An analysis of the DSC data in the Herrit-Jones paper

Originally posted by turbofan

Originally posted by pteridine
I am happy to see that you now stand corrected regarding the erroneous figure you posted from LLNL. The labs are not infallible.

There is no correction. Your opinion is not a correction. Your opinion means nothing. If you would like
to disprove the LLNL data, feel free to provide some scientific sources. A debate requires that you
qualify your answers with proof, not dribble of text from your "thoughts".

Excess energy is not an excuse, it is just another failing of Jones paper and another reason he is unable to claim thermite.

He never claimed thermite. Get that out of your head. I already corrected you on the term "thermitic".
Thermitic does NOT mean thermite.

The products of elemental iron, and oxidized aluminium in spherical form however is the signature for an aluminothermic reaction. Please understand the difference. Jones proved an aluminothermic reaction, not thermite.

Got it after 6 pages?

We are looking at total caloric output. A match is much hotter than 1000 gallons of room temperature water. Guess which has more heat. Your statement "The fact is, an aluminothermic reaction such as Al/Fe203 can produce 1500'C by itself. The additional heat by combustion is irrelevent." shows that you have temperature and heat hopelessly confused.

Not at all. I've already linked you to an explantion of heat vs. temperature in a thread I posted weeks ago.
Proving once again, you don't read links. Energy release over time is what I meant by that comparison.
There is no confusion. Power is what this is all about.

You confirm that you do not know the difference between temperature and heat and then you assume a thermite reaction to prove a thermite reaction. Jones' paper provides no evidence of any reaction other than combustion and no spheres of iron are shown.

FOr the FOURTH TIME: The signature of thermitic reaction is not 100% iron.

A thermitic reactoin requires the reduction of a metal oxide and the oxidation of a fuel metal.

Do you understand this SIMPLE concept? This exactly why I wanted to step through these points before
engaging in a debate.

Now we must go backwards and do what should have been done first.

Pteridine, do you agree that the spheres are not supposed to 100% iron to show a thermitic reaction
as per any scientific reference, and Tillotson

You are still confused about heat and temperature and you do not read the material that you post. Refer to the energetics figure in the initial post in your "Jones' Dust Analysis: Comparing Known Nano-Energetics ( A Response to "Pteridine" )." Note the key on the figure is backwards; energy per unit mass and energy per unit volume are reversed. Yes, I am correcting a figure by a national lab and the GoogleU reference is just what you posted in your thread. Refer to Jones' figure 30 for energetics. You are corrected, again.

In the Tillotson paper in JNonCrystalline Solids 285 (2001) 338-345, the energetics are measured and on page 343 are found to be only 1.5 kJ/g; far below the 3.9 kJ/g of the theoretical maximum. Do you still want to use this material and paper as your standard of excellence?

As to thermite and aluminothermitic reactions; the reaction between aluminum and iron oxide is called the thermite reaction whether it has gas generation materials mixed in with it or not. This is the reaction in question and changing the term does not change the underlying reaction. You may use "aluminothermic" if you like. This reaction runs in the absence of air and to show that it might be present, the first experiment that must be done is to show that it occurs without air. This is the point that has eluded you all this time and the point that you are desperately trying to evade.

You avoid the question once more and bring up iron containing spheres without addressing the energy discrepancies as measured by Jones. As a point of reference, you claimed "I've proven that a thermitic reaction occurred by showing that Iron Oxide has been reduced to elemental iron..." and used the melting point of elemental iron in your argument. Now you say that "iron containing" spheres are diagnostic for the thermite reaction. This is not correct.

You have also not clarified your position on the additive to the purported demolition material that resulted in combustion. First it was a matrix and then it was finely divided carbon that burned to cause the excess heat energy. If you need this to explain your position, pick one and we will discuss it.

Wow, this is like the ' teach PLB ' thread, and "show him his quotes a few replies' ago

Originally posted by -PLB-So why are you so upset when someone calls it a thermite reaction? Arn't you turning this into a game of semantics in order to avoid the hard questions?

For the second time: the chips are not thermite. You cannot call it a thermite reaction.

Again playing semantics games. I of course mean the sharpness of the slopes of the peak. What on earth could I else be talking about.

No, it's not semantics. You clearly do not know the width of the exotherm in your graph.

Tell me the span of the complete exotherm in YOUR graph.

Just look at the width of the blue peak of your home made graph, and write down how much degrees it spans

30 degrees

Now do the same for the original Tillotson graph.

I didn't re-draw the Tillotson graph

I redrew Jones' graph

No wonder you're so confused!!!!!!

I am sorry but I am not going to redraw this for you. You can just keep doing the simple test I wrote above until you do it right yourself.

Sure...see the reply above

So do you finally agree they are in the same order of magnitude? For example, in the Tillotson DSC the rise time is about 4 minutes. Just one minute difference from combustion. So proof, including sources, why a full combustive reaction can not take place in a time span of 2 minutes. You already accepted the proof it is possible in 5 minutes. Why not in 2?

See, there's your PROOF you DO NOT GET IT!

Please stay out of thie debate!!!

Once you learn how wide your exotherm is, you will see you are DEAD wrong!!!

Not only do you include the introduction of heat from ignition to peak, you INCLUDE THE DECAY FROM PEAK
to REFERENCE!



And again - NO, the SLOPE is NOT the same. Not even close!


Maybe once you compare your graph to the proper reference (IE: Jones and NOT Tillotson), you will clue in.

Originally posted by pteridinein your "Jones' Dust Analysis: Comparing Known Nano-Energetics ( A Response to "Pteridine" )." Note the key on the figure is backwards; energy per unit mass and energy per unit volume are reversed. Yes, I am correcting a figure by a national lab . Refer to Jones' figure 30 for energetics. You are corrected, again.

Wow, after 3 pages you were finally able to provide details so I could figure out what you were referring to.

All of this time, I thought you meant this graph as only since I posted it, did you bring up the 'key'
files.abovetopsecret.com...

So guess what, I agree with you...partially! The key is backward. However, that is not my problem, nor
my correction. Unfortunately for you, the X-axis label is correct and so are the values for heat of reaction.

We'll pretend the colour key is correct for now. Do you agree with the values?

thermite reaction whether it has gas generation materials mixed in with it or not. This is the reaction in question and changing the term does not change the underlying reaction.

I agree with that too...partially. So, the mixture is not classic Thermite due to the presense of other material...
so it's NOT "thermite". Correct?

If the aluminothermic reaction started as 2Al/Fe203 and ended as elemental iron, and oxidized aluminum
it would be considered a thermite reaction.

Do you agree?

Let's stop there and get your comments before moving forward on the rest of your reply.

Originally posted by turbofan

Wow, after 3 pages you were finally able to provide details so I could figure out what you were referring to.

All of this time, I thought you meant this graph as only since I posted it, did you bring up the 'key'
files.abovetopsecret.com...

So guess what, I agree with you...partially! The key is backward. However, that is not my problem, nor
my correction. Unfortunately for you, the X-axis label is correct and so are the values for heat of reaction.

We'll pretend the colour key is correct for now. Do you agree with the values?

thermite reaction whether it has gas generation materials mixed in with it or not. This is the reaction in question and changing the term does not change the underlying reaction.

I agree with that too...partially. So, the mixture is not classic Thermite due to the presense of other material...
so it's NOT "thermite". Correct?

If the aluminothermic reaction started as 2Al/Fe203 and ended as elemental iron, and oxidized aluminum
it would be considered a thermite reaction.

Do you agree?

Let's stop there and get your comments before moving forward on the rest of your reply.

No the vaues are not all correct. I refer you again to Jones' figure 30 for our discussion to prevent inconsistencies and errors in conversion between kCal and kJ.

If you claim components of thermite caused the exotherm, then you have to consider the thermite reaction. Call it whatever you like but accept that there is no other material present that would produce energy without combustion or show what that substance might be, based on the data in Jones' paper.

reply to post by turbofan


Your poor drawing skills made the blue line look like Tiltsons graph. The peak is about 3 pixels wide, which corresponds to about 5 degrees.

I have been responding to your argument that the "sharp slope" is evidence of thermite (or whatever you like to call it, not that interested in your semantics game), not the argument about the entire width of the exotherm (I can go into that one too if you like, as you have not supported that either with any source). And I am, to my knowledge, consistently referring to the width of the peak, not the width of the exotherm (if I did it was a mistake). The combustion DSC and the ones of Jones do show similar sharpness in the slopes. Of course the DSC of crude oil and Jones unknown sample are not exactly the same. I only used it as example of combustion showing a sharp slope. Nothing more.

As for your width argument, if a small width of the entire exotherm indicates a thermite or explosive reaction, Tiltsons DSC fails to pass this criteria.

Originally posted by -PLB-
reply to post by turbofan

 

Your poor drawing skills made the blue line look like Tiltsons graph. The peak is about 3 pixels wide, which corresponds to about 5 degrees.

Only 'god' knows how you thought Tillotson's graph was drawn when we were totally discussing Jones trace
vs. your oil trace.

Thanks for wasting all of that time though!

I have been responding to your argument that the "sharp slope" is evidence of thermite (or whatever you like to call it, not that interested in your semantics game), not the argument about the entire width of the exotherm (I can go into that one too if you like, as you have not supported that either with any source). And I am, to my knowledge, consistently referring to the width of the peak, not the width of the exotherm (if I did it was a mistake). The combustion DSC and the ones of Jones do show similar sharpness in the slopes. Of course the DSC of crude oil and Jones unknown sample are not exactly the same. I only used it as example of combustion showing a sharp slope. Nothing more.

As for your width argument, if a small width of the entire exotherm indicates a thermite or explosive reaction, Tiltsons DSC fails to pass this criteria.

Well, consider yourself off-line in this discussion.

YOu obviously don't know what you're talking about as you try to relate one part of the exotherm trace
to prove your case.

Too bad, so sad but the energy over time is figured by the entire exotherm trace...not ... just... the
"ignition slope"or whatever YOU want to call it...

Not even Pteridine will agree with you on that.

PLease stay out of this debate.

Originally posted by turbofan

Only 'god' knows how you thought Tillotson's graph was drawn when we were totally discussing Jones trace
vs. your oil trace.

Thanks for wasting all of that time though!

Does it change the fact the graph is completely wrong? Nope.

Well, consider yourself off-line in this discussion.

YOu obviously don't know what you're talking about as you try to relate one part of the exotherm trace
to prove your case.

Too bad, so sad but the energy over time is figured by the entire exotherm trace...not ... just... the
"ignition slope"or whatever YOU want to call it...

Not even Pteridine will agree with you on that.

PLease stay out of this debate.

edit on 19-12-2010 by turbofan because: (no reason given)

It wasn't me who came with the sharp slope argument. It is kinda amusing how you ridicule your own arguments, but it seems like we agree. So the only argument left now is the width of the entire exotherm. That rules Tiltsons out as being a typical thermite trace.

Originally posted by pteridineAs to thermite and aluminothermitic reactions; the reaction between aluminum and iron oxide is called the thermite reaction whether it has gas generation materials mixed in with it or not.

Reading your quote it appears you agree that an aluminothermic reaction will occurr whether gas producing
materials are mixed, or not.

Do you also agree that combustion is not a factor since the redox took place between the Iron Oxide and
Aluminum leaving elemental iron and oxidixed aluminum?

You also opine that the figures in LANL are incorrect. What is incorrect about the heats of reaction for
the mixtures listed?

Lastly, what will you accept as supporting evidence to prove the science? I've listed several government
lab sources and it appears you wont agree with any of them. Why is that?

You do realize that I'm going to ask you for sources to back up your claims. YOu are hardly holding your
end of the deal by constantly refusing to provide a scientific source for your opinions.

I refuse to continue this debate if your only response is to offer your opinion.

On a side note, for those others than make up their own definitions and skew my quotes, here are the criteria
for the exotherm once again:

The height of the peak; the slew of the trace; the duration between Temp 2 -Temp 1 indicate the amount
of energy released.

Pteridine, do you agree that a more narrow exotherm indicates a reaction which is closer to that of an explosive
rather than combustion? Do you also agree that a sharp slope (positive , or negative) indicates the speed of a reaction closer to that of an explosive rather than combustion?

In the figure below (From Tillotson's paper), the scientists conclude that thermitic reaction begins at 500'C,
and the exotherm centers at the 530'C point along the x-axis. Even though there is presence of heat over the
control temperature at 400'C through 500'C, this section is excluded as the 'active' region

Finally, do you conclude that the quick drop, and slope of the exotherm indicates that the available energy
was spent in quick fashion and more closely resembles an explosive event, over a combustion event?

reply to post by turbofan


Thermite reactions do not need gas generating material. In order to occur, the reaction needs the energy of activation and close proximity of the reactants.

Combustion is certainly a factor as the DSC was run in air instead of under argon. They have no idea how much of the exotherm was from combustion and how much was from some other reaction. There is no evidence that thermite was in the paint. You can't assume thermite to prove thermite.

As I have said all along, the only reference you need is Jones' paper. The paper is the basis for his claims and my position is that they are unfounded, based on his paper. I have been using his data and have shown its discrepancies. You also need a knowledge of some basic arithmetic, which seems to elude some on this board. I have explained things simply, based on Jones' own numbers. You demand references and Jones paper is it. You have never responded to the main topic of this thread other than to try to shift the argument away from the topic.

Now you can answer some questions:
Explain why there is excess energy in the DSC and the cause of the excess energy. Do you claim combustion of carbonaceous binder or finely divided carbon? If so, which?

Explain what simple experiment should be done to show only non-combustion reactions. I know you won't answer this and we both know why, don't we Turbo.

Do you yet understand that peak shapes of DSC traces are extrinsic and not diagnostic and that the Jones paper made no attempt to use them as evidence? Remember we are discussing the inconsistencies in the energetics data in Jones paper. Jones didn't use peak shape as evidence for his claims. My contention is that he is not justified in his conclusions based on his data. The data we are talking about on this thread is his energetics data.

reply to post by pteridine


I'll answer your questions when you finish answering mine. You left one out again.

Let's try it this way:

Do you agree that a redox reaction between the Iron Oxide and Aluminum will take place whether there is
air present, or not?

reply to post by turbofan


Of course the reaction will take place. I never said anything else. The problem has always been the presence of an unknown amount of combustion. That must be ruled out to measure the energy from non-combustion reactions.

Originally posted by pteridine
reply to post by turbofan

 

Of course the reaction will take place. I never said anything else. The problem has always been the presence of an unknown amount of combustion. That must be ruled out to measure the energy from non-combustion reactions.

What does it matter if material is combusting if you admit that the thermitic reaction will take place whether
air is present, or not?

The excess heat is of no concern as you admit that redox takes place in the presence of air.

This proves an aluminothermic reaction beyond all doubt as the oxygen in the air will NOT react with the bonded
Iron Oxide and Aluminum.

Therefore the only way to reduce the iron oxide is for the aluminum to attract the oxygen.

The presence of elemental iron is the proof as is the oxidized aluminum.

Originally posted by turbofan

Originally posted by pteridine
reply to post by turbofan

 

Of course the reaction will take place. I never said anything else. The problem has always been the presence of an unknown amount of combustion. That must be ruled out to measure the energy from non-combustion reactions.

What does it matter if material is combusting if you admit that the thermitic reaction will take place whether
air is present, or not?

The excess heat is of no concern as you admit that redox takes place in the presence of air.

This proves an aluminothermic reaction beyond all doubt as the oxygen in the air will NOT react with the bonded
Iron Oxide and Aluminum.

Therefore the only way to reduce the iron oxide is for the aluminum to attract the oxygen.

The presence of elemental iron is the proof as is the oxidized aluminum.

What elemental iron? Jones never claimed elemental iron. Stick to the topic.The excess heat is of concern because you do not know how much of the heat is combustion. It could be all of it. You are assuming that the thermite reaction is occurring but that is what you have to show.

Here's how it should be done:
1. DSC under argon. If there is no reaction, it isn't thermite, it's just paint, so you don't have to look further. If there is a reaction, it might be thermite so you should look further.
2. If there is a reaction, you have to determine what reacted. You first might want to do some analyses just to get an idea of what you have. XRD will show you the iron oxide, which you know you have, and any mineral filler that might be in there. You may also see the aluminum, if any.
IR will tell you about the matrix and may allow you to match it with known materials. TV shows are always doing this with car paint but they make it seem much easier and faster than it really is.
You could also dissolve the matrix and recover what was in it for analysis if the matrix was obscuring things. MEK is a weak solvent and unsuitable. Methylene chloride should work but there are better ones if need be. I once had to dissolve set potting epoxy and used a hot DMF-DMSO mix.
3. Aluminum metal is the key ingredient; you know you have iron oxide. EDAX is always questionable because of the aluminum stage so you'd need to use another method. If you find aluminum then you have to show how the material could be used. Some paints contain aluminum metal so you'd have to show that the stuff was intended as a demolition material or people could just claim it was paint.
4. If you find no records of a red primer paint containing aluminum from that time period, things get more interesting. You might want to make a batch of it and see what it can do to a steel beam. Calculations say not much, but the experimental imperative cannot be denied.
5. If the theory stays together after all of this, publish it in an actual journal and wait for the legal fireworks.

I believe that you said you would answer some questions.....

Originally posted by pteridineWhat elemental iron? Jones never claimed elemental iron. Stick to the topic.

He claimed an energetic nano-material.

He FOUND elemental iron in the post ignition residue.

You admitted this as you acknowledged the spheres contained iron.

You are assuming that the thermite reaction is occurring but that is what you have to show.

WE ALREADY DID PROVE IT.

You ADMITTED TO IT.

There is elemental Iron and oxidized aluminum. That is the product of an aluminothermic reaction.

See here AGAIN:

In this reaction iron (III) oxide is reduced to metallic iron by aluminum. It is reported that the reaction will reach a temperature of about 3000°C, meaning both reaction products are molten (mp Fe = 1530°C; mp Al2O3 = 2030°C).

www.thecatalyst.org...

Therefore, since the residue was found, Jones PROVED a thermitic reaction.

You do not need to run the test without air, because the oxygen in the air WILL NOT react with the bonded Iron
Oxide and Aluminum. The redox will take place between the Iron Oxide and Aluminim NOT the air!!!!!!!

Proven also by Tillotson:
[atsimg]http://files.abovetopsecret.com/images/member/77fdd4611a10.jpg[/atsimg]

Hence, the discussion about heat is pointless.

This debate is over once you understand that air will not react with the 2Al + Fe203 bond!!!!!!!!!!!!!!

Here's a quick summary:

Start with 2Al+Fe203
Use air, or don't use air...it DOESN"T MATTER BECAUSE IT WONT REACT WITH THE 2Al+Fe203
Ignite the chip
Look at the residue
Did the Iron Oxide reduce and Aluminum Oxidize?
Yes? Then a thermitic reaction has been proven
Did you end up with Al2O3 + 2Fe ?
Yes? Then a thermitic reaction has been proven

reply to post by pteridine

What elemental iron? Jones never claimed elemental iron.

From the paper pg 21:

"In the case of this iron-rich spheroid, the iron content exceeds the oxygen content by approximately a factor of two, so substantial elemental iron must be present."



From the paper pg 29, point #8:

"In several spheres, elemental iron was verified since the iron content significantly exceeded the oxygen content."


From a press conference on 5/6/10:

"and furthermore we find iron oxide beforehand - I'll show you data on that in a moment - and we find elemental iron, that is, not enough oxygen to produce iron oxide after ignition. That means that the iron is reduced, in chemical terms. which means there was a thermite reaction."

at 6:26 in this clip www.youtube.com...

reply to post by NIcon


Finding such non-stoichiometric oxide material does not prove thermite. Note also that the thread topic is about DSC data.

reply to post by pteridine


I noticed this is the second point that I've corrected you about the paper in this thread. If I weren't a neutral observer I would say that you don't appear to have read the paper. But I won't since I'm staying neutral.

Originally posted by turbofan
Hence, the discussion about heat is pointless.

This debate is over once you understand that air will not react with the 2Al + Fe203 bond!!!!!!!!!!!!!!

The combustion in air is one reason why the paper has proved nothing. I note that basic concepts of chemistry also elude you. There is no 2Al + Fe2O3 bond. It is a mixture, even though you have tried to bond it with many exclamation points.

The carbon is combusting but how much carbon is combusting? We don't know and we should find out.

Now explain the energetics. You have avoided doing so since we started. You write about everything else because you don't want to address the issue. It is time for you to address the thread topic.

1. You agreed that combustion in air caused the excess heat in the DSC.

2. How do you show what part of the exotherm came from combustion and what part came from another reaction? Remember, the sample is an unknown so you can't assume thermite did anything.

reply to post by NIcon

You are correct, Jones did claim elemental iron. Jones deduced the presence of elemental iron because the measured oxygen was less than a stiochiometric amount and he didn't notice any other elements in the EDAX. XRD might have been helpful. Note that he did not see elemental iron; it was always combined. My statement should have read "Jones did not measure elemental iron."

It would be interesting to hear your views on how combustion energy and other reaction energy can be discriminated.