Sciencemadness Discussion Board - Tri-Nitrocellulose

Tri-Nitrocellulose

Mr.O-Nitrate - 16-10-2003 at 09:45

Hey, I am new here. And i needed your guys input. I will soon make Tri-Nitrocellulose. I am going to mix 3 ml of HNO3 and H2SO4. And a little over .5 grams cotton. I was wondering if that amount would need a gas mask? I will be doing this outside and possibly with a fan to direct fumes away from myself. Thanks a lot

(oh yeah and the nitric acid is 60%) and for the sulfuric its around 90%

[Edited on 16-10-2003 by Mr.O-Nitrate]

vulture - 16-10-2003 at 10:14

You are referring to cellulosehexanitrate. Nitro is not the correct name and it also implies that you are not familiar with the substance you are going to make.

Please search this board and get your theory/precautions right before attempting the "synthesis".

Nevermore - 16-10-2003 at 10:30

i don't think is gonna work in that way...
better you check your doses and care to follow a correct procedure..
if everything goes fine you won't need a gas mask, if runaway occurr you will need a gas mask and a new tshirt, unless you promptly dump everything in cold water.

Tri-Di-Hex

Mr.O-Nitrate - 16-10-2003 at 14:25

Tri-3 Di-2 Hex-6
Arn't there 3 diff. types of nitrocellulose? or am i just a dumbass? My book shows it as 3 Nitrate groups(ONO2) I am very confused now. I will talk to my grandpa about this, he has a lot of knowledge in chemistry.

ok ok ok, heavily confused...

Mr.O-Nitrate - 16-10-2003 at 20:31

Can someone please supply me with their successful synth. to Nitocellulose? I have looked at the other topics in here and checked sites, they are all diff.

rooster - 16-10-2003 at 22:52

There is no such thing as hexanitrocellulose. As the cellulose polymer only has three -OH alcohol groups, it is only possible with a trinitrate. Although it is a ring structure with 6 carbons, it would bot be a polymer anymore if a nitro group was attached to all carbons!
For the cellulose structure, look at the top of this page (sorry I couldn't find a better structure)

http://www.lsbu.ac.uk/water/hycel.html

DiNitroCellulose is commonly known as colyoxylin, and TriNitroCellulose is known as pyroxylin. I think colyoxylin is the one used in ping-pong balls.

What I don't understand though, is why many nobody uses 99% HNO3 and H2SO4 for NC? I have only seen procedures with 70% nitric. When I nitrated cellulose with 99% acids, my products were fine, better than with 70%.
More prone to oxidation?

vulture - 17-10-2003 at 01:14

It's NOT a nitro compound, but a nitrate, which is a big difference.

If you look at a cellulose monomer, it's a trinitrate. But the nitrated form of cellulose is a polymer. The lower nitrated version have been used as plastic.

http://www.sciencemadness.org/talk/viewthread.php?tid=795

For the structure and more data about cellulosenitrate. Please search, I found this thread in 20s.

AngelEyes - 17-10-2003 at 03:57

For Information purposes only, quoted from a friend:

"I personally use a ratio of 1:3 nitric:sulphuric (the sulphuric is 95%+ drain cleaner) and then simply submerge in that nitrating mix as much cotton as it will take. I then leave this for several days at room temperature, although I cover the top of the vessel and keep it out of direct sunlight, before washing it several times in bottles water and then leaving in a weak solution of sodium carbonate for several more days, or until there is no more fizzing. Dry this at room temeperature for 24 hours or so (depending on humidity) and then it's good to go. Most of my product will dissolve in acetone OK, though I generally don't bother with this as the colloided product doesn't seem as useful as the 'raw' cellulose nitrate. I just use 0.5g (yes, just half a gram) in a paper tube with a clay bung - mostly for airsoft 'grenades'. 0.5g will give a nice report and will easily fit in a tube just an inch or two in length with an ID of no more than 2cm."

Your 60% nitric contains a lot of water so you may need to up the sulphuric level to better absorb this.

Vulture is dead right though - there's more info on NC than you can shake a stick at lurking around the web. Just be specific with your terms, use a decent search engine and don't just stop at page 1 of the results.

Thanks guys

Mr.O-Nitrate - 17-10-2003 at 08:42

Thanks for the links and the snyth. evreyone

Oh and this site www.powerlabs.org has a snyth. for Cellulose Hexanitrate.

(that one is for rooster)

Nevermore - 17-10-2003 at 09:59

i wish to say something about that.
for what i read it looks like you are very young, one of the big defect of younger is lacking of patience, when you are dealing with such matherials, acids, compounds, you should never hurry, or put things together just to make something, or handle wrongly.
One error could mean not death, but probably blindness and deafness..

IgnorantlyIntelligent - 17-10-2003 at 10:40

I had always thought that you could simply put some cotton into a beaker of nitric acid (70%-90%),
wait about 15 min. then remove it and wash it in water, then with a sodium bicarbonate/water solution, then with water again. Let dry, and its ready for use.
Maybe I'm a complete dumbass though.

rooster - 17-10-2003 at 12:10

Vulture, I can't find any info on the structure of hexanitrocellulose, powerlabs only has the formula for trinitro. I don't get this, sorry.

Don't you count the nitro groups on the monomer(or one "part" of the cellulose molecule)? I DO mean the monomer IN the polymer if you know what I mean. Hard to explain.

Do you mean it is a salt(three -ONO2 and three NO3- instead of the hydrogens or somethig? Can't be.

Anyways, you must be thinking different than me, because as I see it, the ring with six carbons, CAN have six nitro-groups, but it still needs two for the polymer bondings.

Sorry for the inconvenience. Hope I'll understand the problem...

right

Mr.O-Nitrate - 17-10-2003 at 14:04

Nevermore, your right. I am young and kind of inpatient. I have tryed to make cellulose nitrate, and it did not work out. I my H2SO4 was not pure enough. When it comes to working with explosives and hands on with chemicals I do not rush. And I respect them

age

Mr.O-Nitrate - 17-10-2003 at 14:14

I am 15, how about you guys?

Nevermore - 17-10-2003 at 14:51

your H2SO4 is not likely to be the cause, usually the drain opener is 96-98% H2SO4, is more likely your nitric is not good as is written on the bottle.
Anyway if you wanna concentrate your sulfuric just boil it up, use a very resistant pyrex becker since is gonna boil at very high temp and also do it outside, so that you won't drown in a sulfuric fog. Do it till the acid is heavily fuming deep thick white fumes.
Instead of nitrating cellulose, try to nitrate sugar first, is a little more easy as long as you follow the steps carefully and watch out for runaway, and the reaction is almost immediate (15min)

vulture - 18-10-2003 at 03:11

Rooster, celluloseNITRATE is an ester of nitric acid, not a NITRO compound.

This means a NO2 group will attach itself to a OH group of the molecule, replacing the H with the NO2, creating a C-O-NO2 bond. The free H combines with the OH from the nitric acid (HNO3 --> NO2 + OH) to form water again.

This is not the exact and correct reaction mechanism, but it's good as a general outline.

If you look at a cellulose monomer, you'll see it has 3 hydroxygroups. Please look at the link to another thread which has a gif which shows the structure.

Nitro compounds have a C-NO2 bond.

I know this is hard to grasp, I've struggled with it myself for quite some time.

Iv4 - 18-10-2003 at 03:53

lots of trial and error info.

Usually a one to one nitric and sulfuric acid is used and the concentrations of sulfuric and nitric acid being the same is said to be good(cant confim it though).

About the nitrate/nitro thing is it like methyl nitrate and nitromethane?

vulture - 18-10-2003 at 06:54

I would like to point out that that bombshock thread contains quite some misinformation and good examples of people who have no clue what they're doing. I'm being euphemistic now...

Yes, it's the same as methylnitrate/nitromethane.

Methylnitrate is an ester of nitric acid and is produced by reacting methanol (1 hydroxylgroup) and nitric acid.
.....H
.....|
H--C--O--NO2
.....|
.....H

Note that ONLY the NO2 is from the nitric acid, the oxygen that interconnects the carbon with the nitrogen atom was present in the "mother" molecule, methanol.

Nitromethane is made by reacting methane with nitric acid.

.....H
.....|
H--C--NO2
.....|
.....H

Marvin - 18-10-2003 at 07:56

That is mostly right vulture.

Nitrocellulose is a perfectly acceptable synonym for cellulose nitrate though, in the same way we call glyceroltrinitrate nitroglycerin. Technically anything with -NO2 in could be called a nitro compound, its not restricted to C-NO2 only.

The difference between nitromethane and methyl nitrate is obvios, however the same is not true generally. You can have nitric acid esters, most frequently called nitrates, C-NO2 compounds, most frequently called nitro compounds, N-NO2 most frequently called nitro compounds and salts of NO3- most frequently called nitrates. In general, to be absolutly clear there are C-Nitro, O-Nitro and N-Nitro compounds. So nitrourea is actually N-nitrourea and nitromethane is actually C-nitromethane. Carrying this furthur would get you C-nitromethanol and O-nitromethanol as equally valid names one would be a nitro compound as youve explained the other would be an ester.

Where there is no danger of assuming the most common form though, I dont see a problem. Nitrocellulose is in the books, so it may as well be used and the logic is more obvios than 'cellulosehexanitrate'.

Ha !

Mr.O-Nitrate - 18-10-2003 at 17:14

I thought so! I was thinking that anything with NO2 would be a nitro. The NO2 bonds to the O in nitocellulose. Same with NG. Some are connected to the carbon and some are connected to nitrogen. But i was thinking they would all be nitro because of the NO2. My book talks about that. Oh i just got 3 chem books for 3$ at this library sale
---------------------------------------------------
I did not want to start a new thread for this question.

I have acid resistant gloves, safety goggles(bought them off sciencelab.com), and I will be doing my Nitrocellulose synth. outside. The batch of nitrating mixture is about 4 mL. How big of a wif does it take to get sick? I know its 2 ppm, but is that a small whiff or a pretty big whiff?( oh and will i be needing an ice bath?)
----------------------------------------------------
I dont think my Drain opener H2SO4 was too pure, because it would not hiss when contacted with water.
----------------------------------------------------

EDIT by vulture: I've combined your 3 posts to one, PLEASE EDIT your posts instead of posting them directly underneath eachother.
[Edited on 19-10-2003 by vulture]

[Edited on 19-10-2003 by vulture]---oohh sorry

[Edited on 19-10-2003 by Mr.O-Nitrate]

KABOOOM(pyrojustforfun) - 19-10-2003 at 21:11

when explaining the structure of polysaccharides you usually need to show multi mono/di.. saccharide unites. in case of cellulose the monomere is a disaccharide called cellobiose. a comparsion between cellolose and amylose(a kind of starch) makes it clear:

cellulose:
<img src="http://www.angelfire.lycos.com/rnb/pjff/cellulose_PJFF.gif"> 
amylose: <img src="http://www.angelfire.lycos.com/rnb/pjff/amylose_PJFF.gif"> 

trinitrocellulose is meant to be cellulose hexanitrate 
btw recently terms such as nitrato and nitroxy are being used for organic nitrates.

Iv4 - 19-10-2003 at 23:56

I know its' proibaby one of the gayest threads there(I say probably because I dont visit the crime secion much)but still it covrs nearly every possible problem and trivial things like that.

rooster - 20-10-2003 at 00:13

KABOOOM: That was what I tried to put words on, the monomer/dimer thing. Now I get it all!

I have taken quite big gasps of NO2, and never become sick of it. Of course, your throat will be sore, but you will not die as long as you get fresh air immedeatly after. Try not to breathe it though!

I would use an ice bath, though you may not need it for those amounts. at least a cold water bath.

thanks

Mr.O-Nitrate - 20-10-2003 at 10:25

thanks. I will have pleanty of fresh air

Well im almost ready for doing that synth.

rooster - 22-10-2003 at 00:22

YESSS! Finally I found microcrystalline cellulose at a lab. It is like powder. When you nitrate it for use as a HE, it is hard to compress the nitrated "cotton wool" type. Also it will be easier to handle.

One question...

Why isn't there any nitrating procedures for NC with 99% HNO3 and H2SO4? I heard 70% HNO3 is more oxidizing than 99%, if so, wouldn't there be less oxydated, unwanted byproducts of cellulose when nitrate with higher % acids?

IgnorantlyIntelligent - 23-10-2003 at 14:24

When nitrating cellulose with ammonium nitrate and sulfuric acid, my cellulose totaly disolves in the acid. Ive tried it 3 times and the same thing happens every time.
I know we arent allowed to post things about failed attempts at synthesis's because of some strange reason but If anyone cares to throw an answer out to what might be going wrong I'd appreciate it alot.
BTW, over 6 threads in this forum alone have been closed in the last 6 days. Its not like closing it takes up less room on the forum right? Why not just leave it open? Im not questioning the great forum admins so dont take this the wrong way...I was simply wondering.

An explanation

Polverone - 23-10-2003 at 14:53

The reason these threads have been closed is because they are not focused on chemistry, are not about novel procedures, and tread ground that has already been tread many times before in other forums. Discussion of these well-known topics is discouraged here as a matter of policy. Beginners are welcome here, but only beginners who are able and willing to be self-directed learners. If you haven't read the FAQ, let me remind you of good sources of information for most simple questions:

The Usenet groups alt.engr.explosives and rec.pyrotechnics, and their archives on Google Groups
The Explosives and Weapons Forum archives
books, from an actual library or in electronic form (http://bcis.pacificu.edu/~polverone/, for example)

The books are especially important, since you can't tell BS from good information until you have some basics down.

IgnorantlyIntelligent - 23-10-2003 at 21:03

Ok, I'm not questioning the way you run the forum. I like being able to use this forum and read the very informational posts and replies people write.
And at the E&W forum, they ban people left and right. The admins here do not do that which is very much appreciated. Sorry if i ofended the forum or its admins in any way...it wasnt my intent to do so.

Now for a word on NC.
Since DDT occurs very fast, and with VERY little confinment. Would NC make for good detonators ignited by a fuse?
Also, what happens to the chemical structure when NC deflagurates or detonates? (what is given off)

Iv4 - 2-11-2003 at 05:17

NC wont detonate.I know that some smokeless powders can detonatw when initiated but those are just the ones with a high enough amount of nitroglycerin which prety much makes them gelled dynamite.

Polverone - 2-11-2003 at 13:45

No, nitrocellulose does detonate. IIRC, it undergoes DDT pretty easily when it's low density (freshly prepared from cotton or the like), which is one reason it took so long before it could be used to replace black powder as a propellant (it had to be tamed first).

Mr.O-Nitrate - 10-11-2003 at 15:21

At what temp does the tri nitrate isomer form for Nitrocellulose? I made some about 3 days ago. I deflagrated it but it burnt slow. More like the Dinitrocellulose version. I was using an ice bath and I let the cellulose sit in the acids for 20 minutes. After nitrating I washed it in a bicarb solution and then let it sit in water. Dryed it for 2 days out in the open. What could be the problem? Or did i just need to separate the un-nitrated cotton with a solvent?

palpy - 11-11-2003 at 06:50

i think that the level of nitration depends more on the concentration of used acids, than temperature.
I once made NC with 70ml H2SO4 96% and 50ml HNO3 65% for 5g of cellulose at about 15 deg.C and the NC burnt VERY rapidly.

Burn Rate - Original vs dissolved

hodges - 25-9-2004 at 14:33

I recently made some nitrocellulose out of cotton. Good fast burn rate, almost no ash left behind.

So I dissolved some of this in acetone. Nearly all of it dissolved - just a small thread of cotten left behind. Upon drying in a glass dish, the product resembled scotch tape at the edges where thin (transparent plastic-like substance), and it resembled paper where thicker (white translucent substance). When ignited, it burned much slower than the original nitrated cotton did. Why would this be? It still left very little ash, but the burn rate was not impressive.

The_Davster - 25-9-2004 at 15:18

The same thing has happened to me. The freshly made NC made from the cotton on top of the aspirin bottle, burned well, even with a little "fwump" sound.
After disolving in acetone and crashing into water, it still burned fast but I got no "fwump" anymore and the burn rate was noticable slower.

I believe it has something to do with in the freshly made type having large spaces for flame to propagate through very fast as oposed to the one after disolving in acetone which has fewer spaces.

Also, after disolving in acetone and crashing into water the NC felt more "plastic" as opposed to the "cotton" feel of before. There also seemed to be less NC in terms of volume after disolving in acetone despite the mass being the same so I am led to believe that the density has increased a bit. I believe that a higher density would also slow down flame propagation due to decreased surface area.

redneck - 26-9-2004 at 22:57

Dear IgnorantlyIntelligent
I assume you used too few Ammonium Nitrate. Sulfuric acid dissolves cellulose. If your mixed acid contains too few ammonium nitrate, your cellulose will dissolve like in pure sulfuric acid.
In theory a nitrating mix of 1g AN dissolved in ~1.5ml 98% sulfuric acid corresponds to an nitrating mix of 1g pure HNO3 with 2g H2SO4. The nitating must be cooled to minus 10 degree centigrad prior to adding the cellulose. When as much cellulose as can be drowned in the acid-AN-mix is added, continue cooling for 30 min. Then let the mix warm to room temp. an let it rest for 3 hours. Use toilett paper as cellulose, but you have to boil it in 2% NaOH solution for 30 min and wash it and let it dry prior to nitrating. This removes traces of fat in the cellulose. With unprepared cellulose the quality of the NC will be poorer which means there will be more dinitrat in the NC.

AngelEyes - 27-9-2004 at 03:50

I use cosmetic cotton wool balls, the usual drain cleaner acid (minimum 93% sulphuric) and 70% HNO3.
2:1 by volume of sulphuric:nitric.
I add as much cotton as the mixture will take (so it's all soaked in acid at least) and leave it somewhere cool and dry for at least 24 hours - usually more. Then remove and wash, neutralise with carbonate, wash some more etc until there is no acid reaction with carbonate or litmus. Then dry thoroughly.

My product always burns fast with a nice yellow flame and about 1g in a tube is good a for a firecracker. Never tried to detonate it though, nor have I tried with sulphuric and an inorganic nitrate.

Never managed to use it in a cap though - it just doesn't seem to DDT.

[Edited on 27-9-2004 by AngelEyes]

Ouality of the NC

redneck - 28-9-2004 at 21:01

Hallo AngelEyes
Please could you report me the quality of the NC obtained by your process. Take some NC and rub it betwenn your thumb and your forefinger to get a small ball (about 4 mm in diameter). Then light it.
Is there any carbon risidue?
My NC burns without risdue when fluffy, but when I squeze the air out of it there is some porous carbon left after burning.

tokat - 29-9-2004 at 00:34

" When ignited, it burned much slower than the original nitrated cotton did. Why would this be? It still left very little ash, but the burn rate was not impressive."
I think its like when you add water to BP to cake it, maybe the componds bonded together rather than be beside each other.

AngelEyes - 29-9-2004 at 03:03

There is a tiny amount of residue but it's negligible. The more I squeeze it together the slower it burns...but not that much slower. If you colloid it (with Acetone) and let it dry then the resulting plastic burns quite predictably and stably and leaves the same negligible amount of residue.

I sometimes take the neutralised NC and dunk it into an inorganic nitrate solution then dry it again. This gives a little more kick and helps to increase the Oxygen balance.

By and large I use it for firecrackers and lacquer (when mixed with Acetone to thge consistency of thin honey).

To Tokat: The reason un-nitrated burns much slower is because the nitration process implants the nitrate ion (NO3) into the cotton. The Oxygen (contained within the NO3 ion) is therefore present on a molecular level and it's this molecular combination of fuel (cotton) and oxidiser (NO3) that allows the flame to propogate waaaaaay faster than if it were to burn in atmospheric Oxygen alone. That's probably not a great explanation but I think it's accurate. I'm sure I will be corrected if it ain't...

[Edited on 29-9-2004 by AngelEyes]

tokat - 29-9-2004 at 23:25

How does the plastic effect happen does NC bond with NG or does NG type of deffuse in NC.

thanks angeleyes.

[Edited on 30-9-2004 by tokat]

AngelEyes - 30-9-2004 at 03:37

When did NG get into this thread?
It matters little as I have never prepared NG so have no experience with it.

I think it's the NC dissolving in the NG but don't quote me on that. There are plenty of other members here who know far more about it than I.

EDIT: Ah, he means Acetone not NG....I think.
Raw cotton (normal or gun) is like a maze of tiny, tiny tubes. When nitrated it's like a big ball of quickmatch. When colloided (with Acetone) it forms a plasticky type material and all the tubes are gone. So it takes longer to burn as the flame can't flash through the whole thing.

[Edited on 30-9-2004 by AngelEyes]

Huzzah! NC

MephistosMinion - 31-3-2005 at 06:28

Sorry to bring up an older thread but I thought it best not to make a new one.

When he mentions NG I think he is talking abouit the preperation of blasting gelatin.

I finnaly bought myself some more (25 kilos) of KNO3 and a bottle of analytical H2SO4 (98%). I also got some cotton face/makeup pads.

Here is my acid:
http://img.photobucket.com/albums/v466/mephistosminion/SANY0...

Here is Cotton:
http://img.photobucket.com/albums/v466/mephistosminion/SANY0...

Here is It nitrating in a bat of 90ml H2SO4 and 75g KNO3:
http://img.photobucket.com/albums/v466/mephistosminion/SANY0...

Here is the yeild:
http://img.photobucket.com/albums/v466/mephistosminion/SANY0...

Here are consectutive from a video of my NC burning:
http://img.photobucket.com/albums/v466/mephistosminion/NCfra...

chemoleo - 31-3-2005 at 13:39

Did you add water to the mix at all? I am surprised your batch looks so 'liquid'.
If not, then the degree of nitration should be high. Adding more H2SO4 should further that purpose.

MephistosMinion - 31-3-2005 at 15:18

I didnt add any water but I started with only 60ml H2SO4 and 50g KNO3. I added alot of cotton and felt it was too thick. So I mixed another 30ml H2SO4 and 25g KNO3 in a seperate beaker and added that to the reaction.

Ajantis - 1-7-2005 at 01:42

i attempted the procedure 2 times... in the first, with powerlabs proportions, the product was not very good, lots of residue left, slow burning... the second with brainfever proportions, that are triple of that's of powerlabs (concerning acid quantity/cotton) and it worked perfectly, instant combustion, pratically no residue left, and with the no raffinated in acetone product!
powerlabs proportions are uncorrected or i could have done an error during the first procedure?

Sorry for my bad english

Rosco Bodine - 2-7-2005 at 07:15

Microcrystalline cellulose should be easily nitratable , but I have never seen it described . IIRC , cellulose flour is what is the name for it as a food additive and it is soluble like starch , but has a small number like 8 cellulose units which has a crystalline form . There are small bottles sold as a dietary supplement ,
" soluble fiber " type of material for an inflated price . But the same material is sold cheaply in bulk as a thickener additive for foods , similar to rice and potato flour .

ordenblitz - 2-7-2005 at 08:34

Roscoe,

You are correct that microcrystalline cellulose is easy to nitrate, much easier in fact since it is more dense that cotton and you can get more in the mixed acids. You can stir it more effectively and it nitrates faster since the small crystals are better exposed to the acid. After nitration is complete, leaving it to stand causes the MCNC to float to the surface of the acid in a dense layer that can be pulled out of a beaker in virtually one chunk. This brings along less spent acid and allows faster quenching thus keeping the N content as high as possible. Stabilization is a breeze as well since MCC does not have the tubular cellulose structure that cotton has therefore it traps less sulfuric acid esters. A short boil is all that's needed. The best thing about MCNC is that it retains the physical characteristics of MCC. It compresses very well in a hard and durable plastic form. Tabletted material looks very much like ivory.

I know a little bit about this since a while back, I applied for a patent on MCNC. They are slow at the USPTO it's not even in the pending list yet. My last patent took 1.5 years to show up on the website after filing.

Rosco Bodine - 2-7-2005 at 10:05

It makes sense that the nitrated product would likely be a superior material as a base for smokeless powder too . It would probably function especially well as a fast pistol powder or rimfire powder where a small granulation is desirable , and a highly nitrated dense cordite of very
regular and dense grain , and high loading density would be a real power boost in small caliber cartridges .

When the grain size of nitrocellulose is at about 100 mesh and smaller , it is also readily initiated when compressed as a base charge in a detonator and initiated by a primary explosive . If my guess is right , nitrated microcrystalline cellulose should have properties more similar to PETN than to the more common nitrocellulose from long fibered sources .
The stability and power and economy of manufacture is probably somewhere between the two .

If the material compresses easily to a dense grain structure , it may also have interest as a rocket propellant .

It should be a versatile high energy material , of economical manufacture .
I'd be a bit surprised if the powder manufacturers were not already onto its use , perhaps as a component in some
powder formulations having different blends of cellulosic precursors . There are such things practiced in the art and known but not published , and it wouldn't be surprising if this proved to be one of those " trade secret " sort of items .

ordenblitz - 2-7-2005 at 11:40

That's exactly what I thought when I started making MCNC some years back. But a thorough patent and chemical search revealed exactly no mention of the substance.

I came across the idea while working with nitrocellulose as high nitrogen fuel for use in indoor pyrotechnics. Regular fibrous NC is very difficult to compress to a sufficient density for my uses with out colloiding or the addition of other chemicals functioning as binders. Another problem was scrubbing in the dies upon ejection after high pressure compression. This required the addition of lubricants which further slowed the combustion. I happened to be looking at a bottle of vitamins and it mentioned MCC as an ingredient. After searching the chemical I was immediately struck with the idea, what if it could be nitrated.. would it retain it's favorable characteristics of density, compressibility and inherent lubricity. To my surprise and glee, it does! I have done no testing of MCNC as a high explosive.

The only thing that probably would limit it's usefulness in firearms and explosives would be the cost. Different grades of pure MCC in particle sizes favorable for nitration are on the order of $5.00/lb. One idea that has struck me is it could possibly be compressed into a case form such that it could accept both primer and projectile for case less firearms rounds. Upon compression the strength and machine ability of this material is almost identical to the plastic, "delrin" also known as acetal.

ordenblitz - 2-7-2005 at 11:46

Upon reading this thread from the beginning, I see that Rooster mentions MCC and it's characteristics back in
17-10-2003
He was on the right track and probably should have continued with his research.

Rosco Bodine - 2-7-2005 at 12:24

So don't leave us wanting for the details of the methods for syntheses which you tested

I have wondered if the nitration might be optimized in ways more like for
nitrostarch , given the physical similarity .

ordenblitz - 3-7-2005 at 14:15

Nitration of MCC is straight forward and easy using about any of the typical nitration schemes.

Doing some research on MCC will show that it is formed by the chemical removal of the amorphous cellulose regions with mineral acid usually HCL, leaving practically pure crystalline alpha cellulose. These regions gelling are usually the problem that people have when using incorrect ratios of nitrating acids. Nitric acid will cause degradation of amorphous cellulose and it will get soft and gooey hindering the nitration itself and making handling the product difficult or impossible. MCC is very forgiving in this regard. An incorrect or weak nitration mix will result in a visibly identical process as well as finished product except for the actual nitrogen content. In essence, you really can’t screw it up.

I find it most convenient to use an alkaline metal nitrate in combination with H2SO4. Typically when nitrating cotton, mixed nitric and sulfuric are preferred since cotton absorbs so much of the acid liquor you normally need an excess of acid to keep it physically in the solution, separated and able to give off its initial heat of the reaction so as not form hot spots or cause a run away. Using a nitrate/H2SO4 mix to nitrate cotton usually just increases the viscosity of the mix thereby making it necessary to use even more sulfuric. You will find that it is most easy to load the acid mix with more MCC than can be nitrated by any given amount of acid. Most amateur nitrators will enjoy this inherent efficiency of their hard to come by acid.

Separation, washing and quenching, as I said in previous post, is a breeze. Upon standing, the MCNC will rise to the surface of spent acids in a semi soft mass that can be scooped out with ease and quenched in water. This mass carries very little acid with it in contrast to cotton. When said mass is plunged into water, the acid/water ratio falls below the nitration region very quickly thus greatly reducing the de-nitration of the product during the first few seconds of washing. As you know nitration of cellulose is reversible and is equilibrium depending on the strength of the acid mix or its water content. If the cotton is in a large mass, or if one is slow in getting the cellulose washed, or plunges into an insufficient amount of cold water, the N content will begin to decrease until dilution of acids falls below a certain level. MCNC typically will result in higher finished N contents with a given acid mix compared to cotton or wood derived cellulose. Since MCC is not tubular cellulose structures as is cotton, it is less likely trap formed metallic sulfates as well as acids, so neutralization is a snap. I wash with cold water a few times in a fine screen and then a short boil. I will admit that I haven’t done extensive research of storage stability as of yet so your results will almost certainly vary.

Time to reach equilibrium depends both on the strength of the nitration mix AND the particle size of the MCC. 10 to 30 micron material will complete in a matter of minutes where as 200 micron material may take a few days. Think of each MCC particle nitrating from the outside in. If you use coarser sizes, 50+, and shorter soak times, you will have overall lower N contents. At this point I must tell you that my aim is not highly nitrated material. I make pyrotechnics and my goal is a high nitrogen fuel, not propellants or explosives. For my purposes 10 to 11.5 percent nitrogen is best. Therefore I have tuned my processes to that end. I prefer KNO3/H2SO4 because I have a lot of both, and also want to keep sodium to a minimum.

All that being said, I don’t envision everyone falling in love with MCNC, especially this crowd. Anyone who has played with gun cotton is usually enamored by a small quantity burning with a pleasing thump when touched off with a flame. Compared to fibrous NC cotton, MCNC will burn much slower than a similar quantity of NC cotton. For use as a loose propellant, such as how gun cotton is employed in toy and novelty items, MCNC would be useless. However, if one wants to mix NC with other powders or liquids or if one aims to compress it or machine it… MCNC is a dream!

P.S. MCC is said to be able to hold a great amount of liquid and still be compressed in a dry mass. This should be something quite of interest to those who would seek to use MCNC as a carrier of other energetic liquids. However, I have done no research in that area.

Enjoy!

Rosco Bodine - 3-7-2005 at 15:13

Yeah I did some reading on the MCC product called Avicel . And I need to correct what I said earlier about cellulose flour being the same thing because it is not . Evidently cellulose powder or flour
is simply finely granulated sawdust basically which has been leached of nearly everything else but the cellulose it contains . It is however an amorphous material not as dense as microcrystalline cellulose . Further treatment with acid is
required to strip away the exposed fiber layers which surround the core nuggets of crystalline cellulose averaging about 250 molecules of cellulose per crystal .

I think a similar process is known for a material called " cyclodextrin " , the nitrated form of which is used in military explosives . I have a patent on this material somewhere , and MCNC seems
very similar . It may be the cyclodextrin which has the 8 unit ring structure . I'll try to dig up the patent if anyone is interested .

MCC is used also as a chromatography absorbent . It does form thixotropic gels but is actually insoluble , forming a dispersion and not a true solution .

It would be intersting to find out how sensitive compressed MCNC is to initiation , and at what lower percentage limit it may function as a binder for lead azide , silver azide , ect. Since it sounds like it is pressure flowable and tough , it may make an exceptional binder for other
materials . Caseless ammunition is a great idea , and caseless detonators too ,
where the case itself participates in the detonation . Some interesting ordnance could be contemplated for stealth applications , since the structure of a glide bomb for example , including the circuit boards for the electronics would every part be a contributor to the detonation , and there would be very little left as a signature to provide any intel on what it was or from where it came .

Caseless ammunition

MadHatter - 4-7-2005 at 14:14

IIRC, the HK G11K3 was experimented with by (then) West Germany's special forces.
Bore diameters include 4.7mm and 4.92mm. It appears to have largely abandonded
because the rounds could autoignite after 7 or 8 shots were fired.

chemoleo - 7-7-2005 at 05:56

Re microcrystalline cellulose:

I was thinking that maybe regenerated cellulose (see this) solubilised with the cuprammonia solution could be a good target for nitration; i.e. it could be either neutralised by pouring the whole mix into a large amount of water, and filtering the cellulose as single molecule fibres, or alternatively spinning fine fibres from it (i.e. pressing it through a syringe into the neutralisation solution).

In any case, this may be something to play with, it may have different properties from the normal NC.

Ajantis - 11-7-2005 at 01:07

In purifying nitrocellulose, to extract the unnitrated cotton from the acetone solution it must be used a coffee filter or filter paper?

Ajantis - 16-7-2005 at 12:52

nc dissolved in acetone is very dense, my dubt was if unnitrated cotton would obstruct filter paper, because i tried with a coffee filter and a very small quantity of nc dissolved passed... i needed to know if my nc was awfully nitrated or if filtering metod was mistaken... excuse me...

Quince - 10-8-2006 at 00:26

I'm still not clear on what specific H2SO4/HNO3/H2O/cellulose mix to use to get a nitration level optimal for making NC that will gell NG well.

Deceitful_Frank - 10-8-2006 at 09:28

Check out Boomer's post (6th from top) in the Nitrostarch thread in the HE section over in APC.

Not sure if I've seen you over there so you may not have access but if you send Mumbles a PM...

It relates to the quality of NC (from how well it burns and hence nitrogen content) that is gotten using varying ratios of acid, nitrate and starch and IMO could be extrapolated for use in a nitrocellulose synth.

Boomer - 11-8-2006 at 05:47

Generally speaking, higher temps and longer soaking give better soluble NC (for a given N content).

Instead of *diluting* the precious nitric to get lower nitrogen, try re-using the mix. It takes so little cotton because of the bulk that you can use it at least 4 times. This is limited more by the losses you cannot squeeze out after each use, than by the dilution from reaction water.

This way you have some fast but insoluble stuff for other things, and from the later batches some soluble NC. Way better acid usage IMO.

woelen - 14-9-2006 at 07:03

I also have made some nitrated cellulose (a.k.a. nitrocotton, but I know that is a bad name).

http://woelen.scheikunde.net/science/chem/exps/nitrocotton/i...

This experiment is easy to perform and fairly fool-proof. But now I'm wondering, could this also be done with perchloric acid instead of nitric acid? What if you mix 60 .. 70% HClO4 with concentrated H2SO4 and then press the piece of wadding into the liquid? Does it form the perchlorate ester, or does it explode, or nothing happens? If anyone has tried this, I would be pleased to read about the results. I could try it myself also, but then I first need to prepare a setup for really tiny amounts, my supply of HClO4 is almost gone and it is a chemical which is not easy to obtain

(maybe I can obtain a small amount again, but that is not sure yet).

I did try the variation with chlorate (I have a reasonable amount of that), but that does not work. It simply is impossible to make a chlorate ester. I made a tiny amount of KClO3/H2SO4 mix and added a piece of wadding. The mix ignites on contact with the piece of wadding, giving a purplish orange flash and crackling noise.

[Edited on 14-9-06 by woelen]

garage chemist - 14-9-2006 at 07:37

Perchloric esters of cellulose have never been obtained, I read somewhere.
I also can't see why it should work, as HClO4 is a much stronger acid than H2SO4. The HClO4 would catalyze the formation of cellulose sulfate, not the other way round.

On the topic of NC: A much better product is obtained if the cotton is boiled in 2-4% NaOH solution for a few hours to clean it from resins and cell plasma residues. It is then washed, dried and nitrated in the usual way. The nitrating acid can reach and wet the fibers better then.
This greatly improves the quality, stability and nitrogen content of the NC.

Zinc - 19-11-2007 at 09:40

I know this is off topic but I didn't want to start a new tread about it.
I have some cannon grade smokeless powder from WW2. It was in rods and plates and it is very hard. I grinded it to 1-2 cm pieces by putting it in a bag and hitting it with a hammer. But I want to grind it to 1-2 mm granules. How can I do that?

quicksilver - 19-11-2007 at 12:11

That WAS pretty wildly off topic but what the Hell....I'd put it it water and use a blender. Depending upon whether it was glazed or not it may break into very fine particulate with a blender and be quite recoverable. Some of the long rod material was true Cordite (very high NG content: higher than todays canister powders!).

[Edited on 19-11-2007 by quicksilver]

Zinc - 19-11-2007 at 12:38

Quote:

Originally posted by quicksilver
That WAS pretty wildly off topic but what the Hell....I'd put it it water and use a blender. Depending upon whether it was glazed or not it may break into very fine particulate with a blender and be quite recoverable. Some of the long rod material was true Cordite (very high HG content: higher than todays canister powders!).

So if it is glazed it will be recoverable and if it s not it will be unrecoverable or?

What do you mean by HG?

And the powder was 60 years under water and still lives

quicksilver - 19-11-2007 at 16:38

My bad, I meant NG. The original cordite had a great deal of nitroglycerin; more so than today's Bullseye. Well, if it's highly glazed via graphite and a related process the "stick" may be more resilient than if it were not. Only one way to find out - try it! Some time back some experiments were conducted to determine if it were possible to pull the NG out of the DBSP. It was determined that (if it were not too effectively glazed) ethanol or ethyl acetate were utilized - the NG could, indeed be brought back into solution and the solvent evaporated off. You see the glazing forms a sort of tough shell on the product.

I tried to find some source on this and from what I remember Bullseye has 46-48% NG (Alliant Corp)and Cordite from UK gov't sources had 55-57%. but I think it's printed on the canister as well.

[Edited on 19-11-2007 by quicksilver]

Bert - 19-11-2007 at 22:15

There is extensive information on NG recovery from finished and semi-finished smokeless powder in Naoum's NG and NG Explosives. At the end of WWI. they had to do something to reclaim it for mining explosives, and developed techniques.

~TCM~ - 22-12-2007 at 18:56

Forgive me if this is a stupid question, but I have searched extensively and cannot find a definitive answer.
I know blasting gelatin is made using collodion nitrocellulose with a nitrogen content around 11-12%.
My question is, can nitroglycerin be soaked into cellulose hexanitrate,(I know there is controversy about what hexanitrate actually is), so let me just say cellulose nitrate with a high nitrogen %.
I have made cellulose nitrate that detonates well, so I presume it has a high nitrogen%,(guncotton).
Can I soak nitroglycerin into the guncotton in it's fibrous state, or is this a waste of time.
I have made nitroglycerin that worked very well, I simply soaked it into saw dust and it detonated fully with a small amount of HMTD.
I was thinking that soaking it into guncotton instead of saw dust would be more affective?

MephistosMinion - 22-12-2007 at 19:30

Make sure your NC is fully neutral before you mix it with NG. I haven't mixed the two for a while but im pretty sure that NG will dissolve NC... Hence making it a jelly...

~TCM~ - 22-12-2007 at 19:37

I thought NC with a high nitrogen% (hexanitrate) was insoluable in NG?

MephistosMinion - 23-12-2007 at 01:41

Could well be. I made some fresh NC this afternoon. I will go get some more glycerin from the chemist and see what happens.

The_Davster - 23-12-2007 at 11:56

Yes NC with a nitrogen percentage above a number(13.5 or 14 ish IIRC) is insoluble in NG.

~TCM~ - 23-12-2007 at 13:33

Could it still be used as a medium to soak NG into or would it be pointless

MephistosMinion - 25-12-2007 at 02:00

I think with the added NG through the NC you would fairly easily achieve a full detonation of both compounds. Using an explosive filler will be more powerfull than an inert one, say diatomous eath, saw dust, clay etc. For making the ammount of NC/NG dynamite that would be practical for my usues (I blast on a large property) the sheer size of a reaction vessel for NC synths would be impracticable. For a small scale go it though.

Nitrocellulose question

Skrinkle - 1-7-2008 at 11:01

Hello,
I Nitrated a cotton ball using a 50/50 solution of 68% nitric acid and 97% sulphuric acid. (nasty fumes btw)
I used an ice bath to slow it down when the reaction started to get a little frisky. I added the cotton ball all at once and submerged it in the nitration bath. It later occurred to me that i should have perhaps added it a little bit at a time to ensure proper saturation. I used a stirring rod to expel all of the air from the cotton ball while it was in the nitration bath but i am unsure how well it will turn out. It was in the bath for approx 7 minutes if that helps at all. My question is: Did i achieve enough saturation to fully nitrate the cellulose or do you think that it will turn out to be only partially nitrated?

P.S.
What should i do with the excess nitration solution? The best i could think of was to pour it in my backyard where there wasn't any grass, cover it with sodium bicarbonate and then pour water on it to dilute. I know this sounds like an EPA disaster but i feared it might corrode my plumbing.

[Edited on 1-7-2008 by Skrinkle]

Edit by Chemoleo: Please post in the appropriate thread next time, there is a search engine. Also, many of your questions can be answered by reading this thread (and other related ones) more carefully.

[Edited on 1-7-2008 by chemoleo]

Skrinkle - 1-7-2008 at 11:19

Quote:

Originally posted by rooster
YESSS! Finally I found microcrystalline cellulose at a lab. It is like powder. When you nitrate it for use as a HE, it is hard to compress the nitrated "cotton wool" type. Also it will be easier to handle.

One question...

Why isn't there any nitrating procedures for NC with 99% HNO3 and H2SO4? I heard 70% HNO3 is more oxidizing than 99%, if so, wouldn't there be less oxydated, unwanted byproducts of cellulose when nitrate with higher % acids?

Rooster:
I think that 68-70% nitric acid is easier to come by. It is for me anyway.

Microtek - 6-7-2008 at 00:53

It is actually quite easy to make MCC yourself. Boiling cotton wool in ca. 10 % HCl for about 2 hours will produce a nice fine powder with properties that are consistent with MCC. The yield from the process was ca. 80 % when I tried it and the product could be compressed into qan extremely durable pellet at moderate pressures. It was fairly easy to nitrate but had a tendency to clump when added to the mixed acids. When NG was added to the nitrated MCC it formed a granular colloidon over a few hours. This granulate could be pressed whereupon it flowed plastically and formed a single body. Great for propellant grains for rockets (if you can solve the other technical problems of NG/NC based rockets).

specialactivitieSK - 21-11-2014 at 05:42

Methods for making spherical particles of cellulose nitrate : http://www.google.com/patents/US2915519

EXAMPLE III 60 grams of cellulose nitrate (13.55% N) were dissolved in 600 ml. ethyl acetate. The lacquer was dispersed in 450 ml. water containing 9.6 grams of a petroleum sulfonate (Petromix #9) as the emulsifying agent under vigorous agitation in a homogenizer. Agitation was continued and the ethyl acetate was removed from the dispersed lacquer particles by distillation at 22-39 C. and a pressure of 6.5 cm. The resulting cellulose nitrate particles were 1-20 micron spheres having a density of 1.56.