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Author: Subject: extract nitrocelulose from ping pong balls
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[*] posted on 7-9-2011 at 10:04


Quote: Originally posted by Rosco Bodine  
You aren't making the distinction correctly for danger in manufacture of nitroglycerin versus nitrocellulose, or for the use of a dynamite compared with the use of nitrocellulose....nitroglycerin based dynamite wins that safety contest and probably wins on stability too. Nitroglycerin is safer, easier, and cheaper to manufacture commercially than nitrocellulose. But yeah given the easier processing if a person just insists that nitrocellulose is their preferred explosive, then it would make more sense to nitrate a particulate form of cellulose already in the mesh desired, to shortcut the otherwise tedious process. If you are looking for a practical explosive there are many better choices than nitrocellulose, just about anything else is better, less expensive and easier to make.
Probably the closest thing to any widespread use of an explosive containing nitrated cellulose was blasting gelatine, or gelatine based ammonia dynamites, or similarly a cheaper nitrostarch based dynamite.


Rest assured that a someone trying to improvise dynamite starting from scratch will have plenty of more chances of having an accident while preparing and handling the nitroglycerine than if he were to tinker with nitrocellulose. Nitroglycerine is dangerous even in small batches. I have made nitrocellulose a bunch of times and I have yet to have any incidents.

[Edited on 7-9-2011 by Blasty]
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[*] posted on 7-9-2011 at 10:34


I agree with Rosco on the practicality if cellulose nitrate as an explosive. Many other cheap alternatives exist that are both easy to obtain and easier to employ. When you think of ammonium nitrate and potassium chlorate based compositions and how easy they are to make cap sensitive, then using cellulose nitrate seems unnecessary. I have attempted detonating it only out of curiosity, but I had to keep scaling up my booster to an unpractical amount to get unadulterated, pressed cellulose nitrate to go full order.

As far as the hexanitrate issue, I have been exposed to this word in many different places over the years. Powerlabs is one of them. I just did a quick search but couldn't really find a credible source to clear this up. I don't remember what Davis had to say on this. I am on my phone right now, but once I get back to the computer I'll check COPAE. If you are right on this, and I bet you are, then I will edit my posts, and my thinking.

[Edited on 7-9-2011 by Bot0nist]




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[*] posted on 7-9-2011 at 10:51


Nitrating mixtures that won't really mix very well is trouble waiting to happen. Give it time.


Getting back to the OP the likelihood of this "rocket project" going anywhere using pyroxlin as a binder for rocket fuel is somewhere between slim and none, even before "ping pong ball extract" ever enters the proposition. Why not use shellac or red gum binder for which formulas and test data already exist?
Are ping pong balls cheaper? Anybody actually building rocket motors has a wealth of proven designs and fuel and binder systems from which to choose, so this entire proposition of extracting ping pong balls is lamely unbelievable. And using a trinitrated nitrocellulose binder has been reported leads to explosions.
Before this even goes further to well the military uses even double based propellants in rocket motors .....yeah and their munitions plants and ordnance designers spent millions developing the formulas and methods which isn't happening and isn't going to happen here. Based upon the foregoing, I would say to the OP ......get real.
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[*] posted on 7-9-2011 at 11:43


Quote: Originally posted by Rosco Bodine  
Nitrating mixtures that won't really mix very well is trouble waiting to happen. Give it time.


Are you referring to KNO<sub>3</sub> and sulfuric acid? Don't you employ a similar method in your TNP synthesis? Do you have trouble getting the potassium nitrate to dissolve in the sulfunated ASA mix?




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[*] posted on 7-9-2011 at 12:24


What I used for TNP was a hundred year old war time cottage industry proven NaNO3 and H2SO4 method which is better than using KNO3 in terms of economy of acid, adapted to use aspirin instead of phenol. Aromatic nitrations are quite different and better in safety and predictability than are the nitrations producing nitroesters which are inherently more unstable and susceptible to oxidation. The thermal dynamic is much different for aromatic nitrations where you need to conserve heat or add supplemental heating for modest sized batches, but cooling is required for even small nitration batches of nitroester. With aromatic nitrations it is much easier to stay out of trouble. With nitrations involving nitroesters, trouble can arrive quickly and the batch can cook off. The reaction temperature range is more narrow, and so are the other process parameters more sensitive to variables. Working with materials that are thixotropic, fibrous, makes matters worse than dealing with liquids that can mix more easily. You get variable local conditions in spots in a mixture that can't be kept blended well and those spots can be where decomposition sets in and cascades from there very rapidly. Usually if the contents can be ejected, the scattering itself cools things off, but if the mass is too large or is contained .....it can detonate.
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[*] posted on 7-9-2011 at 13:50


Quote: Originally posted by Rosco Bodine  
Be careful about generalizations with regards to nitrations because nitrations are specific to the thing being nitrated, as regards which nitrate is "best" or if any nitrate is best at all, as they are simply not interchangeable at will. There are specific combinations of acids, water content, temperature that definitely are governed by a kind of process curve and certain combinations are optimized while others simply are not optimized with regards to yield, safety, purity of product ect.
This is nitration process algebra....for sure not simple arithmetic. Actually the physical chemistry aspect is operative for most or many chemical processes, and nitrations are especially affected in ways where subtle changes can have substantial effect on how a nitration proceeds.



There was a discussion about this some time back. It was noted that in order of quantity with ammonium, potassium and sodium nitrate, sodium nitrate was more efficient, in that, less (solid nitrate) yielded more nitric percentage in a mixed acid.
I had basically thought that this was more of a question of "efficiency" in nitrogen bonding, yet experimentally it appears that those subtitles you mentioned throw a monkey wrench in the whole concept. Even from a simple distillation there doesn't seem to be THAT much of a difference.
So how did people arrive at this concept ?

One issue that I had thought was puzzling was that sodium had the lightest atomic weight of the three (with potassium being next and so forth). Superficially I would imagine this means little; however is it possible that it is contributory? I still tend to use sodium nitrate in a mixed acid although it demands more care in solution preparation than ammonium nitrate






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[*] posted on 7-9-2011 at 14:48


There's a chart in Urbanski concerning the general progression of nitrates activity for nitrations when mixed with sulfuric acid but there are exceptions where some
particular thing being nitrated will be peculiar in somehow having a preference for a particular ion. All of these haven't been identified to my knowledge. My educated guess is some nitrations may work even better still with a mixed nitrate, like a double salt in combination with sulfuric acid. Nitrocellulose is reportedly a material that will nitrate more fully in the presence of magnesium nitrate, and I am pretty sure I have seen the same thing claimed for ammonium and sodium nitrate. Somebody mentioned RDX nitrolysis being improved by lithium nitrate. Copper nitrate is another one I recall being mentioned but I don't recall what was being nitrated. And I have seen other metallic ions claimed to have catalytic effect on aromatic nitrations. How this was discovered I don't know if it was deliberate or accidental. But it is true that different nitrates behave differently and are not just arbitrarily interchangeable. There is also the acid loss involved with nitrates which form acid sulfates, which must factor into the reaction, but going by that logic alone it would be counter intuitive to expect sodium nitrate to perform better, yet somehow it does work very well so something mysterious is occurring.

One thing I know for a fact is that nitrosylsulfuric acid is produced when sodium nitrate is added to sulfuric acid, and there is plenty of it remaining in the spent nitration mixture
before it is quenched. The nitrosylsulfuric acid may even be the actual nitrating agent rather than free nitric acid.

This was discussed awhile back, about six years ago in another thread
http://www.sciencemadness.org/talk/viewthread.php?tid=4457&a...

Page 46 from Urbanski vol. 1

http://www.sciencemadness.org/talk/files.php?pid=52553&a...

blinded.midi
http://www.sciencemadness.org/talk/files.php?pid=52975&a... :D

[Edited on 8-9-2011 by Rosco Bodine]
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[*] posted on 7-9-2011 at 19:07


Quote: Originally posted by Bot0nist  
I agree with Rosco on the practicality if cellulose nitrate as an explosive. Many other cheap alternatives exist that are both easy to obtain and easier to employ. When you think of ammonium nitrate and potassium chlorate based compositions and how easy they are to make cap sensitive, then using cellulose nitrate seems unnecessary. I have attempted detonating it only out of curiosity, but I had to keep scaling up my booster to an unpractical amount to get unadulterated, pressed cellulose nitrate to go full order.


For easy to produce bulk explosives, nothing beats those cheap and widely available oxidizer salts you mentioned, no contest there. Making an explosive out of kerosene or xylene with ammonium nitrate or potassium chlorate is just about as easy and cheap as it will get. However, sometimes you can't resist the urge to experiment with other things, specially with those that have higher brisance/VOD, and nitrocellulose does have this advantage.

Nitrocellulose can work very well as a main charge. It was used as such by the military in the past (which speaks for its safety; the military has a reputation of being strict on what they approve as explosives based on several criteria, including safety.) The only tricky part is turning it into a powder and detonating it. Plain mercury fulminate seems to do the job very well on dry nitrocellulose, as Abel's classic experiments on the subject show. A dry nitrocellulose booster is enough to detonate the even safer damp/wet nitrocellulose.

Was the nitrocellulose you experimented with produced from cotton or from cellulose powders (microcrystalline or otherwise)? What I am interested in knowing is whether these nitrated cellulose powders work as well as the powdered gun-cotton of the old days.
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[*] posted on 7-9-2011 at 20:58


It was cotton and also filter paper I nitrated using mixed acid.

The guncotton used long ago as an explosive was wet with water and compressed in metal cans. A booster was used to detonate the wet material. It was kept wet for safety and because of the deterioration of the inherently unstable nitrocellulose. If it was a practical explosive then it would not have been replaced quickly by other more stable explosives. Guncotton is a low density explosive and is obsolete on several counts. If you are convinced guncotton is just the thing for an explosive then it is a real mystery why.
You are banging your head on a wall seeing practicality that isn't there.

How come a thread about extracting pyroxlin from ping pong balls ostensibly for use as a binder in a "rocket project" has morphed into a thread about the dubious utility of guncotton for use as an explosive, none of this seems to be tracking very well. There seems to be an impracticality about that idea too.

If you want a lot of detailed info on nitrocellulose

http://books.google.com/books?id=n6aEAAAAIAAJ&printsec=f...

http://books.google.com/books?id=3Y8PAQAAIAAJ&printsec=f...



[Edited on 8-9-2011 by Rosco Bodine]
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[*] posted on 8-9-2011 at 01:54


Quote: Originally posted by Rosco Bodine  
It was cotton and also filter paper I nitrated using mixed acid.

The guncotton used long ago as an explosive was wet with water and compressed in metal cans. A booster was used to detonate the wet material. It was kept wet for safety and because of the deterioration of the inherently unstable nitrocellulose. If it was a practical explosive then it would not have been replaced quickly by other more stable explosives. Guncotton is a low density explosive and is obsolete on several counts. If you are convinced guncotton is just the thing for an explosive then it is a real mystery why.
You are banging your head on a wall seeing practicality that isn't there.

How come a thread about extracting pyroxlin from ping pong balls ostensibly for use as a binder in a "rocket project" has morphed into a thread about the dubious utility of guncotton for use as an explosive, none of this seems to be tracking very well. There seems to be an impracticality about that idea too.

If you want a lot of detailed info on nitrocellulose

http://books.google.com/books?id=n6aEAAAAIAAJ&printsec=f...

http://books.google.com/books?id=3Y8PAQAAIAAJ&printsec=f...


The reason why nitrocellulose was gradually abandoned as the main explosive charge is because its even greater value as a propellant outweighed its value as an explosive. Other explosive materials, like TNT, which could not be made into suitable propellants, gradually displaced it for reasons of material economy (not necessarily because they were better or easier to produce; nitrocellulose is in fact more powerful than TNT, and seems less complicated to make too.)

The gradual abandonment was not that quick either. As late as the 1910s you can still find praise for nitrocellulose, specially when wet, the combination of its force + safety making it an unsurpassed explosive for mines, torpedos and demolition purposes:

"Gun cotton is recommended for use (when wet) for mines, torpedoes and demolitions of all kinds. Its great value as a disruptive agent rests upon its great force and in its safety in manufacture, storage and handling. It is less liable to accident or spontaneous explosion than any other explosive now used, and when kept in storage in a wet state it is non-explosive except with a powerful detonator or a small piece of dry gun cotton." (Frank Thomas Hines, Franklin Wilmer Ward, "The service of coast artillery", 1910)
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[*] posted on 8-9-2011 at 06:08


It would never make sense for a government, especially a government at war to use many different explosives (with all the expense and inefficiencies of many different processes), if one explosive and one process would have done. It is much more inefficient to use many, and would never be allowed unless there was a very good reason.

Rosco is right as far as I am concerned. I haven't done a detailed study, but from what I have seen its use as an explosive was in some very specialized applications like torpedoes where some of its characteristics (like the ability to detonate when wet with water) were desirable. Nitrocellulose was used in some other military ordnance too, but from what I have read it was normally only used when supplies of TNT and other cheaper, normally safer and more effective explosives were in short supply. Nitrocellulose is relatively more expensive and problematic to manufacture and utilize for the most part. Its best use is in smokeless powder. It is an invaluable component of gelatin dynamites though, of which I am very fond. For the last two examples the lower nitrated form of nitrocellulose would be used. Some people call this dinitrocellulose, but in reality all samples are actually a mixture of nitrates. The more highly nitrated form is insoluble in nitroglycerin.


I believe cellulose trinitrate and cellulose hexanitrate are basically the same thing. Cellulose is a polymer made up of the monomer glucose, so cellulose hexanitrate is just describing two cellulose trinitrate units. I think this is what is going on anyway.



Thought this might be of use. The following is taken from the Encyclopedia Britannica, from the section on nitrocellulose. Google the webpage if you want to see the diagram described in the first line of the write-up.

"In unaltered cellulose the X in the molecular formula represents hydrogen (H), indicating a presence on the cellulose molecule of three hydroxyl (OH) groups. The OH groups form strong hydrogen bonds between cellulose molecules, with the result that cellulose cannot be softened by heat or dissolved by solvents without causing chemical decomposition. However, upon treatment with nitric acid in the presence of a sulfuric acid catalyst and water, OH groups are replaced by nitro (NO2) groups. In theory, all three OH groups can be replaced, resulting in cellulose trinitrate, which contains more than 14 percent nitrogen. In practice, however, most nitrocellulose compounds are dinitrates, averaging 1.8 to 2.8 nitro groups per molecule and containing from 10.5 to 13.5 percent nitrogen. The degree of nitration determines the solubility and flammability of the final product.

Highly nitrated cellulose—i.e., nitrocellulose containing more than approximately 12.5 percent nitrogen—will dry to a fluffy white substance known variously as pyrocellulose and guncotton. Guncotton is unstable to heat, and even carefully prepared samples will ignite on a brief heating to temperatures in excess of 150 °C (300 °F). Guncotton is employed in gunpowders, solid rocket propellants, and explosives. Moderately nitrated cellulose (containing approximately 10.5 to 12.5 percent nitrogen) is also flammable, though less violently so than guncotton, and is soluble in alcohols and ethers. Nitrocellulose of this type, once referred to by various names such as pyroxylin, xyloidin, and collodion cotton, is employed as a film-forming agent in solvent-based paints, protective coatings, and fingernail polishes.

In the commercial manufacture of nitrocellulose, wood pulp is the primary source of cellulose. Cellulose sheet and nitrating acids are fed into a reacting vessel, where nitration proceeds until the acids have been centrifuged from the nitrated product. Remaining acid is removed by washing the nitrocellulose slurry in water and boiling it in a caustic solution. The product is often treated with various stabilizers to reduce degradation under exposure to light and heat. In order to reduce the likelihood of combustion, nitrocellulose is usually stored and transported in water or alcohol."


[Edited on 8-9-2011 by Hennig Brand]
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[*] posted on 8-9-2011 at 07:03


Quote: Originally posted by Hennig Brand  



I believe cellulose trinitrate and cellulose hexanitrate are basically the same thing. Cellulose is a polymer made up of the monomer glucose, so cellulose hexanitrate is just describing two cellulose trinitrate units. I think this is what is going on anyway.

[Edited on 8-9-2011 by Hennig Brand]


Thanks! I needed clarity.:)




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[*] posted on 9-9-2011 at 08:54


I hope no one minds me posting this. I think Mr Cool from E&W provided a pretty good explanation as to why cellulose hexanitrate is probably named the way that it is.

This is a copy/paste from an archived copy of the E&W thread on cellulose hexanitrate.

"Mr Cool May 10th, 2002, 02:28 PM
To try and answer the qn. about why good NC can be called cellulose hexanitrate:

A glucose molecule has 5 hydroxyl groups, take two off for it to join to it's neighbours and it has three left. So this part of the cellulose polymer can be nitrated 0, 1, 2 or 3 times.
The hexanitrate refers to two of these units joined together. I suppose this is because it's possible to have NC with, for example, an average of 2.5 nitrates per monomer, but you could hardly call it cellulose di-and-a-half-nitrate, so they use two monomers and call it pentanitrate. I dunno what you'd do if you had an average of 2 1/3 nitrate groups per monomer...
That's why I think it is anyway. I could be wrong.
The N% is a much better scale to use."


[Edited on 9-9-2011 by Hennig Brand]
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[*] posted on 9-9-2011 at 09:21


Quote: Originally posted by Rosco Bodine  

The guncotton used long ago as an explosive was wet with water and compressed in metal cans. A booster was used to detonate the wet material. It was kept wet for safety and because of the deterioration of the inherently unstable nitrocellulose. If it was a practical explosive then it would not have been replaced quickly by other more stable explosives. Guncotton is a low density explosive and is obsolete on several counts. If you are convinced guncotton is just the thing for an explosive then it is a real mystery why.

If you want a lot of detailed info on nitrocellulose

http://books.google.com/books?id=n6aEAAAAIAAJ&printsec=f...

http://books.google.com/books?id=3Y8PAQAAIAAJ&printsec=f...



I would mention in passing —

Can be had at Google.com/books

Compressed Gun Cotton for Military Use

TRANSLATED FROM THE GERMAN of MAX VON FORSTER WITH
AN INTRODUCTION MODERN GUN COTTON, MANUFACTURE,
PROPERTIES AND ANALYSIS. BY Lieut JOHN P. WISSER, USA
NEW YORK: I). VAN NOSTRAND, PUBLISHER, 23 Murray and 27
Warren Streets. 1886.

Byda - Worden also published Technology of Cellulose Esters
in ten volumes! I own volume 8. I haven't checked Google
Books for this. I own an original copy of his two volume opus.

I am pretty (very) sure you can DL this from G books —

Smokeless Powder, Nitro-Cellulose , and Theory of the
Cellulose Molecule
John B Bernadou
1901

The British used NC demo charges in WWII.


------
Under-Water Storage of Smokeless Powder
By FRED OLSEN
Army Ordnance IV [24] 372
May-June, 1924

INFORMATION has been received from several sources that the subject of storing
powder under water is receiving considerable attention abroad. The ad-vantages of
immersing nitrocellulose powder in cold mountain lakes were apparent. The constant low tem-
perature conditions prevailing there could be expected to retard the decomposition of
nitrocellulose which would normally take place in powders stored in magazines the average
temperature of which would be considerably higher and in which there would undoubtedly be
rather wide variations in temperature. It was hoped that by so doing the stability life of
propellant powder might be increased by several years, a conservative estimate being that
the life of the powder would be ten years longer than the average expectancy of fifteen years.

In addition to the advantage of prolonged stability, the very important advantage was
indicated, namely, that the hazards would be very materially decreased. Dangers from fire or
explosion would be eliminated and constant supervision of storage areas unnecessary.

To offset these advantages it was recognized that the water might act on the powder in
such a way as to reduce its solvent content, rendering the powder more brittle upon
subsequent drying. This expected change in the volatile content of the powder might also be
shown in impaired ballistic properties and possibly erratic velocities with occasional excessive
pressures. However, the reports from abroad indicated that powder which had been in
storage for several years could be given a simple drying treatment and fired in the gun for
which it was originally designed without appreciable variation in the velocity or pressure, nor
were the results markedly different when the powder was stored in sea water. The stability of
the samples was not injured, and in the case of one sample of powder which had been
immersed in sea water for several years the stability was even better than that of samples
stored in surveil-lance magazines under presumably air-tight conditions. The results quoted in
these reports were, however, entirely too meager to permit the drawing of definite con-
clusions, so that it was believed necessary to initiate a program at Picatinny Arsenal which
would definitely show the advantages or disadvantages connected with under-water storage.

Powder of three widely varying granulations was selected, namely, for the 75-mm. gun,
155-mm. gun, and 12-inch gun, placed in specially prepared boxes provided with numerous
openings to allow free circulation of water, and lowered into Picatinny Lake to a depth of at
least three feet below the surface. An equal amount of powder was stored in a magazine in
order that comparative tests could be made whenever samples were removed from the lake.
A complete chemical and ballistic examination was made of the powder for the 75-mm. and
155-mm. guns and complete chemical examination made of the powder for the 12-inch gun.
The powder at the beginning of the test was normal in every way. At the end of six months,
samples were taken from the lake and subjected to the same tests that were made at the be-
ginning of the program. No appreciable change had occurred in any of the samples. The
stability as judged by the 135° Methyl Violet tests was somewhat better in the case of pow-
der which had been placed under water, but small irregularities in this test are frequently
encountered and it is not contended that these tests constitute evidence that the chemical
stability has been improved. No variation in ballistic properties of the powders tested was
observed.

These first tests indicated one point, namely, that little difficulty was to be anticipated
in reconditioning these powders for use after storage under water. If subsequent tests
corroborate this first result, which is admittedly obtained at a very early date, it will be an
exceedingly simple operation to remove the powder from the water, wash in flowing water to
remove silt or deposited organic matter, and finish the treatment with an air drying operation
at 40° or 50° C. for a few hours.
Even if it should be shown that prolonged storage under water affects the reduction of
the residual solvent to a point at which the powder becomes too brittle, it is quite probable
that it would be more profitable to rework these stocks of powder than to prepare the powder
anew from raw materials. It is further to be considered that in time of stress these stocks
might constitute very valuable sources of the essential raw materials—cellulose and nitric
acid.

In conclusion, it is believed that the under-water storage of smokeless powder offers
many advantages, and the results to date are at least of favorable indication. The only
difficulty which can be foreseen at the present time is the possible clogging of the minute
perforations of the powder grains with organic matter, which will not be removed by any
ordinary washing treatment. This, however, is not regarded as a very serious condition.

-------
A bunch of years ago Unk Sam was offering for sale 1 000 000
lbs of NC [gun cotton?] stored underwater in a lake at Picatinny
Arsenal.

Sorry to say at the time I didn't follow up to see if/who bought
it. Me thinks transporting it would have been a major problem!
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[*] posted on 9-9-2011 at 10:22


This webpage shows the hazard classification of 12.6% nitrocellulose wet with different amounts of water or alcohol.
Notice that once you have at least 25% water the material has a UN hazard classification of 4.1 which is flammable solids and self reactive substances and desensitized explosives.

http://www.ilo.org/legacy/english/protection/safework/cis/pr...


This webpage shows the hazard class symbols and gives a description for each.

http://www.ericards.net/psp/ericonline.psp_adrdangerlabels?p...


This webpage is for aluminum powder. Notice that the second entry for aluminum about half way down the page is for coated aluminum powder, which has the same UN hazard classification as our 12.6% nitrocellulose with 25% or more water by weight.

http://www.inchem.org/documents/icsc/icsc/eics0988.htm


It would most likely be inconvenient but it looks like it could be shipped.


[Edited on 9-9-2011 by Hennig Brand]
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[*] posted on 9-9-2011 at 10:32


Quote: Originally posted by Hennig Brand  


This webpage is for aluminum powder. Notice that the second entry for aluminum about half way down the page is for coated aluminum powder, which has the same UN hazard rating as our 12.6% nitrocellulose with 25% or more water by weight.

http://www.inchem.org/documents/icsc/icsc/eics0988.htm


It would most likely be inconvenient but it looks like it could be shipped.


Sure. However.... 1 000 000 lbs of NC and 250 000 lbs of
water.... is going to need one impressive box! And a lot of
stamps.
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[*] posted on 9-9-2011 at 11:16


It is even worse than that I think. I think they mean 25% of the total weight is water. So 1 000 000 lbs NC and ~333 333 lbs of water. Yes, a very big box and a lot of stamps.;)

edit:
IIRC, the last time I checked a lot of the transport trailers around here were hauling about 40 tonnes to the load. So 16 loads should just about do it, if hauling 40 tonne loads. Unless I goofed somewhere.



[Edited on 9-9-2011 by Hennig Brand]
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[*] posted on 9-9-2011 at 12:06


Quote: Originally posted by Hennig Brand  
IIRC, the last time I checked a lot of the transport trailers around here were hauling about 40 tonnes to the load. So 16 loads should just about do it, if hauling 40 tonne loads. Unless I goofed somewhere.



Yup. And unless you store it in your lake, I hope
you have a really large magazine well isolated!

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Julian S. Hatcher

Curtis Bay Powder Fire

During 1928, when I was Ordnance Officer of the Third Corps Area of the U. S.
Army, a magazine containing 600,000 lbs. of small arms rifle powder burned at
Curtis Bay Ordnance Depot, only a short distance from my office, and I had a
chance to see what happened .

The magazines were situated in rows, no magazine being closer than 400 feet to
the next, according to the Army tables of distances for magazines in force at the
time.

Two laborers with a team of mules were about to start some earth moving
operations with a scraper, and they stopped by a magazine, set their bags of
lunch on the ground, stood their shovels against the magazine wall and hung
their overalls on them. About that time they heard a loud rushing sound from the
magazine next in line, which was 400 feet away. This was described as sounding
like the lifting of the safety valve on a locomotive. Almost instantly flames burst
out of the doomed building, and the men started to run, but the heat became so
intense that they fell to the ground, fortunately in a small depression, which
shielded them slightly, and they escaped with blisters on the backs of their necks
but no serious injury. The team of mules simply trotted around the corner of the
building, where they stood, shielded from the direct rays of the heat. The men's
lunch bags and overalls burst into flame, and the shovel handles were charred.

The whole thing was over almost as suddenly as it began. In a minute and 50
seconds the fire was out, and where a magazine had stood containing 600,000
lbs. of powder, there was only a concrete foundation strewn round with seared
and twisted sheets of steel which a few minutes before had been the walls and
roof of the building.

An airplane was flying nearby at the time at an altitude of 1600 feet, and the pilot
said that a yellow pencil of flame shot up an estimated 2000 feet higher than he
was, then slowly died down. The recording thermometer on the outside of the
headquarters building over half a mile away showed a sharp rise in temperature
lastinq a minute and fiftv seconds, from which the duration of the fire was
deduced. This fire was thought to be due to spontaneous combustion of the
powder, sometimes possible when powder is stored in bulk, but which does not
occur when it is in small cans such as are used by handloaders, where any
incipient rise in temperature can easily be dissipated.


----------
DE Jarrett
Derivation of the British Explosive Safety Distances
Prevention of and Protection Against Accidental Explosions of Mutions, Fuels and
Other Hazardous Mixtures
Annals of the New York Academy of Sciences Volume 152, Art. 1 Pages 1-913
October, 28 1968


4.3 Correctness of Categorization

It has been assumed in the foregoing that the only important effect of an incident with
a Y-type explosive is radiant heat, and unconfined cordite has been quoted as the main
example. However, the effects produced on ignition of a propellant depend on various
factors such as confinement, surface area, composition. Theoretical and experimental
work on burning to detonation is not sufficiently far advanced to enable a prediction to
be made, theoretically or by extrapolation from laboratory tests, as to behavior of large
amounts of propellants in all the Situations encountered, and reliance still has to be
placed on ad hoc practical testing, sometimes on a very large scale.

A few trials in which large quantities of cordite were burnt under confinement were
carried out at Heligoland**. In the first trial, 40 tons of cordite in boxes were placed in a
thick concrete room, sunken, with a light wooden roof at ground level. The fire lasted
only for a few minutes and did no damage beyond burning all the wood of the structure.
Some boxes of cordite were thrown out without being ignited.

In the second trial, 20 tons of cordite in boxes were stacked in a reinforced concrete
building with 6-inch reinforced concrete roof, three sides earth mounded, with a steel
door. The pressure on ignition blew off the door intact, lifted and revolved the roof.
Some burning boxes were thrown out.

In the third trial, 80 tons of cordite in boxes were stacked in a similar but stronger
building with 12-inch RC roof and 2 feet of earth cover. The flames initially emerged
through the door, then the roof was lifted and burning boxes were thrown out. Charred
boxes, many filled with unconsumed cordite, were thrown up to 200 yards.

In the fourth trial, 25 tons of boxed cordite were packed tightly into a very heavy
concrete underground command post. The door was heavy steel. Ignition produced a
violent explosion, chunks of concrete were thrown more than a mile, and a deep crater
was produced. No flame was observed but considerable smoke was. Technical
investigation of the debris showed that detonation had not in fact occurred.

Finally 100 tons of bulk cordite were loaded into an underground air raid shelter on
Heligoland which had about 60 feet of overburden and about 40 feet of burden to the
cliff face. A violent explosion was produced, which blew away the cliff face.

It is reasonable then to regard cordite as a risk for all normal storage conditions,
and to regard behavior of cordite as the standard for categorization.

To categorize propellants other than cordite, where no other information is available,
reliance is placed primarily on a simple test of heating a sample under heavy
confinement. For convenience in early trials, shell or bombs were used as the
containers, replaced at present by 3/8-inch mild steel cylinders, length 18 inches and
internal diameter 3 inches.

Although no direct comparison can be made with actual full-scale conditions, the
various propellants can be arranged in order of the violence of fragmentation of the
container. The various U.K. double base propellants fall in the lower half of such a list,
and there is a sudden jump in violence between these stick cordites and the propellants
in the top half of the list. At present, no propellants fit into this gap, and it forms a
convenient and reasonable dividing line, propellants showing more violence being
categorized as ZZ, those showing the same or less as Y.

The position of a particular propellant in the list is affected materially by its surface
area. Thus cordite in flake or powder form gives one of the most violent results. In the
case of cannon powders (single base propellants) the dividing line between ZZ and Y
behavior is drawn at a diameter (or in case of tubular propellants a web-thickness) of
0.0 18 inch, the thinner sizes producing an explosive effect due to surface area.

At the higher end of the list, the categorization may be obvious from simple tests.
Thus some small arms propellant may produce explosive effects without confinement
when the mass of propellant exceeds a critical value. It is possible in process rooms to
prevent the development of explosive effects by controlling the depth in the equipment
or containers. Practically all propellants could be thus limited to flame risk in storage
and transport, but the space required is generally prohibitive

------------------
** Helogland a small cliff-girded red sandstone island of some 520 ac located in the
North Sea 65 km offshore Northwest of Cuxhaven. Originally occupied by Friesian
herdsmen, was in turn controlled by the dukes of Schlwswig-Holstein in 1402. In 1714 it
became a Danish possession. 1807 the British seized it and 1890 transferred back to
Germany in exchange for Zanzibar &c.. The Germans at a cost of some $175,000,000
(19 something dollars!) transformed it into the "Gibraltar of the North Sea" to protect the
Ring of the Nibelung. Hütet das Gold! Vater warnte vor solchem Feind. Its military and
naval works were demolished in 1920-22 in accordance with the treaty of Versailles.

During WW II it like the famous ring reappeared. Severely bombed by the Allies its
final demise as a military instillation came at 1 P.M. on April 18,1947, when an
apocalyptic explosion shook island as 6,700 tons of bombs and ammunition in 14 miles
of bunkers and tunnels went up in a black mushroom cloud that curled 6,000 feet into
the sky. And the Ring was one again lost never to be seen again.


[Edited on 9-9-2011 by The WiZard is In]
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otonel
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[*] posted on 11-9-2011 at 10:40


You give me a lot of information like a library but more unnecessary for my research
I purified ping pong balls of camphor but the resultant product don`t have a visible burning speed improvement to initial material
Bot0nist , I use you synthesis and tomorrow will see what power and speed give that product and if is to explosive i will mix with some ping pong balls material
I read on the internet about nitrocellulose synthesis and I have a question: is nitrocellulose synthesis for rocket engine the same with nitrocellulose used for smokeless powder simple based
Anyway thank you for a lot of information that you give to me, and of curse for help in my research
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[*] posted on 11-9-2011 at 15:28


Quote: Originally posted by otonel  
"Ping-pong balls are made of nitrocellulose [pyroxylin] (cellulose dinitrate), specifically celluloid that consists of roughly 75% cellulose dinitrate and 25% camphor"
When I read this I thinking if I can make a rocket motor using nitrocellulose from ping pong balls
The problem in to find a solvent for camphor but not to disolve nitrocellulose
I try alcohol and acetone to separate nc. without any result
If you can help me with some suggestion I will be grateful



Title: Camphor
CAS Registry Number: 76-22-2
CAS Name: 1,7,7-Trimethylbicyclo[2.2.1]heptan-2-one
Additional Names: 2-bornanone; 2-camphanone; 2-keto-1,7,7-trimethylnorcamphane; gum camphor; Japan camphor; Formosa camphor; laurel camphor
Molecular Formula: C10H16O
Molecular Weight: 152.23
Percent Composition: C 78.90%, H 10.59%, O 10.51%
Literature References: Naturally occuring in both the d- and l-forms; orginally obtained commercially as the d-form from the camphor tree, Cinnamomum camphora T. Nees & Ebermeier, Lauraceae. Primarily manufactured from pinene as the racemate. History of isolation and production of natural and synthetic forms: I. Gubelmann, H. W. Elley, Ind. Eng. Chem. 26, 589 (1934); J. M. Derfer, M. M. Derfer in Kirk-Othmer Encyclopedia of Chemical Technology vol. 23 (John Wiley & Sons, New York, 4th ed., 1997) pp 865-866. Enantiomeric composition in oils of coriander, sage, and basil: F. Tateo et al., Anal. Commun. 36, 149 (1999). GC determn in human plasma: J. S. Valdez et al., J. Chromatogr. B 729, 163 (1999); in pharmaceutical formulation: E. Gonzálea-Penas et al., Chromatographia 52, 245 (2000). Review: Camphor and Camphor Containing Products (PB293503, 1979) 65 pp; J. S. Mossa, M. M. A. Hassan, Anal. Profiles Drug Subs. 13, 28-93 (1984). Review of use as starting material for syntheses: T. Money, Org. Synth. 3, 1-83 (1996).
Properties: White or colorless crystals or crystalline masses; also colorless to white translucent masses. Characteristic fragrant and penetrating odor. Pungent, aromatic taste. d425 0.992. mp 179°. bp101.3 kPa 209°. Volatilizes slowly. uv max (CHCl3): 292 nm. At 25° one gram dissolves in about 800 ml water, in 1 ml alcohol, 1 ml ether, 0.5 ml chloroform. Freely sol in carbon disulfide, petr. benzin, fixed and volatile oils. Also sol in concd mineral acids, in phenol, in liquid NH3 and in liquid SO2. LD50 orally in mice: 1.3 g/kg (PB293505).
Melting point: mp 179°
Boiling point: bp101.3 kPa 209°
Absorption maximum: uv max (CHCl3): 292 nm
Density: d425 0.992
Toxicity data: LD50 orally in mice: 1.3 g/kg (PB293505)

Depending upon the degree of nitration the NC in la balls
may/may not be soluble in alcohol.

It has occurred upon me ... given the weight of ping-pong balls
... this is going to be an expensive project!


djh
---------
Extracted from :--

Journal of the Society of Chemical Industry.
No. 5, Vol,. XXXIII. MARCH 16, 1914.
New York Section.
Meeting held at Rumford Hall, New York, on Friday, January 23rd, 1914.
Mr.. C. W. THOMPSON IN THE CHAIR.
PRESENTATION OF THE PERKIN MEDAL TO Mr. JOHN WESLEY HYATT.

At this meeting of the Now York Section of the Society of
Chemical Industry, it is our pleasant duty to award the Perkin
medal to the person selected as most worthy for valuable work
done in applied chemistry………

What is the mental faculty which has made the recipients of the
Perkin medal what they are ? In what respect do these men
differ from their fellow chemists, so as to render them
especially successful in the applica¬tion of chemistry to the
arts ........ in the case of Hyatt, who saw in the drop of dried
collodion the possibility of producing a plastic mass, which was
finally obtained in celluloid.

Mr. JOHN WESLEY HYATT acknowledged the receipt of the
medal in the following words :—

From my earliest experiments in nitrocellulose, incited by
accidentally finding a dried bit of collodion the size and
thickness of my thumb nail, and by my very earnest efforts to


find a substitute for ivory billiard balls……


Other seriously objectionable features became apparent. In
order to secure strength and beauty only colouring pigments
were added, and in the least quantity ; consequently a lighted
cigar applied would at once result in a serious flame, and
occasionally the violent contact of the balls would produce a
mild explosion like a percussion guncap. We had a letter from a
billiard saloon proprietor in Colorado, mentioning this fact and
saving he did not care so much about it, but. that instantly
every man 'n the room pulled a gun…..


My brother took some samples to the American Hard Rubber
Company, with the view of interesting them. They employed
the late Professor Charles A. Seeley, who had made collodion
for the Government during the Civil War, to investigate the
matter. He came to our place in Albany, N.Y., and we
conducted the whole process for his inspection, very
successfully. He remarked that he had come prepared to detect
some chicanery, but could see no deception, and expressed
himself as satisfied. He kindly advised us that if, accidentally or
otherwise, we were to apply a little too high temperature, the
quantity we were dealing with would inevitably destroy us with
the building and adjacent property. While we did not accept this
as true, it was disturbing. The following day between 12 and 1,
when all were out, I rigged up a four-inch plank used as a vice-
bench, braced it between the floor and ceiling, between the
hydraulic press and the hand pump, intending it to shield me
from possible harm. I then prepared the mould, heating it
to about 500 degrees Fahrenheit, knowing it would certainly
ignite the nitrocellulose and camphor, and would abide by the
result. The gases hissed sharply out through the joints of the
mould, filling the room with the pungent smoke. The mould,
press, building and contents were there, including myself, very
glad that I did not know as much as the Professor………

Chance favours the prepared mind: 3
Chemistry in Action #31 Summer, 1990

Three discoveries from collodion

Collodion, a solution of cellulose nitrate in ether and alcohol,
figures in at least three accidental discoveries of industrial
importance. The first successful synthetic plastic was celluloid,
which was originally made to replace ivory in billiard balls. In
1863 a manufacturer of billiard balls offered a prize for a
successful substitute and two brothers, John Wesley and Isaiah
Hyatt began experimenting with various materials. John cut his
finger white investigating mixtures of paper and sawdust,
bonded by glue. He went to the cupboard to put some collodion
on the wound, a popular treatment at that time. He found the
collodion bottle overturned, with its contents spilled leaving a
hard sheet of cellulose nitrate on the shelf. Hyatt realized that
this might be a better binder than glue for his paper and
sawdust mixture. Several experiments later the Hyatt brothers
discovered that cellulose nitrate and camphor, mixed with
alcohol and heated under pressure made an ivory substitute.
They didn't win the prize, however, as their balls were apt to
explode unexpectedly. But in 1870 they patented their plastic
under the name of "Celluloid" and it was used for plastic collars
and cuffs, knife handles, buttons etc.

An expl ode to John Hyatt

Now John Hyatt's 'Wild West' billiard balls
Where the talk of the saloons and halls
When they hit the road
They were apt to explode
You can bet that they started some brawls
PEC


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[*] posted on 6-4-2012 at 13:04


Quote: Originally posted by Hennig Brand  



This webpage is for aluminum powder. Notice that the second entry for aluminum about half way down the page is for coated aluminum powder, which has the same UN hazard classification as our 12.6% nitrocellulose with 25% or more water by weight.

http://www.inchem.org/documents/icsc/icsc/eics0988.htm
and if you want a rocket engine, use a CO2 tube, and fill it with a mix of Zn and S with a ratio of: 2.04g Zn/1g S
(launch it from a tube like an AT4)


It would most likely be inconvenient but it looks like it could be shipped.
[Edited on 9-9-2011 by Hennig Brand]

if you want Al powder you should just go to a paint store,
its pretty cheap, and they have all types of metal powders for pigments and stuff

[Edited on 6-4-2012 by Pyro]
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[*] posted on 5-4-2021 at 11:32
Celluloid is gone


Ping pong balls are made from a different material since 2014/2015. Due to its flammable nature. Increasingly harder to find celluloid based PPB.
1,
https://www.tabletenniscoach.me.uk/guide-to-the-best-table-t...
2,
https://www.rocketryforum.com/threads/nitrocellulose-ping-po...
3,
https://www.ittf.com/2020/01/28/transition-celluloid-plastic...

"The transition from celluloid to plastic balls

28 Jan 2020

Always aiming to take the sport of table tennis in a bright and innovative direction, the International Table Tennis Federation (ITTF) agreed upon a bold decision in 2014 to move away from the long-established celluloid ball in favour of a new approach based around a new compound.

One man who played an important role in the transition process was Equipment Committee member, graduated mathematician and actuarial analyst Dr. Torsten Küneth who has kindly taken the time to speak about the evolution of the table tennis ball over the past six years.


Celluloid is gone

It was the key aim when the so-called plastic ball was introduced on 1st July 2014 after several years of research and development: the ITTF wanted to move on from celluloid and now it has become a reality. The last supplier of celluloid balls has withdrawn approval, and by end of 2020, the last of these balls will disappear from the list.

With safety awareness growing worldwide, the flammability of the ball had become a risk driver. There was no doubt that the ITTF had to act, also to anticipate regulations which might make the use of the balls impossible in certain countries. However, action had to be taken thoroughly and not in a rush.

Not only was it decided that the specifications for the new ball be almost identical to the celluloid one – in addition, ITTF took the opportunity to tighten the requirements for size and roundness, keeping the hurdles quite high for manufacturers when they experimented with new materials.

It was a huge challenge to get approvable balls on time. Especially the right combination of hardness, roundness and bounce height was tricky and led to a series of trial-and-error, but we did not respond by weakening the Technical Leaflet, and to me this was very important.

The decision proved the correct one, because in January 2014 all manufacturers managed to present models which passed the required lab test series, and by end of that year a total of 26 different suppliers had a celluloid free ball approved....."


[Edited on 5-4-2021 by Mush]
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