Discussion:
Chlorate/sulfur flash powders
(too old to reply)
matthew
2008-03-13 19:20:34 UTC
Permalink
Chlorate flash powders containing sulfur were used in the past. What
was the safety record of these mixtures? How did they fare in long
storage?
mikes2653
2008-03-13 22:36:27 UTC
Permalink
Flash powders of any type have a chequered history.

The old chlorate/sulphur flash powders typically used a varnish
aluminum as the metal powder. Such powders are coarser than German
black or many atomized grades. They are also coated with stearic or
oleic acids as a consequence of the manufacturing product, and this,
together with their particle shape, gives them a lubricity not found
in other types of aluminum. It is true that machine tests (which may
understate physical differences between ingredients) show chlorate
flash powders to be somewhat more sensitive than perchlorate types, in
practice the slipperiness of the aluminum used in the typical chlorate
flash mix compensated for the additional sensitivity. Also,
perchlorate flash powders aren't a great deal less sensitive than the
chlorate type. The hazard in actual use is high for both.

As for keeping, I have shot old shells that have been in storage for
years and havr not had problems with them. Worries about the acidity
of sulphur and spontaneous combustion resulting from deterioration of
chlorate/sulphur compositions are relics of the nineteenth century,
when star compositions containing perhaps 20% sulphur with a chlorate
oxizider were dampened, generally using something like gum arabic
solution, which has a bad tendency to turn sour. Potential for an
unwanted reaction is much higher under such conditions is much greater
than in a dry mixture like flash powder. There were also
characteristic impurities left by the then-current processes of
chemical production. Modern match-grade potassium chlorate, and
sulphur extracted by the Frasch process or removed from petroleum by
the amine process are of much higher and more uniform purity than the
materials of 150 years ago. These points should be borne in mind when
reading the older pyrotechnic literature.
Post by matthew
Chlorate flash powders containing sulfur were used in the past. What
was the safety record of these mixtures? How did they fare in long
storage?
matthew
2008-03-13 23:42:39 UTC
Permalink
Post by mikes2653
Flash powders of any type have a chequered history.
The old chlorate/sulphur flash powders typically used a varnish
aluminum as the metal powder. Such powders are coarser than German
black or many atomized grades. They are also coated with stearic or
oleic acids as a consequence of the manufacturing product, and this,
together with their particle shape, gives them a lubricity not found
in other types of aluminum. It is true that machine tests (which may
understate physical differences between ingredients) show chlorate
flash powders to be somewhat more sensitive than perchlorate types, in
practice the slipperiness of the aluminum used in the typical chlorate
flash mix compensated for the additional sensitivity. Also,
perchlorate flash powders aren't a great deal less sensitive than the
chlorate type. The hazard in actual use is high for both.
As for keeping, I have shot old shells that have been in storage for
years and havr not had problems with them. Worries about the acidity
of sulphur  and spontaneous combustion resulting from deterioration of
chlorate/sulphur compositions are relics of the nineteenth century,
when star compositions containing perhaps 20% sulphur with a chlorate
oxizider were dampened, generally using something like gum arabic
solution, which has a bad tendency to turn sour. Potential for an
unwanted reaction is much higher under such conditions is much greater
than in a dry mixture like flash powder.  There were also
characteristic impurities left by the then-current processes of
chemical production. Modern match-grade potassium chlorate, and
sulphur extracted by the Frasch process or removed from petroleum by
the amine process are of much higher and more uniform purity than the
materials of 150 years ago. These points should be borne in mind when
reading the older pyrotechnic literature.
Post by matthew
Chlorate flash powders containing sulfur were used in the past. What
was the safety record of these mixtures? How did they fare in long
storage?- Hide quoted text -
- Show quoted text -
Thank you for the good information.

Another question: how does the performance of these flash mixtures
compare to that of the perchlorate/dark aluminum compositions?
f***@cableone.net
2008-03-14 05:07:01 UTC
Permalink
Post by matthew
Post by mikes2653
Flash powders of any type have a chequered history.
The old chlorate/sulphur flash powders typically used a varnish
aluminum as the metal powder. Such powders are coarser than German
black or many atomized grades. They are also coated with stearic or
oleic acids as a consequence of the manufacturing product, and this,
together with their particle shape, gives them a lubricity not found
in other types of aluminum. It is true that machine tests (which may
understate physical differences between ingredients) show chlorate
flash powders to be somewhat more sensitive than perchlorate types, in
practice the slipperiness of the aluminum used in the typical chlorate
flash mix compensated for the additional sensitivity. Also,
perchlorate flash powders aren't a great deal less sensitive than the
chlorate type. The hazard in actual use is high for both.
As for keeping, I have shot old shells that have been in storage for
years and havr not had problems with them. Worries about the acidity
of sulphur  and spontaneous combustion resulting from deterioration of
chlorate/sulphur compositions are relics of the nineteenth century,
when star compositions containing perhaps 20% sulphur with a chlorate
oxizider were dampened, generally using something like gum arabic
solution, which has a bad tendency to turn sour. Potential for an
unwanted reaction is much higher under such conditions is much greater
than in a dry mixture like flash powder.  There were also
characteristic impurities left by the then-current processes of
chemical production. Modern match-grade potassium chlorate, and
sulphur extracted by the Frasch process or removed from petroleum by
the amine process are of much higher and more uniform purity than the
materials of 150 years ago. These points should be borne in mind when
reading the older pyrotechnic literature.
Post by matthew
Chlorate flash powders containing sulfur were used in the past. What
was the safety record of these mixtures? How did they fare in long
storage?- Hide quoted text -
- Show quoted text -
Thank you for the good information.
Another question: how does the performance of these flash mixtures
compare to that of the perchlorate/dark aluminum compositions?- Hide quoted text -
- Show quoted text -
Matthew,

At the 2005 PGI convention staged at Mason City, Iowa, Jim Freeman
presented a seminar in which he mixed and then compared the confined
and unconfined burning charactertistics of 7 different flash
compositions. These included mixtures using different oxidizers and
metals, different particle shapes and sizes and, in one case, a
mixture that employed no metal of any kind. There was no
instrumentation employed and conclusions, such as they were, were
subjective in nature.

With the legalese out of the way, which mixture provided the biggest
"bang" and most aggressive PWAS (pressure wave at sternum)? A mixture
of potassium chlorate and two other components (no elemental metals).
Compared with the rest, this mixture was to my senses the best
performer.

On the flip side, it goes without saying that mixtures based an
potassium chlorate and certain other compounds/metals deserve respect
and caution. Handled incorrectly, they can maim and/or kill you
literally in a flash.

Tom C.
matthew
2008-03-14 17:08:32 UTC
Permalink
Post by f***@cableone.net
With the legalese out of the way, which mixture provided the biggest
"bang" and most aggressive PWAS (pressure wave at sternum)? A mixture
of potassium chlorate and two other components (no elemental metals).
Compared with the rest, this mixture was to my senses the best
performer.
Thanks!

What was were the two other components in this mixture? Antimony
trisulfide and sulfur?
f***@cableone.net
2008-03-14 22:36:40 UTC
Permalink
Post by matthew
Post by f***@cableone.net
With the legalese out of the way, which mixture provided the biggest
"bang" and most aggressive PWAS (pressure wave at sternum)? A mixture
of potassium chlorate and two other components (no elemental metals).
Compared with the rest, this mixture was to my senses the best
performer.
Thanks!
What was were the two other components in this mixture? Antimony
trisulfide and sulfur?
Mathew,

That is correct. Jim's choice of mixture was 12:4:3 by weight with
sulfur being the minority component.

Tom C.
r***@bestweb.net
2008-03-14 18:22:09 UTC
Permalink
Post by f***@cableone.net
At the 2005 PGI convention staged at Mason City, Iowa, Jim Freeman
presented a seminar in which he mixed and then compared the confined
and unconfined burning charactertistics of 7 different flash
compositions. These included mixtures using different oxidizers and
metals, different particle shapes and sizes and, in one case, a
mixture that employed no metal of any kind. There was no
instrumentation employed and conclusions, such as they were, were
subjective in nature.
With the legalese out of the way, which mixture provided the biggest
"bang" and most aggressive PWAS (pressure wave at sternum)?
Probably these should be referred to collectively as "salute mixes"
rather than "flash compositions", although some of them would've
provided a flash as well.
robert g smith
2008-03-14 23:16:05 UTC
Permalink
IF YOU MIX POTASSIUM CHLORATE AND ALUMINUM POWDER IT WILL BLOW UP IN YOUR
FACE ! DON'T DO IT ! Only Potassium Prechlorate is relatively safe with
aluminum powder and either sulfur or antimony sulphate ! Some books and
internet formulas show mixtures of potassium chlorate and aluminum powder
but they are all insanely instable ! I don't know where or how these
formulas were concocted.
Post by matthew
Chlorate flash powders containing sulfur were used in the past. What
was the safety record of these mixtures? How did they fare in long
storage?
mikes2653
2008-03-15 01:00:57 UTC
Permalink
Do you know this from experience, or are you just repeating something
you heard or read?

All flash powders are inherently hazardous. The danger of hyperbolic
anti-chlorate warnings like yours is not that they warn folks off a
hazardous mixture, but that they lull the reader into thinking that
"Only Potassium Prechlorate [sic] is relatively safe with aluminum
powder..." Probably as many or more industry deaths have resulted from
the use of perchlorate flash powders as of the chlorate type.

Test data as published by reputable authorities like Takeo Shimizu
show that the sensitivity of perchlorate flash powders is not much
less than that of chlorate flash powders. Making flash powder with any
ingredients is a risky activity and should not be undertaken without
prior pyrotechnic experience, appropriate equipment, and a suitable
work space.
Post by robert g smith
IF YOU MIX POTASSIUM CHLORATE AND ALUMINUM POWDER IT WILL BLOW UP IN YOUR
FACE !  DON'T DO IT !  Only Potassium Prechlorate is relatively safe with
aluminum powder and either sulfur or antimony sulphate !    Some books and
internet formulas show mixtures of potassium chlorate and aluminum powder
but they are all insanely instable !  I don't know where or how these
formulas were concocted.
Post by matthew
Chlorate flash powders containing sulfur were used in the past. What
was the safety record of these mixtures? How did they fare in long
storage?
h***@yahoo.com
2008-03-15 07:05:57 UTC
Permalink
Post by mikes2653
Do you know this from experience, or are you just repeating something
you heard or read?
Noble and valiant effort Mike, but simply give up on some of these
guys. I'm sure that Jack Drewes didn't give their facts to them via
AFN, nor did intentionally the PGI literature. So I too am starting to
question where some posters obtained these presumed facts. Certainly
there is nothing in Shimizu's FAST or or FAPS to suggest that a more
than nominal difference in frictional senitivity exists between
chlorates and perclorates exist, nothing in Lancater, Davis, Weingart,
Hardt, Conkling or any book published during the 20th century seems to
suggest that there is a significalt difference in the hazards
presented between chlorate and perchlorte composition, so where is
this perception that they is some great difference originating? Now
Mike, my library is far less vast than yours, but I believe I have
have a majority of the the 20th centurury literature available at my
fingertips (not that as you don't know, I sometimes need help in
locating small details in the texts.) Every one of the old guys from
whom I was didn't ever use PERC, and for the most part they died in
bed, usually at home with the "death watch" surrounding them. Sure,
there were numberous mentions of potassium perchlorate in the
fireworks literature even at the time, but until about 1980, nobody I
knew used it for anything.

Of course at that time all stars were being cut, and no one owned a
ball mill in the industry no one even knew was a ball mill was, let
along have one. Times and perceptions change. Now this small fact will
likely shock some readers. No old master in fireworks quite likely
ever owned a textbook...they had simply been tought by their fathers,
and very likely their fathers had been taught the craft from their
grandfathers, and their grandfathers that went before them. I guess
that I am a little weird, because I consider that to be a fine and
beautiful tradition. Trust me in telling you that both the arts and
the traditions are worthy of preservation.

Harry C.



.
Lloyd E. Sponenburgh
2008-03-17 11:49:39 UTC
Permalink
Post by h***@yahoo.com
Sure,
there were numberous mentions of potassium perchlorate in the
fireworks literature even at the time, but until about 1980, nobody I
knew used it for anything.
Of course at that time all stars were being cut, and no one owned a
ball mill in the industry no one even knew was a ball mill was, let
along have one.
A) Santores were rolling stars then.
B) G.W. Weingart had a ball mill, and described its purpose and its use
in his book.

But, then, we've had this discussion before.

LLoyd
Lloyd E. Sponenburgh
2008-03-17 11:55:50 UTC
Permalink
Post by h***@yahoo.com
Sure,
there were numberous mentions of potassium perchlorate in the
fireworks literature even at the time, but until about 1980, nobody I
knew used it for anything.
Sorry, I missed addressing that.

That you did not know anyone who used perchlorates isn't cardinal
evidence of its not being used.

"Numerous mentions" goes back.... way back. Even that little blue book
"Formulas and Trade Secrets" of 1932 has several perc formulae in its
fireworks section.

LLoyd
mikes2653
2008-03-17 17:33:49 UTC
Permalink
Some allowance has to be made in discussing general industry practice
for its innate conservatism and the dearth of published information
during the mid-20th century. I have in my collection a number of
manuscript formularies from both Italian and Italo-American
pyrotechnists from the period c. 1850 - mid 1960s. Rarely does one
find anything in them that was not in contemporarily published
literature, and in the later ones, even some of that is absent.

Both ball milling and stamp milling were used through the 1920s and
'30s, I suspect because commercial meal was expensive and Depression-
era economics gave a strong incentive to save every penny one could.
In compositions of this period one finds a distinction between home-
made meal and "A dust" of commercial origin. After WWII, the home
production of meal was mostly dropped. This reflected the rising cost
of labor with respect to that of materials. In the 'sixties it was
still possible to buy commercial powder for 50 cents a pound. At that
price, why would anyone ball-mill? I saw a stamp mill like the one
illustrated in Davis's book when visiting Rozzi's plant, but it had
not been used for years.

Some things we take for granted today as standard pyrotechnic practice
seemed largely unknown to the trade until the mid-seventies or even
beyond. Right up until it disappeared from commerce, Paris green was
the usual chemical employed for blue colors, typically with potassium
chlorate, stearine, and dextrine. Calomel had become too expensive as
early as the 'twenties, and fell out of use during the Depression; the
newer organic chlorine donors had been introduced in military
pyrotechnics, but my impression is that they were not used in civilian
fireworks until after the publication of Lancaster's first edition in
1972.

Thomas G. Hitt was an early advocate of potassium perchlorate and
patented a perchlorate flash powder in 1915. This was by no means
original, because a German patent had been taken out in 1898 on the
use of such a composition for photographic illiumination. Apart from
Hitt, though, I find little evidence of perchlorate either in flash
powder or in colors through the 'sixties amongst display fireworks
manufacturers. I think it caught on a bit earlier for consumer
fireworks as perchlorate colors are listed in a formulary I have from
Fabrizi (N.J. Fireworks Co.).

There was enough contact with the Japanese industry that maybe two or
three U.S. makers tried rolling stars before then, but here again I do
not think much was done here with round stars before Lancaster's first
edition appeared, with its translated excerpt from Shimizu's
"Hanabi" (1957). One maker I knew went to the trouble of getting
copies of that book (I got mine from him, c. 1968-9). He had a
Japanese woman he knew make a partial translation, the ms. of which I
now have, but she gave up before she could finish because of
difficulty with the technical vocabulary. So far as I know this book
had very little circulation here and Lancaster's book is the first
notice that drew much Western attention to round stars. Cut and pumped
stars were all most U.S. makers knew until the 'seventies.

I well remember the use of dichromates in photography and
photolithography from my first consciousness of the family printing/
publishing business - we used to make our own gum-bichromate (sic)
plate emulsion, apply it to a grained unsensitized plate in a
'whirler,' then expose the plates under carbon arc lamps - but so far
as I know the first published notice of potassium dichromate for
protecting powdered metals in pyrotechnics was Shimizu's article in
Pyrotechnica VIII (June, 1982).

Many innovations in fireworks that have now become standard industry
practice first were published in issues of Pyrotechnica. Winokur gave
us alternatives to the old standard meal, antimony, bright aluminum
tremalons. Shimizu - what hasn't he touched on? Ammonia strobes,
firefly, crackle, on and on. Jennings-White showed that crackle could
be made with bismuth instead of red lead. Roger O'Neill brought to our
attention the varied performance of different charcoals - something
that hadn't been discussed in print since the days of MM. Bottée and
Riffault, and had been forgotten in the interim. When we compare what
we have today with what there was 30 years ago it is astonishing. It
shows the value of open discussion and the sharing and publishing of
information.

I wouldn't be too hard on Harry, because it seems to me that his
picture of what was widespread industry practice during the period he
was active in the trade is basically accurate.





On Mar 17, 6:55 am, "Lloyd E. Sponenburgh"
Post by Lloyd E. Sponenburgh
 Sure,
there were numberous mentions of potassium perchlorate in the
fireworks literature even at the time, but until about 1980, nobody I
knew used it for anything.
Sorry, I missed addressing that.
That you did not know anyone who used perchlorates isn't cardinal
evidence of its not being used.
"Numerous mentions" goes back.... way back.  Even that little blue book
"Formulas and Trade Secrets" of 1932 has several perc formulae in its
fireworks section.
LLoyd
Mitich
2008-03-18 04:55:47 UTC
Permalink
[...his usual thorough and thoughtful knowledge]
Mike,

Thank you for continuing to share your knowledge in such a thoughtful
and complete way. It is a rarity for Usenet (and almost anywhere else,
for that matter). I'm a pyro tyro (but an middle aged scientist and
engineer of the old school) and I enjoy your posts here and on
Passfire for both the content and perspective.

-Mitch

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