Abstract
Mark Basile analysed red-gray chips he found in dust samples collected in lower Manhattan very shortly after the collapse of the World Trade towers on 2001/09/11 [1.1]. In particular, he shows how vigorously his chip reacts when heated on a steel strip, producing rapid ejections of gas [1.2]. Basile suggests that this reaction is best explained by the thermite reaction, apparently affecting the organic matrix.
In an earlier blog post [2], I have shown that his data reveals that at most 4.7% by weight of the "energetic" red layer of one particular chip could possibly be stoichiometric thermite, while most of the layer (ca. 88%) must be a matrix of some unidentified polymer.
Some 9/11 Truth Movement adherents who believe that these red-gray chips are "thermitic material" claim that organic substances are typically a component of modern nano-thermite preparations, both as collateral residue of the synthesis (e.g. ca. 10% [3.1]) and as an additive to give nano-thermite explosive properties [3.2] (the organic material is rapidly turned to gas and can do volume work).
In this post, I will show that, at a mass ratio between thermite and organic matrix of about 1:19, as Basile's data implies, the chemical energy of the thermite does not nearly suffice to turn organic polymers to gas. It follows that the rapid reaction and creation of gas is powered by organic combustion and perhaps externally applied heat, not a thermite reaction.
Data
Basile's "lucky" chip #13
As I showed in [2], under the most "thermite friendly" assumptions, and taking Basile's data as it is, the red layer of his "lucky" red-gray chip #13 contains, by weight,
- At most 4.74% ideal (stoichiometric) thermite (of the common Fe2O3+Al variety)
- At least 87.8% solid hydrocarbon matrix, unknown chemistry. It is safe to assume that this matrix is some form of organic polymer (or a mix of polymers), that contains no Fluorine or Chlorine
- Ca. 7.1% (the balance) inorganic compounds, assumed to be inert
Thermal properties of various polymers
The Appendix of [4] lists many combustion-related thermal properties of many organic polymers. The following values will be used in the discussion. I chose Epoxy as the reference material, since James Millette [5] has identified epoxy as the matrix material for some red-gray chips. The properties of many other non-halogenic organic polymers are in roughly the same magnitude as those of epoxy. I will state ranges for most polymers in parentheses, even though the extreme values usually are for materials that wouldn't make much sense for a matrix:
- Onset of decomposition: Td 427 °C (250 - 570 °C, Table A-1, first column). This property describes at which temperature the matrix will beginn to decompose, a process that usually involves some charring and some release of gas. It will also show in DSC curves.
- Ignition temperatur Tign: 427°C (271 - 600°C, Table A-1., third column). Note the ignition temperature may be influenced by association / mixing with other materials. Note also that some polymers don't ignite (don't burn with atmospheric oxygen) and just decompose
- Enthalpy of gasification hg: 1.5 kJ/g (1.1 - 2.6 kJ/g, Table A-2, third column). This value describes how much energy must be expended to break the molecules down to gas molecules such as CO2 or water vapor during burning or decomposition - not including the heat necessary to bring the polymer to the temperature where the molecukle structure begins to break down. Note that most polymers leave behind some solid residue (char) after gasification: Epoxy 4% of its mass (column two of table A-2), others up to 75%.
- Heat capacity cp: 1.7 J/g/K (0.93 - 2.09 J/g/K, Table A-3, third column). This value describes how much energy is expended when heating 1 g of polymer by 1 °C (or by 1 K, which is the same). This value changes with temperature, it is given for normal "room temperature" conditions, but it typically increases somewhat with rising temperature. I will consider it as constant, which is a "thermite-friendly" imprecision.
- Effective heat of combustion HOC: 20.4 kJ/g (14.4 - 41.9 kJ/g, Table A-5, first column). This is the energy effectively released by 1 g of polymer under air and takes into account that the theoretical maximum is not reached in praxis. Epoxy for example burns with only only 75% effectiveness in experiment. This is again a "thermite-friendly" choice, as I will use the theoretical max for thermite (3.96 kJ/g) and not actual effective heat release (perhaps 3 kJ/g or less).
Discussion
Heating epoxy with thermite
To simplyfy things, let's ignore the inorganic components other than stoichiometric thermite, and mix thermite and epoxy in the proportions according to Basile's data: 4.74 g of thermite, 87.8 g of epoxy. Let's further assume we could ignite this thermite and have it react perfectly within the epoxy matrix without heating the epoxy first, and have all of the heat of reaction be absorbed by the epoxy. Could the thermite reaction turn the matrix to gas and cause the rapid gas ejections seen in Basile's video? Let's see!
4.74 g of thermite contain at most (theoretical maximum) 4.74 g x 3.96 kJ/g = 18.7 kJ
If you put these 18.7 kJ of heat into 87.8 g of epoxy, which has a specific heat capacity of 1.7 J/g/°C, you warm it by 18,700 J / 87.8 g / 1.7 J/g/°C = 125 °C, reaching ca. 150 °C. Neither epoxy nor any other polymer would come close to the start of decomposition just from this thermite reaction!
Gasifying epoxy with thermite
Of course, the assumption that the epoxy isn't already heated to the brink of decomposition isn't realistic - thermite wouldn't ignite at room temperature, and you can't heat only the thermite inside the matrix. So next up. let's assume the epoxy is already heated to its decompostion temperature of 427°C, as is the thermite - which is concidentally (???) the temperature at which Harrit e.al. [6] observed ignition of red-gray chips. How much epoxy could the reaction of 4.74 g thermite turn to gas? Let's see!
Epoxy has an effective enthalpy of gasification of 1.5 kJ/g. The energy release of our thermite, 18.7 kJ, could thus gasify 18.kJ / 1.5 kJ/g = 12.5 g of epoxy, out of 87.8 g of epoxy in our sample, that's about 14%.
What causes the gas jets and the heating of "lucky" chip #13?
Marc Basile had heated his chip on a thin (50 µm) steel strip through which he sent a constant electrical current. Here a screenshot from 40:17 in his presentation [1]:
This is, obviously, an important heat source. He gives is no idea how hot the strip got during the experiment. Hot enough apparently to ignite and gasify something - but potentially much hotter than just that. At the very least, this external heat infused 400 K x 1.7 J/g/K = 680 kJ/g into the probe just to heat the epoxy - thermite's theoretical max would be about 180 J/g, or 26% maximum compared with the heating strip.
It is obvious from my calculations above that thermite, even if present at all and in the maximum possible amount, contributes only minimally to the reaction of the organic matrix.
In particular: Every Joule expended on heating the matrix can't be expended to gasify it. Every Joule expended to gasify the matrix can't be used to heat any bit of matrix. And every Joule expended to do work on the matrix is lost to heat and ignite the next thermite particles to continue the thermite reaction. This material could never burn if the matrix were inert and the probe weren't externally heated. What is the use of thermite in such low concentration?
The organic matrix on the other hand is assured to release enough energy to: Heat the probe including all minerals and the gray layer, achieve full gasification, and warm its environment: of the 20.4 kJ/g effective energy density, only 1.5 kJ/g are expended on gasification, 0.7 kJ/g (1.7 J/g/K x 400 K) are expended to heat the same mass of epoxy from room temperature to ignition temperature, and then 18.2 kJ/g are left to do work on everything else
Conclusions
The three obvious and available heat sources in Basile's ignition experiment provide this much energy per gram of probe:
- Combustion of epoxy: 12.6 - 36.8 kJ/g (Epoxy: 17.9 kJ/g = )
- Heating strip: 0.7 kJ/g or more
- Thermite: 0.18 kJ/g or less
5% Thermite in an organic matrix make no difference. On its on, it couldn't warm the matrix even to onset decomposition, it could not destroy more than a small fraction of the polymer molecules, and it would be incapable of doing any significant work on anything outside of the chip
Whatever reaction is observed in the video of chip #13 burning, it is not driven by a thermite reaction. It is simple organic polymer combustion, helped to an unknown but probably significant degree by the external heat of the heating strip underneath.
Additional remarks
1. I believe almost all red-gray chips found in WTC dust, including Basile's chip, are some sort of red primer paint on spalled steel / steel mill. Gauging the composition of LaClede standard primer [7], I suspect that Basile's quantification of the elemental composition is a bit off the mark - I would expect to see closer to 30% inorganic materials rather than the 12% according to Basile. I suspect in particular that he underestimates the amount of iron: His red layer is red paint, and the red pigment most certainly is iron oxide. There should be closer to 10% of the element iron rather than Basile's 2.6%. However, I am only guessing here, and I can only go by the data Basile provides
I am convinced that Millette [5] and Harrit e.al. [6] looked, most closely at LaClede standard primer, which according to my own analysis [7] can be expected to contain 2.4% aluminium. Harrit's chips a-d match the expected elemental composition of LaClede paint so closely, that I would say definitely these chips contain about that much of the elememnt Al. If, hypothetically, all that Al were elemental, it could react with three times as much of the iron oxide to form 10.4% thermite - against 71.5% epoxy. This ratio, 1:6.9 thermite:epoxy, is still insufficient to either heat epoxy from room temperature to ignition point, or gasify most of it, and the heat content of the epoxy would still outnumber that of the thermite by a ratio of at least 50:1, rendering the thermite insignificant.
In further, unpublished work, I have estimated that the total Al content of Harrit e.al.'s MEK-soaked chip ([7], Fig. 14) is only 0.6%, to allow for a maximum of 2.4% thermite. It should be obvious by now that this is even less significant than the hypothetical thermite-content of Basile's chip or the chips a-d that resemble LaClede so much. It is interesting that this MEK-soaked chip, with its very low overall Al-content, is the only one where the "thermite" theorists seem to have identified any elemental Al at all.
References
[1.1] Mark Basile: 911 Dust Analysis Raises Questions. Videotaped presentation at the Porcupine Freedom Festival in Lancaster, New Hampshire on 26th June 2010, 4pm (On YouTube; 59:22 minutes, Last retrieved: June 16 2012)
[1.2] Mark Basile ignites a chip (nano-thermite) - 9/11. This szene is shown in [1.1] between between 41:43 and 42:00 minutes. (On YouTube; 0:16 minutes, Last retrieved: June 16 2012)
[2] Oystein: How Mark Basile confirms that red-gray chips are not thermitic. Posted in author's blog on March 18 2012
[3.1] T.M. Tillotson et al: Nanostructured energetic materials using sol-gel methodologies. Journal of Non-Crystalline Solids 285 (2001) 338-345
[3.2] (Currently too lazy to find an exemplary paper)
[4] Richard E. Lyon and Marc L. Janssens: Polymer Flammability. May 2005 - Final Report for the U.S. Department of Transportation and FAA. Report No. DOT/FAA/AR-05/14
[5] James R. Millette: Revised Report of Results: MVA9119. Progress Report on the Analysis of Red/Gray Chips in WTC dust. Prepared for Classical Guide, Denver, 01 March 2012.
[6] Niels H. Harrit et al: Active Thermitic Material Discovered in Dust from the 9/11 World Trade Center Catastrophe. The Open Chemical Physics Journal, 2009, 2, 7-31. Figure 19 shows ignition temperatures around 430°C
[7] Oystein: Another primer at the WTC: LaClede Standard Primer
. Posted in author's blog on March 16 2012