Inulin Nitrate ( nitrated dietary fiber )

[Rosco Bodine]

There is a natural soluble dietary fiber called inulin ,
which is similar to starch , but derived from
fructose units , something like a fructose polymer .

And similarly as starch and cellulose , inulin forms
a nitrate which is an explosive , and has useful properties .

Dietary inulin is a common food additive cheaply available .

The single reference which I have found concerning the
nitration of inulin and the properties of the product is a patent .

US1922123

[cutefix]

How it is related to starch and celllulose nitrate?Being both derived from carbohydrates they are expected to have similar characteristics...

+++++++++

No need to quote the whole post, as it's only a paragraph long anyways.

NBK

[Rosco Bodine]

As best I understand it , inulin is an isomeric form
of the same polysaccharide structure as is cellulose and
starch and dextrin , only the chain length is different ,
probably having fewer units and a lower molecular weight
polymer than cellulose , starch , or dextrin .

Inulin is a polysaccharide based on fructose units instead
of glucose units like cellulose , starch , and dextrin .
Therefore it could be regarded correctly as being a polymeric
form of fructose , structurally different from those other materials .

The interesting properties of inulin nitrate which caught my notice ,
are that it is non-crystalline in nature , and has a low melting point ,
solidifying to tough film when its acetone solutions are evaporated .
That combination of properties would make inulin nitrate a very good
candidate as an energetic binder material , or as a component of
a mixture useful as an energetic binder . Inulin nitrate might be a
possible ingredient also for a plastic ETN based composition which
could surpass semtex and C4 . It has interesting possibilities ,
and the inulin starting material is ten bucks a pound from nutrition
supplement suppliers .

[0EZ0]

Mention of some poeple's attempts to nitrate xylitol, a simple sugar alcohol, in the Erythritol Tetranitrate thread sparked my interest a week or so ago about the other possible candidates for nitration in the large array of monosaccharides and polysaccharides. Obviously this is nothing new, but some compounds that may have been discarded for industrial use before due to expensive production methods or due to high sensitivity may find a use in the expeimental world.

A bit of research and a few notable things popped up. Looking at sugar alcohols (polyols, polyhydric alcohols) reveals a few names that many of us are probably familiar with. Sorbitol, maltitol, mannitol, erythritol, xylitol, lactitol and isomalt. Nitrated compounds of mannitol, erythritol and sorbitol are known to have been produced before. I'm sure there would have been someone who investigated the use of other compounds in the same series in the energetics field.

Looking at large molecule polysaccharides you will probably find other compounds that have found considerable mention in our field like cellulose and starch. Inulin is in the same polysaccharide group as the above two. It is a possibility I guess.

Although one must not make the assumption that being chemically related that nitration would produce a similarly useful end material, or that you would only get one type of nitrated compound. I do however see that there may well be some good possibilities that have been overlooked.

[cutefix]

Nitrated carbohydrates and cellulose tend to exhibit polynitrate structural characterestics. However since the time that these products became reality, the only items that have practical explosive applications which were even used during wartime is the starch and cellulose nitrates. Other things such mannitol hexanitrate did gain prominence as initiating explosives, but the rest of the sugar nitrates were only appreciated in the academic level( laboratory scale).
It is difficult to find extensive data on other carbohydrate polynitrates which was actually used in real life such as the starch nitrates( nitro starch). The known examples such as sucrose nitrates were mentioned in the past but it was not widely applied in practice.
Now going back to the possibility that inulin nitrate could be a potential energetic plasticizer, one the primary requisite for that is its soluble in solvents commonly used to form colloiidal solution with other explosives.
It should also have the ability to form a gel with other explosives.
It is a common knowledge that nitrocellulose will dissolve in acetone and gelatinize in nitroglycerine, but how about inulin nitrate what are its peculiarities as exhibited by its chemical/physical properties with respect to solubilities and solvation characterisitics?

I familiar about the issue that inulin was used to prepare tequila :p not as an explosive material ;)
But its still interesting information anyway....

[Rosco Bodine]

Certainly the economics regarding the starting materials
was a major consideration in determining which explosives
found practical use , or were even subject of extensive
experiments . The present cheap availability of raw materials
should bring a reexamination of early research in this area ,
and even possibly entirely new experiments to investigate
what may have never been examined by the early researchers .

What makes inulin nitrate so interesting is those properties
it shares with nitrocellulose , with one very important added
feature , its low melting point . For example , suppose that
lead azide was suspended in a stirred acetone solution of
inulin nitrate which was precipitated upon the lead azide as
a coating by addition of water . The granulated material is
filtered and dried . Then the coated lead azide is compression
loaded with sufficient low heating to cause softening and flowing
under pressure of the inulin nitrate . Upon cooling , you have
a compressed pellet of initiator , bindered with a thermoplastic
and waterproof energetic binder which also excludes air from
any detrimental effect on the azide , while physically securing
the pellet of lead azide in a detonator capsule , by literally
gluing it to the inside walls .

And there are many other possibilities where the low melting point
and glue like properties of such a nitrated polymer could be useful .

Besides , what should be better than a nitrated colon cleaner
for helping you to blow the shit out of stuff :D

[cutefix]

Blowing the shit with a nitrated dietary fiber would have been more effecient if nitrocellulos or the higher nitrated esters are used :D
It is more easily accessible as there are more countless source of cellulose than inulin.

It is a good idea also to disperse the lead azide in an already energetic agent.But I have not seen any evidence that it was really applied in such way.
The usuall way to do that is to use dextrin and other inert filler.
Somehow I am not concerned much about initiator application if that is one feasible way.
It would be interesting to know the use of such nitrate for main charge.
Unfortunately there is not much data available.

[Rosco Bodine]

Doing further reading on the matter of nitrating
"vegetable gums" or soluble "cellulosic" type fiber ,
I found a patent related to the nitration of guar gum ,
which is another OTC dietary fiber , the nitrated
product of guar having usefulness as a gelling agent
for nitromethane , and other possible uses as well .

The similarity of guar gum to inulin probably makes
the nitration process for one , applicable to the other .
The nitration of guar gum is described in detail and
also a method using methylene chloride as a thinner
for the nitration mixture , which is a special technique
that has been mentioned having value in many nitrations .

The patent is a good read and has information about this
nitration method using methylene chloride which could be
applied to nitrations of other materials which ordinarily
may be difficult to manage due to the very thick mixtures
which tend to form during nitration .

US4112220 Nitrate Esters of Galactomannan Gums

Regarding my speculation about using inulin nitrate as an energetic binder
having the property of a "hot melt" glue , it first seems a good idea but
it may not work if inulin nitrate is further polymerized by a cross-linking
effect on contact with the traces of lead compounds on the surfaces
of lead azide crystals . The patent related to guar nitrate reports
that lead oxide catalyzes the gelling of acetone solutions of guar nitrate ,
and the same complication may occur for inulin nitrate . That complication
could result in problems depositing the binder as a coating upon the crystals ,
and the coating could have an elevated or non-existent melting point
due to further polymerization catalyzed by the lead . If that complication
occurs , there may or may not be a workaround , such as using chromated
lead azide , since chromate itself has a known catalytic effect upon polymerization .

Anyway , there are many different vegetable gums , having similar
yet differing specific properties , and the same would likely follow
regarding the nitrated products of those gums . There isn't much
information published on these materials so there are plenty of unknowns
to be the basis of experimentation with those materials . Many of
the nitrated gums are probably useful for binders and gelling agents
in specific compositions where they are found to be compatable .

[cutefix]

Guar gums is a galactomannan a carbohydrate which was commonly used as thickener for water gel explosives.
Having a structure similar to cellulose would make it possible to be nitrated.
Unfortunately the difficulty lies in the fact that this material is moisture absorptive so that the carbohydrate conformational structure tend to be less open to the attack by the nitrating groups. This galactomannan when solvated tends to form into lumps and to harden.
It is unlike starches , sugars, and starches that are more open to such treatment.
Therefore the use of anhydrous nitration was needed to affect better nitration conditions.
BTW, these so called anhydrous nitration was already a tried procedure even 50 years ago. It was even tried in the preparation of nitroglycerine, TNT etc with better results than so called aqueous phase nitration(where H2SO4 tends to remove the water formed in the nitration process). It was maybe due to the fact that for several years the traditional nitration process were doing well and cheaper than if using solvents so it was never adapted to the synthesis of well known explosives made with mixed acid nitration.
Regarding the gelling of guar gum IIRC there was an old post in Roguesci about the use of chromates as cross linker for guar gum. And this latter practice was even used in the industrial manufacture of such kind commercial explosives.
Indeed there are many vegetable gums available . Such as Xanthan, locust bean, gum Arabic. But the Guar is the most abundant being a legume as easier to raise in farms; therefore cheaper than the rest.

If you compare that with inulin nitrate( 12.80% nitrogen); guar nitrate (12.6% nitrogen). The amounts looks similar to normal nitrocellulose.
If dry it would definitely be flammable.
Unfortunately it did not describe its chemical properties well.
BTW your inulin nitrate is similar to collodion as its tends to form films. Theortically it can be used to gel nitroglycerine to make a blasting gelatine type explosives.

Do not show this patent to the Mexicans!. ;) They might nitrate their inulin instead of processing for tequila! Then America will have a problem then from their close neighbor in the south. :)

[Rosco Bodine]

The desirability of an energetic binder which could be
used as a hot melt glue for other crystalline explosives
is evident . Mr. Cool has mentioned this before in regards
to its use as a binder for forming a pellet of initiating explosives
so that for example in a detonator , the primary would not
require press loading , but could be cast in place , and thereby
firmly secured in intimate contact with the base charge in
a detonator . By using different melting point binders ,
both the base charge and the initiator could be cast
sequentially , and the result would be a detonator having
superior performance , whose construction would not
require any fancy loading equipment . The higher melting
binder could be used to first load the base charge and
allowed to cool and solidify . Then the capsule could be
loaded with the initiator and lower melting binder and reheated
just sufficiently to melt and cast the initiator pellet , without
using a high enough temperature to cause remelting of the
base charge .

The meltable binders should desirably solidify on cooling to a glass
having adhesive properties . Candymakers use a combination of
sugars and perhaps polyols and starches for making hard candies
which are formed from molten mixtures , and do not crystallize upon
cooling and solidification to a glass . The same idea should be
applicable to the nitrated products of similar materials as is used
by the candymakers in their art .

The melting of mixtures of nitrated polyols , nitrated sugars , and
nitrated "cellulosics" of some combination and proportion should
result in a non-crystalline glass of the sort desired as an energetic binder .

But I have never seen such a mixture described in the literature ,
even though it seems a perfectly reasonable idea .

Among the polyols , the nitrated products of erythritol ,
dulcitol , maltitol , isomalt , lactitol , xylitol , and sorbitol
would seem logical candidates for such a mixture .
Some combination or one of these alone may have
the desired properties as a fusible energetic binder .

The additon of a low melting nitrated cellulosic material
like inulin nitrate to the melt could inhibit cystallization
and increase the film strength of the glass .

A small amount of non-volatile liquid explosive like
sorbitan tetranitrate could be used as a solvent/plasticizer/ "stickifier"
and melting point reducer additive for the energetic binder composition .

There is plenty of room for experiments with such materials
and many other ways in which such binders could be used for
cast shaped charges , also for plastiques that should
result from certain sticky non-hardening binder formulations .
PETN or RDX bindered within such an energetic matrix would
give superior performance beyond the performance of
those present compositions which use inert binders .

[cutefix]

Therefore your primary interests is to use such nitrated catbohydrates as energetic binders.
It is a fact that carbohydrates and cellulosic materials had been tinkered by explosive researchers for several years.
Historically it was Alfred Nobel who initiated it by combining nitroglycerine and collodion( lower nitrogen nitrocellulose) as the gun cotton ( higher nitrogen is not suitable.
I see the possibility for that with inulin nitrate and guar nitreate.IF these two materials did not catch the eye of the so called researchers in energetic binders; it might have come into their mind that all those substances tend to mimic nitrocellulose in performance. In terms of practicality and cost effectiveness they are wary in testing other substances that tends to add complexity to the logistics. They want to simplify the process. If nitrocellulose is perfectly okay then why look for other less known material that have not been extensively tried.
The primary difficulty in the development and application of new explosives is that it had literally had to pass the eye of the needle before its approved for application.
If a lot of potential explosives never reach such level of extensive testing before approval.
IF you happen to browse on the explosive patent literature, there are myriads of compositions that remains only in the mind of he patentee and the paperwork are gathering dust in the archives.
If you had to closely look at the properties of the starch and polyol nitrates the amount of data stored is not extensive meaning it did not get the concerted interest of the explosive developer. The reason probably is it does not offer advantage to the existing cellulose based binder.
Now you talk about the glass qualities of the effect of these materials in the explosive matrix.
If I had to follow your line about the application of the principle of candymaking. Incidentally I had some experience in this area as I also love to cook and bake and had some food science training as well.
IF you travel a lot you must know how to cook your own meals.
The structure of candy in particular the hard candy such as the candy cane, acid drops lollies etc. which exhibits glassy or amorphous qualities.
The base of that candy structure is primarily sucrose( or cane or beet sugar).It is made by boiling an appropriate proportion of water, sugar,
and glucose( a sugar syrup ) to a certain temperature( 150 degree C) to attain the optimum value in terms of its desired physical properties
The glucose supply the desired structural quality by ‘doctoring ‘the crystalline properties of the supersaturated sugar solution which is prone to recystallize when cooked. Therefore dispersing the sucrose in the glucose matrix will prevent the candy from graining ( crystallization). In the same manner any acidulant added ( tartaric acid, citric acid, malic acid) do the same thing by reducing part of the sucrose to invert sugar which confer the same properties as glucose to the sucrose crystal which can be described as stabilization .
Now if you think about the addition of polyols such as sorbitol and glycerol in candies. ITs main function is to improve the water activity value and enhance shelf life by binding more the free moisture and preventing free water it from being used as substrate by microbes that cause spoilage.. In addition such polyhydric alcohol have humectancy effect due to the same reason.
If we have to apply that candy cooking in the current principle to composite explosive formulation. It will never occur. solutions (as how we understand it in common chemistry) Because the main crystalline explosive such as RDX ,HMX,PETN, CL-20 remains in its cryslalline structure.(not solvated into iits ions) If you look at he simple example such as C-4 plastic bonded explosive. The RDX crystal remains as it is in the plastic structure of C-4. If you reclaim the cyclonite it will come out in the same crystalline state it was incorporated.
Now if you will question . what is the purpose of energetic binder ?such as the BAMMO, POLYGLYNN, PGN and the plasticizer FEFO etc. It is the improve the energy evolved during the explosion if compared to being bound by inert binder and plasticiser which tends to dilute the explosive performance.
But still( even with these energetic additives, the crystalline properties of the main explosive mentioned still retains its pristine form it was incorporated.
If you look at the scanning electron microscope image of such plastic bonded explosive you can identify which is RDX( or other explosive ) and which is the binder plasticizer. Matrix. Meaning there was no presence of (what we call) solution ( in typical chemical terminology) but a dispersion.
This might be the reason of your keen interest of these other less known nitrated polyols.. But they had already been in existence for long time already and it never caught the interest of the explosive manufacturers who find that alternative materials that exhibit the desired properties that are absent in the previous binder but present in the new crop of energeitc binders and plasticizers.
One of he concern of the explosive manufacturers while they are wary about using nitrated polyols and cellulose-carbohydrates materials is its low storage stability and the need for stabilizers to miinimize decomposition which will pose a hazard toe explosive storage. There had been many accidents that occurred in the storage of military explosives bound with these existing standard plasticizers; and it was pinpointed that the reason was the tendency to release the nitrogen oxides during storage which can cause degradation of explosive quality , stability., and safety.
The quest for perfect energetic plasticizer and binder is a never ending story ever since in the 1960’s and still on going even in the 2000’s. But knowing the peculiarity of nitrated carbohydrates and the less advantageos quality of nitrated common alcohols The developers in the energetic material division will keep a safe distance from such substances.
Indeed its cheap to make these natural products based energetic binder plasticizers but its not the cost effectivity but the robustness of the newer materials which is compatible the current trend in insensitive high explosive/ insensitive munition/ LOVA grade propelllants and the like.
Now going back to the newer alcohols and sugar replacer like lactitol, maltitiol , xylitol,,isomalt. These materials are expensive to use than if you just nitrate your table sugar. In addition being modified from the original sugar: maltitol from maltose( malt sugar), xylitol from xylose( wood sugar) and isomalt from a complex process of hydrolysis and hydogenation of sucrose they do not exhibit the same accessibiility to the nitration procedures.
It so happens that the chemical conversion from the parent sugar tend to modify the reaction rate and even solubility ( from its parent sugar) as well.
From that vantage point any R&D explosive chemist who find the properties of these so called modified sugars peculiar may try to do in laboratory scale to determine the explosive potential of such substances.
But it will only remain scientific curiosity.
If sorbitol polynitrates had been known to be feasible and already in existence for many decades but was never tried to be evaluated in the grander scale; then presumably the quality that the explosive developer were looking were absent in it. Specially in the light of the current trend of insensitive munitions technology.
In regards to Mr Cool study, the use of energetic binder in initiating explosive is an interesting posibility but that needs extensive trials. One drawback of such concept is it does again does not fit the requirements of the insensitive munition demands of robustness and stability.
If there is an energetic binder In the primary explosive composite, that will not enhance the safety of the explosive device. It may even make the primary explosive susceptible to premature detonation which had catastrophic effect in a munition storage.
That is why the primary explosive is usually dispersed in an inert filller to guarantee safety.
That idea look good in theory but poor if looked from the practical point.
But having separate components in the explosive train will guarantee explosive safety and easier disassembly of explosive parts if its accidentally armed .
It has never been applied in munitions that an embedded iniitiator on the base charge due to safety issues.
In the same reasoning that in chemical weapons as applied in artillery shells its usually a binary device. To be assembled at the moment when needed and not to allow the active components to be at close proximity to each other for safety reason.
In the same line even up to this point in time.
Field soldiers manning artillery position still had the attached the fuse of the munition at the time when its needed. The fit is snug ( between the fuze assembly and the main charge)but not embedded to the base charge ;with a thin measurable distance between the main charge and the detonator/booster assembly.
Explosive safety is of critical concern specially in the time of combat.
An errant enemy shell can possibly detonate a cache of fully armed munitions located in the gunnery range. If such incident happened in the past it will likely happen again and that can be aggravated by drastic change in munition design.
On the other hand there is no limit how developers can conceive a munition design but the pragmatic aspect and the long term effect of such design is crucial as well and must be borne in mind before even going beyond the drawing board.

[Rosco Bodine]

Many of the compositions which are of interest in this forum
would never be acceptable for use in military applications ,
but remain useful for other purposes such as demolition ,
or for having value as compositions which may be improvised
from fairly ordinary raw materials easily and cheaply obtained .

Some of these compositions are more powerful , safer , and
in general more practical than others . So non-military grade
energetic materials do still have value . It is not my purpose
to detract from anyones admiration of the best military compositions ,
but to suggest alternatives that may be of value for experimentation
in the context of the same interest of many who post in this forum .

It is not good to presume that everything practical or worthwhile
in the art of explosives has already been covered before , and I
cannot make such sweeping presumptions about earlier researches ,
even though I do still admire the genius of those early researchers .
If the research was done , and the data is unavailable to me in my
world , it is the same as if it never happened , and may become the
subject of my own experiments . Also in my own experiments are
sometimes quite different results than what some experts already
have reported , leaving me to legitimately question the true extent
of their expertise . Some patents are an embarrassment to the inventor
who even for all their formal credentials know little about what they are
claiming as their invention , especially so when their invention does not work .

The polyols and cellulosic materials are close relatives of materials of
already proven value , so it is not any great leap to suppose that these
materials may also have usefulness , particularly in the context of those
"laboratory curiosities" which are the focus of most of our experiments .
It is entirely possible that beyond the properties of a composition which
would make it undesirable for military use , are simplicity and economy
which may commend its use otherwise .

There are thousands of tons of commercial explosives used each year
which are compositions having a limited storage life that would rule them
out for military use , and yet those compositions remain commercially
viable products , practical for the use they are intended .

I believe it is possible to make a practical energetic binder based upon
such materials . When I melt cast my first nitrated polyol composite ,
which was an ETN/PETN melt composite , I was astonished by the
brisance of that composition , as well as the stability and economy .
It made a good impression that has left me interested in what value
other similar compositions may have .

[nbk2000]

The explosive of choice for any purpose has many contexts to be considered.

Cost, availability of materials, difficulty of process, stability, power, decomposition products, reactivity with metals and other explosives, storage life, pressability/castability/machinability/etc.......

What's good for the Navy may not work for the Army, nor that which is acceptable in the last days of a world war would be acceptable any other time, or legit uses compared to criminal uses.

I admire the robust design principles of the military armaments industry, as well as the power and safety, but also realize that such things are neither needed or desireable in my own applications.

My critera, as a criminal, is universal availability of precursors with no ID or questions, easy synthesis in primitive conditions with no lab equipment, and high power. Storage life and high sensitivity are non-issues as anything I made would be used within a day or two and be handled carefully, but it would have to function every time and with violent effect, as failure to detonate is not acceptable.

It could be liquid, powder, or cast, because the form is secondary to the function, the device being built to hold the explosive in whatever form it may be, and directing its energy in the desired manner at the target.

Now, if I'm designing for military armaments, the critera is much different.

Stability and insensitivity to unintended initiation are primary, as the weapons will be stored for decades in hostile enviroments, and subjected to enemy attack.

The explosive must be reliable and adequately powerful, but a failure to function when the fuze impacts the target is preferable to the explosive going off at any time other than impact with the enemy, as spontaneous functioning can lead to catastrophic failure and destruction of irreplaceable war materials and loss of confidence in the weapon by your troops.

So, cutefix and roscoe, you both have your points of view, and both are correct, depending on the intended purpose, so there's no need to argue about it.

Both ends of the spectrum, sensitive/insensitive, weak/powerful, on and on, need to be explored as all of them have their uses. :)

Study the updates by the state-of-the-art weapons labs and get inspiration from that, but realize that you live among mortals who have to pay for toys with their own money (and not with the limitless pockets of taxpayers), and pay homage to the anarchists and guerrillas who improvise explosives from dirt and aspirin. ;)