2SO4, con HNO3)  Given the
carcinogenicity, I can see no reason to "fiddle with it" needlessly.


---

If I was smart, I'd have a clever .sig

From: glhurst@onr.com (Gerald L. Hurst)
Newsgroups: rec.pyrotechnics,alt.engr.explosives
Subject: Re: Hydrazine was: Bomb recipe GUARANTEED to work!
Date: 2 Sep 1995 19:26:55 GMT
Organization: Consulting Chemist

In article <428ubl$6mr@odo.PEAK.ORG>, billn@PEAK.ORG (Bill Nelson) says:

> Repeated
>exposures may cause toxic damage to the liver (fatty liver) and kidney
>(interstitial nephritis), as well as anemia. The threshold limit value of
>hydrazine is 1 ppm (1.3 mg/m^3)."

It would be good to heed these long-exposure toxicity warnings.
When I worked with hydrazine on a daily basis, we were nor aware
of potential health problems. Much later I encountered all of
the above symptoms to an extent you don't want to hear about.

Jerry

From: glhurst@onr.com (Gerald L. Hurst)
Newsgroups: rec.pyrotechnics,alt.engr.explosives
Subject: Re: Hydrazine explosive (was:Hydrazine)
Date: 1 Sep 1995 21:39:21 GMT
Organization: Consulting Chemist
Lines: 62

In article <pas16.230.30476EDC@psu.edu>, pas16@psu.edu (Noodle) says:

>In article <DE8KqF.1xIF@austin.ibm.com> mikedean@austin.ibm.com () writes:
>
>>> We're talking about _anhydrous_ hydrazine, right? The hydrazine that,
>>> when two parts are mixed with one part NH4NO3, creates the most
>>> powerful chemical explosive in existence? And the same hydrazine that
>>> manufacturers use moon 
>>
>>Could you give details about power of explosive? Is it useful, or is it
>>just a laboratory curiosity? (Not debating, but really wanting to know
>>some facts).
>
>Totally useless. You're right, it's just a lab curiousity. For
>ultra-high-power explosives, there's always C-4, and Astrolite, and a
>couple other exotic ones. I don't know of any case where someone has
>actually used the hydrazine/nh4no3 explosive, and it just came onto the
>survivor scene a few years ago, who knows why.

Noodle, you are a veritable fountain of misinformation. I would
guess that the N2H4/AN suggestions came on the scene because 
someone bothered to read the Astrolite patents or talk with 
someone who knew about Astrolite. Allow me to introduce myself. 
I'm Jerry. Now you know someone who has used N2H4 based 
explosives.

The Astrolite you are referring to is reasonably energetic and
brisant, but hardly "ultra-high-power." Its relatively low
density does not allow it to achieve the peak detonation
pressures reached by PETN, RDX, etc. The energy release per
pound compares favorably with other non-metallized military
explosives but is considerably less than such materials as H-6.

The chemical sensitivity, corrosivity, toxicity and water
solubility dictate against Astrolite or N2H4 explosives in
general ever becoming standard military or commercial products, 
but they do have utility for special purposes and are 
interesting theoretically because some of them yield only gaseous, 
transparent, carbon-free detonation products.

Jerry

From: glhurst@onr.com (Gerald L. Hurst)
Newsgroups: rec.pyrotechnics,alt.engr.explosives
Subject: Re: Hydrazine was: Bomb recipe GUARANTEED to work!
Date: 1 Sep 1995 22:10:17 GMT
Organization: Consulting Chemist

In article <pas16.229.30471E3D@psu.edu>, pas16@psu.edu (Noodle) says:

>In article <426dls$s3@odo.PEAK.ORG> billn@PEAK.ORG (Bill Nelson) writes:
>
>>Wrong again. You really should research your subjects before posting such
>>nonsense.
>>
>>Hydrazine is easy to ship, does NOT dissolve steel, and is toxic - but NOT
>>instantly lethal.
>>
>>Still, I do not recommend messing with it. It IS a rather nasty chemical.
>
>We're talking about _anhydrous_ hydrazine, right? The hydrazine that, when 
>two parts are mixed with one part NH4NO3, creates the most powerful chemical 
>explosive in existence? And the same hydrazine that manufacturers use moon 
>suits and respirators to handle, and costs $146 for 500g? The hydrazine that 
>DOES eat through any metal? The hydrazine that will blister an animals' lungs 
>with one diluted whiff? That hydrazine, right? Well I did my research and it 
>looks like I'm not the one peddling the nonsense.

Bill Nelson is correct:

Hydrazine does not "eat through any metal." In order to do so it
would have to oxidize the metal, but it is a powerful reducing
agent, not an oxidizer. Some metals, like platinum may act as a 
catalyst to decompose N2H4 ultimately into nitrogen and hydrogen
but the same can be said of ammonia.  Hydrazine as well as 
hydrazine and many of its mixtures can be conveniently stored
even in aluminum containers. The material may react with some
metal oxides or other metal salts because it can reduce these 
to the respective elements.

If one whiff of the vapor were fatal to animals I would have
been dead many years ago, because I've blended literally tons
of the stuff with a canoe paddle.

In a manufacturing plant making lots of any liquid other than
water and booze. a sudden dose all over the body can be fatal
so if you can tolerate a protective suit, it's a good idea.

We paid a buck or two per pound for hydrazine in the 70s. I
suppose with inflation its more now. At $140 per pound you're
talking reagent prices. This is cheap compared to what they 
sometimes get for 2 cents worth of table salt.

Do not misunderstand me. Hydrazine is toxic and it is caustic.
Prolonged exposure to the material may be fatal. In fact,
it may have cost me a liver - I do not know. However, the
picture painted of this material in this forum needs to be
moderated so that its place in the spectrum of nasty 
chemicals is more accurately defined. ClF5 is NASTY, N2H4
is merely nasty.

Jerry

From: glhurst@onr.com (Gerald L. Hurst)
Newsgroups: rec.pyrotechnics,alt.engr.explosives
Subject: Re: Hydrazine explosive (was:Hydrazine)
Date: 4 Sep 1995 06:30:13 GMT
Organization: Consulting Chemist
Lines: 17

In article <42e3tb$7ke@its.hooked.net>, youngin <uhunh@nowhere.com> says:

>I had heard of Astrolite A-1-5 (an ammonium nitrate/hydrazine mixture) 
>that was supposed to be the strongest non-nuclear explosive.  The 
>statistics given put its detonation velocity over 8,600 mps 
(meters/sec.). 
> I'm no expert, but that is stronger than RDX etc., am I wrong.

Astrolite A-1-5 was pretty fast, but I'm not sure it quite hit
the 8600 m/s mark. It was indeed much more energetic than RDX
and the like because it was designed for high cratering and
air blast. For these applications it is in the class of tritonal 
and H-6 and, on a bulk strength basis, probably somewhere in
between these two materials. On a pound for pound basis the
material is close to H-6 in strength, which is very good.

Jerry

From: glhurst@onr.com (Gerald L. Hurst)
Newsgroups: rec.pyrotechnics,alt.engr.explosives
Subject: Re: Hydrazine explosive (was:Hydrazine)
Date: 6 Sep 1995 03:10:12 GMT
Organization: Consulting Chemist
Lines: 67

In article <DEFv54.1sJJ@austin.ibm.com>, mikedean@austin.ibm.com () says:

>In article <42e6dl$7mi@geraldo.cc.utexas.edu>, glhurst@onr.com (Gerald L.
>  Hurst) writes:
>> In article <42e3tb$7ke@its.hooked.net>, youngin <uhunh@nowhere.com> says:
>> >
>> >I had heard of Astrolite A-1-5 (an ammonium nitrate/hydrazine mixture) 
>> >that was supposed to be the strongest non-nuclear explosive.  The 
>> >statistics given put its detonation velocity over 8,600 mps (meters/sec.).
>> 
>> > I'm no expert, but that is stronger than RDX etc., am I wrong.
>>
>> Astrolite A-1-5 was pretty fast, but I'm not sure it quite hit
>> the 8600 m/s mark. It was indeed much more energetic than RDX
>> and the like because it was designed for high cratering and
>> air blast. For these applications it is in the class of tritonal 
>> and H-6 and, on a bulk strength basis, probably somewhere in
>> between these two materials. On a pound for pound basis the
>> material is close to H-6 in strength, which is very good.
>
>I have a report, that is probably available to any Defence Contractor,
>that describes a newer (1986) nitrogen rich explosive with a detonation
>velocity of from about 8.6 Km/Sec to 9.2 Km/Sec. RDX was first
>synthesized in 1899 so there is probably room for improvement. The
>variations are due to how much it was compressed when it was tested. I
>don't have the report with me, but there are several explosives that
>are more powerful than RDX. At least that have higher detonation
>velocities. Most are too sensitive for practical Military or civilian
>use. 

I believe you must have misunderstood my post. The H-6 explosive
mentioned therein is far more "powerful" than RDX in the sense
that it releases more energy and will blow a bigger crater. It
is also slower.

Certainly there are well-known explosives which have detonation
velocities higher than 8600 m/s. Plain old PETN at or near its
crystal density of 1.8 shoots at 8800 and the less common HMX
has been reported at over 9100. However, so-called "power" refers
to energy release or ability to do work, and the fastest 
explosives do not happen to be the most energetic.

Astrolite A-1-5 was quite  powerful on a weight basis but its low 
density made it difficult to compete with other high blast bomb 
fillers when it was shot in the same limited volume bomb casings.
It's detonation velocity, which has relatively little to do with 
its energy, was respectable, but probably not quite up to 8600 as
I remember. I could be wrong - it's been over 25 years since I 
shot my last ton of the stuff.

Detonation velocity is usually associated with brisance, but even
that relationship is sometimes shakey. For instance HMX is said
to shoot a good 700 m/s faster than its cousin RDX, but the
brisance of the two appears to be about the same according to
Picatinny Arsenal.

Jerry

Newsgroups: rec.pyrotechnics,alt.engr.explosives
From: arno@utu.fi (Arno Hahma)
Subject: Re: Hydrazine explosive (was:Hydrazine)
Organization: University of Turku
Date: Sat, 9 Sep 1995 13:45:55 GMT

In article <42j3ek$fh8@geraldo.cc.utexas.edu>,
Gerald L. Hurst <glhurst@onr.com> wrote:

> > that describes a newer (1986) nitrogen rich explosive with a detonation
> > velocity of from about 8.6 Km/Sec to 9.2 Km/Sec. RDX was first

I wonder, if it is a caged, tetracyclic molecule with six N-nitro
groups and six methylene groups. If so, do they give a synthesis for
it in the paper?

>that relationship is sometimes shakey. For instance HMX is said
>to shoot a good 700 m/s faster than its cousin RDX, but the
>brisance of the two appears to be about the same according to

You'd see the difference, if you made, for instance, shaped charges out
of the two materials. The one with octogen will penetrate more if the
same dimensions and geometries are used. The brisance tests are pretty
crude and do not necessarily show differences under 10 % or so.


ArNO
    2

From: glhurst@onr.com (Gerald L. Hurst)
Newsgroups: rec.pyrotechnics,alt.engr.explosives
Subject: Re: Hydrazine explosive (was:Hydrazine)
Date: 10 Sep 1995 08:19:03 GMT
Organization: Consulting Chemist
Lines: 44

In article <DEn4wJ.ABB@utu.fi>, arno@utu.fi (Arno Hahma) says:

>In article <42j3ek$fh8@geraldo.cc.utexas.edu>,
>Gerald L. Hurst <glhurst@onr.com> wrote:
>
>> > that describes a newer (1986) nitrogen rich explosive with a detonation
>> > velocity of from about 8.6 Km/Sec to 9.2 Km/Sec. RDX was first
>
>I wonder, if it is a caged, tetracyclic molecule with six N-nitro
>groups and six methylene groups. If so, do they give a synthesis for
>it in the paper?
>
>>that relationship is sometimes shakey. For instance HMX is said
>>to shoot a good 700 m/s faster than its cousin RDX, but the
>>brisance of the two appears to be about the same according to
>
>You'd see the difference, if you made, for instance, shaped charges out
>of the two materials. The one with octogen will penetrate more if the
>same dimensions and geometries are used. The brisance tests are pretty
>crude and do not necessarily show differences under 10 % or so.

Actually, I based my statement on the 200 gram bomb sand test.
If you can see the difference in shaped charge tests I would 
be able to detect it with the plate dent test also. You and I
both know that shaped charge test reproducubility depends on
accurate work. The same is true of the plate dent test.
Reproducibility is more like 2-3% than 10% with a little care.
I have not compared HMX and RDX with the plate dent test nor
have I seen any data.

I assume you measure hole volume rather than depth. Can you 
give us some examples of relative performance?

Jerry