Sciencemadness Discussion Board

The Definitive Down-low for Nitrocellulose

malford - 14-7-2013 at 11:33

I've read more accounts of nitrocellulose synthesis than I have hairs on my head. Every one of them claims to have special nuances. Sam barros claims to make cellulose hexanitrate which he says it highly explosive with a quick DDT while Roscoe Bodine, a veteran goer of this website, claimed that compound does not exist and that trinitrate is the highest nitration possible.

I've made nitrocellulose of some sort multiple times successfully. It was highly flammable when fibrous and dissolved crystal clear in acetone. But, I want to know I have the most highly nitrated cellulose possible and bouncing around internet anecdotes isn't going to cut it anymore. I'd like to iron out the wrinkles and establish what is the highest nitration possible and how to prepare it.

I'd like to offer this reference.

Hexanitrate is described as an explosive gun cotton, however, later it is listed an a "friable cotton" while other more highly nitrated compounds are listed as gun cottons. I'm not sure what to make of this. This is a very old reference.

I found the following table:


The preparation of Sam Barros' acclaimed cellulose hexanitrate was accounted for in this work as follow:


This chart thoroughly illustrates the properties of nitrocellulose obtained depending on the ratio of nitric acid, sulfuric acid and water. Based on this chart, if you are using 70% nitric acid and 98% sulfuric acid, and assuming that the remaining 30% and 2% respectively are water, then you would use a ratio of 35 ml/65 ml nitric to sulfuric to closely match the highest mark on the chart. This would give you proportions of 18.52% water/sulfuric and 38.46% nitric/sulfuric. Later, they claim to have achieved higher nitrogen content but it is not reflected on this chart.


In another part of this work, I found this to be interesting, though it is perhaps mostly theoretical.


In yet another part of this work, I found this, which seems to be empirically obtained.


Lastly from this reference, this shows both theoretical and as well as what appears to be empirical data.


Another, much more recent reference, contains this:


[Edited on 14-7-2013 by malford]

[Edited on 14-7-2013 by malford]

AndersHoveland - 14-7-2013 at 12:37

Under some acidic conditions, it is possible for cellulose to be hydrolyzed to glucose. Unfortunately, glucose does not take to nitration very easily, since the free aldehyde group tends to be oxidized to a carboxyl group, rendering the product soluble in the mixed acids.

Sucrose can be nitrated to the octonitrate. This has a higher nitrogen content than nitrocellulose.
Quote:

C12H14O3(NO3)8

The crystalline nitrate is very stable even up to temperature of fusion. Heated gradually from 33° up to 87° over a period of nearly two hours, it showed absolutely no signs of decomposition.

The crude product of the nitration of sucrose is a tough, viscous, semi-transparent mass, which can be pulverized on cooling to hardness. It has no definite solidification temperature and is unstable above 30°. It contains an average nitrogen content of 15.3%. Sucrose octanitrate has been separated from the crude nitration product and identified as well-defined crystals belonging to the ortho-rhombic or monoclinic system, more probably the latter. It melts at 85.5° and is very stable. Nitrogen and molecular-weight determinations gave values which are practically identical with those calculated for sucrose octanitrate.

The octanitrate behaves like the crude nitrated product with respect to heating in a flame, and to friction; but it is less sensitive to impact.

E. J. Hoffman, V. P. Hawss, (1918)



Note: for safety reasons, nitrated sugars should only ever be melted with a hot water bath.

[Edited on 14-7-2013 by AndersHoveland]

Trotsky - 14-7-2013 at 12:56

There are very good reasons not to bother with sucrose octanitrate, unless you really enjoy purifying a globby, unstable mess. I've done it and was left with a very difficult to properly neutralize gel shit. Additionally, it was hard to get decent yields without having a runaway. Never liked it.

Nitrocellulose is best, IMHO. At least for old school nitrated sugars. I just nitrated the same material three times at increasing temps and got great stuff that ddt well under confinement. It's best not to consider any nitrocellulose as hexa, penta, tetra or whatever nitrate, and instead consider the overall nitrogen percentage.

Trotsky - 14-7-2013 at 12:58

Oh and someone should rename this thread the definitive low down on nitrocellulose. I'd hate to hear that it's been associated with homosexual activities.

malford - 14-7-2013 at 13:23

Quote: Originally posted by AndersHoveland  
Under some acidic conditions, it is possible for cellulose to be hydrolyzed to glucose. Unfortunately, glucose does not take to nitration very easily, since the free aldehyde group tends to be oxidized to a carboxyl group, rendering the product soluble in the mixed acids.

Sucrose can be nitrated to the octonitrate. This has a higher nitrogen content than nitrocellulose.

Quote:

C12H14O3(NO3)8

The crystalline nitrate is very stable even up to temperature of fusion. Heated gradually from 33° up to 87° over a period of nearly two hours, it showed absolutely no signs of decomposition.

The crude product of the nitration of sucrose is a tough, viscous, semi-transparent mass, which can be pulverized on cooling to hardness. It has no definite solidification temperature and is unstable above 30°. It contains an average nitrogen content of 15.3%. Sucrose octanitrate has been separated from the crude nitration product and identified as well-defined crystals belonging to the ortho-rhombic or monoclinic system, more probably the latter. It melts at 85.5° and is very stable. Nitrogen and molecular-weight determinations gave values which are practically identical with those calculated for sucrose octanitrate.

The octanitrate behaves like the crude nitrated product with respect to heating in a flame, and to friction; but it is less sensitive to impact.

E. J. Hoffman, V. P. Hawss, (1918)



Note: for safety reasons, nitrated sugars should only ever be melted with a hot water bath.

[Edited on 14-7-2013 by AndersHoveland]

With regard to cellulose or sucrose, a higher nitrogen content would mean more gas is produced during decomposition, correct? Thusly meaning that the material would be more energetic for a propellant, binder or explosive, correct?
Quote: Originally posted by Trotsky  
Oh and someone should rename this thread the definitive low down on nitrocellulose. I'd hate to hear that it's been associated with homosexual activities.

It's quite possible that the low-down should be kept on the down-low.
Quote: Originally posted by Trotsky  
There are very good reasons not to bother with sucrose octanitrate, unless you really enjoy purifying a globby, unstable mess. I've done it and was left with a very difficult to properly neutralize gel shit. Additionally, it was hard to get decent yields without having a runaway. Never liked it.

Nitrocellulose is best, IMHO. At least for old school nitrated sugars. I just nitrated the same material three times at increasing temps and got great stuff that ddt well under confinement. It's best not to consider any nitrocellulose as hexa, penta, tetra or whatever nitrate, and instead consider the overall nitrogen percentage.

In fact, the first reference says basically that. Most nitrated cellulose is a mixture of various grades of nitration. So, my main aim is to figure out what the method produces the most highly nitrated cellulose. Could you elaborate on your method? What temps did you use? What ratios of acids?