Rossi's 2009 TOF-SIMS analyses digitized (+ theory speculation)

@axil: could you please indicate where iridium is being mentioned in the context of these iron oxide catalysts? As fas as I'm aware of, the inert binder/support is usually composed of one or more oxides of chromium, aluminium or silicon. Iridium-based dehydrogenation catalysts do exist in commerce, but iridium replaces the iron oxide there. According to Holmlid the reaction can take place with different dehydrogenation catalysts. See paragraph 11 here in his patent application:

https://www.google.com/patents/EP2680271A1

Quote

[0011] A "hydrogen transfer catalyst" is any catalyst capable of absorbing hydrogen gas molecules (H2) and dissociating these molecules to atomic hydrogen, that is, catalyze the reaction H2 → 2H. The name hydrogen transfer catalyst implies that the so-formed hydrogen atoms on the catalyst surface can rather easily attach to other molecules on the surface and thus be transferred from one molecule to another. The hydrogen transfer catalyst may further be configured to cause a transition of the hydrogen into the ultradense state if the hydrogen atoms are prevented from re-forming covalent bonds. The mechanisms behind the catalytic transition from the gaseous state to the ultra-dense state are quite well understood, and it has been experimentally shown that this transition can be achieved using various hydrogen transfer catalysts, including, for example, commercially available so-called styrene catalysts, as well as (purely) metallic catalysts, such as Iridium and Palladium. It should be noted that the hydrogen transfer catalyst does not necessarily have to transition the hydrogen in the gaseous state to the ultra-dense state directly upon contact with the hydrogen transfer catalyst. Instead, the hydrogen in the gaseous state may first be caused to transition to a dense state H(1), to later spontaneously transition to the ultra-dense state H(-1). Also in this latter case has the hydrogen transfer catalyst caused the hydrogen to transition from the gaseous state to the ultra-dense state.

Quote from Eric Walker

For some time Rossi worked with Focardi, and Focardi worked with Piantelli at one point. Piantelli has been pursuing nickel since at least the early 90's. What you say may be true, but absent further information, I'm guessing Rossi has been working with nickel since he started collaborating with Focardi, or perhaps even earlier, as nickel was kind of an Italian thing.

Even if there are reports that thermal anomalies have been occurring in the same catalytic reactions in oil refining processes that Rossi might have been working with for years? And even if incidentally the analyses in the OP show no nickel being present in relevant amounts but rather likely one of the catalysts involved in those reactions? Rossi might have started using Nickel later on, but possibly not in the way most other researchers have been so far.

Quote

There is evidence that impurities are possibly important, e.g., as summarized in Ed Storms's reviews.

I'm not implying that impurities did not have had a role in Pd-D experiments for obtaining some sort of reproducible effect, but rather that for hydrogen in order to penetrate into the bulk (absorption) dissociation at the surface of the metal upon adsorption must take place. If the surface of the metal, in addition of being nano/microstructured, is also free of impurities, this spontaneous process will occur more easily.

However, my conclusion (and Holmlid's) is also that materials catalyzing the H2 → 2H reaction are desirable. The critical impurities in Pd-D experiments might have been operating towards that goal.

@axil: more simply explained, I believe this means Holmlid collected on an Iridium foil the ultra-dense deuterium generated by the iron oxide catalyst (placed in pieces inside a steel tube providing a flow of D2 gas), and used the Nd:YAG laser pointed on it instead of directly on the catalyst as he did in previous experiments. A very simple diagram:

EDIT
axil: as for the other paper, I remember reading it some time ago. I'm not sure I'm competent enough to have an opinion it, but it looks like they ran computer simulations at 0K and found out that potassium-promoted iron oxide catalysts have unexplored properties that can be useful in catalysis. They haven't investigated yet whether the formation of Rydberg states is theoretically possible (at least according to computational models) but they are not ruling it out. I don't think this paper is exceedingly relevant in this case. I also remember reading in a couple of Holmlid's papers that too much potassium content in the catalyst can interfere with Hydrogen Rydberg Matter production, and that some amount of carbon on the surface is needed for the catalyst to efficiently function. See [excerpt 1] and [excerpt 2]. Are they modeling this too?

Sources (paywalled):
1) http://iopscience.iop.org/arti…C7E719C6F500936A1CB75A.c1
2) http://pubs.acs.org/doi/abs/10.1021/ef050172n

I've been collecting a few links and paper references indicating that thermal anomalies, oscillations and runaway do seem to be happening in hydrogenation catalytic beds in the oil processing industry, and that this has been documented for quite some time, even before cold fusion claims. Several explanations have been provided for this phenomenon, which still remains not very well understood. I find quite plausible that LENR processes could be involved and that heterogeneous catalysts are the key for obtaining them. These hydrogenation bed reactors usually include metallic Pd, Pt, Ni catalysts on ceramic supports, or potassium-promoted iron oxide catalysts.

Robert Godes of Brillouin Energy Visits Finnish Officials and Statoil in Norway
Is rust a good candidate for runaway LENR?
Self-sustained oscillations of temperature and conversion in a packed bed microreactor during 2-methylpropene (isobutene) hydrogenation
Thermal oscillations during the catalytic hydrogenation of nitrobenzene

Critical Phenomena in Trickle-Bed Reactors
OSCILLATIONS OF CATALYTIC ACTIVITY IN HYDROGENATION OF ETHYLENE ON Ni-Al2O3
Oscillatory behavior of the ethylene hydrogenation reaction at high temperatures over nickel catalyst in the presence of an applied magnetic field

Rust Catalyzed Ethylene Hydrogenation causes Temperature Runaway
How to Prevent Runaways in Trickle-Bed Reactors for Pygas Hydrogenation
http://www.sciencedirect.com/s…cle/pii/S0167299197800213
CFD study of an evaporative trickle bed reactor: Mal-distribution and thermal runaway induced by feed disturbances

Yesterday I posted this comment on ECW on my view about Pd-D cold fusion experiments:

Quote

[...] What I'm saying is that a lump of solid Pd metal by itself isn't going to work off the bat unless its lattice structure gets heavily modified. In cold fusion experiments like the ones by DeChiaro (as reported on ECW this is usually performed through deuterium loading and electrolysis over prolonged periods of time. This process can radically alter the lattice and with much luck eventually produce the nano vacancies needed for excess heat production.
Alloying Pd with a different metal might further increase chances that right vacancies form in the process, but it still might not be enough.

What Leif Holmlid's research suggests is that by employing a prepared (or commercially available) heterogeneous catalyst one might be able to produce Rydberg Matter Hydrogen (possibly the culprit for excess heat in cold fusion experiments) reproducibly. Besides using potassium-iron oxide catalysts, he suggests in his patent that metallic catalysts could also be used. These usually include a dense micro/nano dispersion of a reactive metal (like Pd) on a porous ceramic support like alumina for structural stability and increased area, so they might already have the needed nano vacancies from the get-go.

It seems therefore possible that one could shortcut the entire loading and electrolysis process with pure metals by using a properly prepared catalyst. Some (like iron oxide Fischer-Tropsch/Styrene catalysts) might work better than others.

My opinion is overall growing stronger towards this effect being a result of unexplained phenomena which have already been occurring in catalysis in certain fields.

I believe that Leif Holmlid's observations, experiments and theories would be consistent with this view and with most LENR experiments, perhaps including also those occurring in a dusty plasma.

Since this has sort of become my personal speculation thread on the implications of Rossi's 2009 analysis and Rydberg Matter Hydrogen, I'm adding some more thoughts.

I changed my mind on one aspect of Leif Holmlid's research. I previously said that him stating that his reaction isn't LENR, but that aspects of LENR experiments might be related with it could have been a way for him to distance himself from cold fusion experiments. That might be true in a way, but if one sees what actually happens in his experiments under a different light, it could be exactly as he's saying.

If the production of denser forms of hydrogen through catalytic reactions at the nano-scale is true, then most of Holmlid's observations are a direct result of their properties. Even though in his case nuclear fusion is observed to occur - spontaneously too - at room temperature or near-room temperature, it is not “cold” fusion in that conditions for “hot” fusion such as density (>130 Kg/cm3 for ultra-dense Deuterium) are already partially fulfilled (also check out on wikipedia what ICF - inertial confinement fusion - is about).

So if LENR experiments are mostly about the production of Rydberg Matter Hydrogen - dense or metallic Hydrogen in Holmlid's words - and its even denser states, it might as well be that LENR have been some sort of optimized hot fusion all along, and that new physics and novel nuclear processes wouldn't be required to explain most observations. However, this would also imply that existing natural phenomena could be explained in different ways than previously assumed.

EDIT
Before somebody else points it out, Holmlid explains the lack of neutrons this way (excerpt from the previously linked paper):

Quote

It is expected that neutrons will be ejected from a nuclear fusion process. However, only relatively small but significant fluxes of neutrons have been detected in experiments using laser-induction. The most important factor is the large density of D(0), which makes it difficult even for neutrons to leave the material without numerous collisions with the deuterons. Mean free paths as short as 150 nm even for 14 MeV neutrons can be calculated. It is also possible that other nuclear processes but normal D + D fusion dominate. By selecting the layer thickness correctly, it is however possible to observe ejected 4 He and 3 He after collisions with D clusters by time-of-flight.

Continuing my exploration on the plausibility of Rydberg Matter Hydrogen and Ultra-dense hydrogen as a possible explanation for most observations in the LENR field, today I found out (a bit late, admittedly) that Edmund Storms regards the Hydroton, a hypothetical hydrogen molecule generated by nano-cracks (or NAE) and responsible for excess heat and fusion products, as having the characteristics of metallic Hydrogen. Remarkably, this would make it similar to the ultra-dense hydrogen observed and studied by Holmlid and colleagues for years.

Besides his book (which I don't have), it looks like there is more on his Hydroton concept on a few papers on LENR-CANR.org:
http://lenr-canr.org/acrobat/StormsEexplaining.pdf
http://lenr-canr.org/acrobat/StormsEresponseto.pdf

And briefly mentioned here at minute 13:24 (I haven't had the time yet to listen to the entire interview):

Transcription of the relevant portion:

Quote

Hydrogen has a very limited possible electronic interaction, meaning there's only one electron involved with each nucleus. So, the number of energy states is very very limited and Hydrogen is one of the more well-known electron states. If I were going to form a particular structure that had the capability that I proposed the Hydroton has, I almost have to accept the same electron state that would be creating metallic Hydrogen. So there's a natural relationship between the two. On the one hand, people have proposed that metallic Hydrogen can initiate a nuclear reaction; I'm saying that I create something that has the characteristics to do precisely that within cracks and so, therefore that it has the characteristics of metallic Hydrogen.

Robert Greenyer suggested on E-Cat World:

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With the 100um Fe2O3 fuel Particle 3 in the Lugano report, free O2 in the air and Al from the LiAlH4, could it be that a dehydrogenation catalyst was being made in-situ in the Lugano reactor by careful decomposition/heat treatment of the reactants and atmosphere?

Following Greenyer's suggestion that a catalyst similar to those used by Holmlid could have possibly been synthesized in-situ in the Lugano reactor, I tried looking more into it.

The "iron-rich" fuel particle in the Rossi/Lugano report on page 51 is interesting. It looks like its composition from the TOF-SIMS analysis is similar to that of a typical potassium/iron-oxide catalyst.

I tried digitizing the graph using the same technique I used for that of the analyses in the opening post of this thread. Perhaps others can come up with a better interpretation, but for the most part it should be something along these lines. Ni-Li (and perhaps other minor elements with the exception of C) were probably contamination from the rest of the powder:

Even more interestingly, particle 3 (d) from EDS analysis on page 44, with Fe, O, Si, Cr, Mn, and some C (in decreasing order of abundance) also seems quite consistent with some sort of typical dehydrogenation catalyst being used. Potassium is missing here, but it's abundant in the TOF-SIMS analysis of the iron-rich particle (together with sodium, which also was in Rossi's 2009 fuel analyses posted on New Energy Times).

So, assuming it's the same particle type, I would guess that there was some sort of ground Fischer-Tropsch/styrene/dehydrogenation catalyst in the initial powder in the Lugano reactor, and that it wasn't made in-situ.

So is the "secret catalyst" indeed a Fischer-Tropsch (or similar) catalyst?

(As a side note, this also gives more support to the initial hypothesis that the reaction in the Lugano experiment indeed occurred within/from the powder as expected, and not elsewhere - reactor walls or even the heating wire - as I and others speculated).

I just recalled that Curt Edström's E-Cat fuel analysis performed in 2013 also might be showing that a typical iron-oxide dehydrogenation catalyst could have been used. When these analyses got released, people did notice unusual amounts of Fe in the fuel. But what about now, under a different light?

In this case, the "new" powder probably only contained Nickel powder, while the "used" powder Nickel powder+catalyst and copper contamination.

http://www.lenr-forum.com/foru…achment/11-Askanalys-pdf/

For example, Fig. 6, showing one of the larger grains in the used powder, could be consistent in content with Fe₂O₃, Cr₂O₃, C (on the surface, although this might be interference from the carbon tape used for the analysis) being present. Chromium oxide is a typical structural metal oxide used in these catalysts as a support and anti-sintering agent (notably, it's also used in the Shell 105 styrene/dehydrogenation catalyst also used by Leif Holmlid).

Fig.15: it looks like silicon dioxide (SiO2)
Fig.16: Fe2O3, Cr2O3, C, and some Ni "contamination"

As far as I know lighter elements cannot be properly detected with EDS analysis, so it's possible that Na was also present in some amount or disguised on purpose by the addition of other elements. Or could this be only wishful thinking?

EDIT: after documenting myself a bit on the process (and referring to the tables on pages 18-21) this doesn't seem likely however. K or Na would have been probably detected if present. Li, on the other hand definitely would have not, as also as noted in the report.

Quote from pjs

Potassium and sodium oxides and also other alkali metal oxides have significant vapor pressure already below 1000 °C.
They would have vaporized from hot areas of the reaction chamber and condensed in cooler areas of the reaction chamber.

High temperature vaporization behavior of oxides. I. Alkali metal binary oxides
nist.gov/data/PDFfiles/jpcrd241.pdf

The powder would have lost alkali metal oxides during long heating time.

I was already aware that alkali metals have a low high vapor pressure, especially lithium (since it's been often used by experimenters in the past year or so and much information about it has been found), but I didn't know that even alkali metal oxides (and compounds with other elements?) would also easily evaporate with a high enough temperature (and low enough pressure).

If this is actually the case, then if I were Rossi I might have wanted, after the experiment ended, to pull the hardest vacuum I could and heat the powder to make most alkali in the "ash" evaporate before handing it out for third party analysis, for added obfuscation. This might have not been possible for the Lugano experiment, but it could have for that of the ash powder of Edström's 2013 analyses.

EDIT:

Quote from axil

In the Lugano test, there is a silica aerofoam inside the tube that kept the big fuel particles near the front of the tube and de facto preselected the big ash particles for ash assay analysis. All the small particles were trapped in the aerofoam and the testers only had access to the big ash particles. Note: There was silica particle in the ash that did not go in as fuel.

The Rossi-Cook theory paper here implies that the ash was scraped off the internal walls of the reactor tube near the center of the charge:
http://arxiv.org/ftp/arxiv/papers/1504/1504.01261.pdf

Quote

[...]Nickel was found to be encrusted on the internal surface of the reactor, from which a 2 mg sample of “ash” was obtained near to the center of the charge.

Besides, there was a small amount of Si in the fuel too if you check the fuel analyses carefully.

EDIT2: anyway, I'm not totally convinced myself as there seems to be way too much Si in the ash compared other elements, and I am going to look into it more in detail later.
It's not clear how the encrusted powder was removed from the inner walls, but I guess it's possible that part of the inner tube material was also removed in the process. In this case, the Si could come be from it, indicating that it was made of a different material than alumina (which is to be expected).

EDIT3: way too many edits...

@axil: I'm really not convinced about the silica aerogel hypothesis, although I think it's possible that some of the reactor material was also removed in the process, and thus that it contained Si, possibly SiO2.

Anyway, I tried performing the same data extraction process for the ash grain analyses in the Lugano report (from page 52) and indeed, as @pjs highlighted, it looks like alkali metals in the ash might have evaporated on the inner tube walls, from where the grains were scraped off (at least according to the Rossi-Cook paper). Both grains appear to show a fairly different composition and are relatively abundant in alkali metal content, and I'm not sure what to make of these results. Hopefully others will try checking out for themselves and correct any error here or improve the data interpretation below. The takeaway message is that is that alkali metals and metal oxides can indeed easily evaporate over time with heat due to their low vapor pressure.

By the way, the fuel ash grain with Li actually didn't contain much Li at all. From a.m.u 20 onward, counts are supposed to be 100x larger than depicted. Or have I got it backwards and counts depicted are actually already 100x larger than normal?

I used this tool to digitize the graphs: http://arohatgi.info/WebPlotDigitizer/app/

@axil: with your discussion about ridges in the internal ceramic tube, are you suggesting that the Lugano experiment might have been internally shaped like a sort of heat pipe?

In principle this could ensure a constant flux of hydrogen on the active sites, needed to observe the effect (ie to form ultra-dense hydrogen according to Leif Holmlid).

EDIT (for better wording):
In real life applications a working fluid (usually water or alcohol) able to exist in both gaseous and liquid state is used in these pipes. How could it work in this case?
That is, unless you meant something else.

EDIT2: again sorry for the number of edits :dead:
Mostly cosmetic changes, though.

@axil: now that it's clearer (from Industrial Heat's patent) that the inner walls of the inner tube in the Lugano experiment might have been made of a different material (eg stainless steel) than ceramic, a corrosive metal such as lithium might have been more easily used. However, while Lithium would probably be a great material for transferring heat at high temperature, I'm not sure it would be ideal for providing hydrogen to the active sites upon condensation. I figured that the working fluid would be one containing hydrogen and capable of more or less easily dissociating at the surface of this iron-oxide catalyst supposedly used in these reactor tubes.

* * *

Back to the topic of this thread. Speaking of stainless steel, I have more thoughts on the matter.

All patents and written information published so far by Rossi have always omitted that it's quite likely he's used a typical iron oxide petrochemical catalyst all along for, at the very least, efficiently dissociating molecular hydrogen into atomic hydrogen (and speculatively for creating hydrogen Rydberg Matter and ultra-dense hydrogen).

However, it's also true that the chemical composition of these catalysts can look like that of stainless steel (with Fe, Cr, Mn content).

I'm wondering if people who somehow managed to replicate the Lugano experiment (assuming no errors or something worse) serendipitously created such catalyst in-situ by using a stainless steel fuel container modified with heat, stress, embrittlement and contaminants from the initial atmosphere and possibly with Li from the LiAlH4 as an alkali promoter instead of potassium or sodium. High temperature steam traces especially, which are expected to be created from hydrogen and oxygen from the starting atmosphere, should be a quite powerful oxidizing and corroding agent to steel, together with hydrogen.

If this is the case, then when Rossi patents mention SS containers being used for the reaction chamber (like AISI 304, 310, and 316 as in [lexicon]Industrial Heat[/lexicon] patents) this might be actually needed, in a way, for including the "secret catalyst" without letting others know.

https://en.wikipedia.org/wiki/SAE_steel_grades

Since Rossi obviously knows what the "secret" catalyst is - assuming it's actually the one I'm referring about, although at this point I'm relatively convinced about it - he wouldn't need in practice to create it in-situ from stainless steel, as he could simply include it in the fuel. The catalyst could then pass as SS contamination in the ash analysis.

Past ash fuel analysis in Rossi's case have always shown particle content consistent in several ways to these iron oxide catalysts. Of course, if these were fundamental in making his devices work, then the idea of Nickel alone as a starting powder might have acted as a smoke screen to conceal the true nature of the reaction.

Quote from Eric Walker

If Rossi has intentionally obfuscated a critical component of the device in the patent, he has not provided an "enabling patent," i.e., one that a practitioner skilled in the art would be able to replicate. If true that brings a number of interesting implications with it. If his intention was bona fide IP protection, he will have made to the best of his knowledge an enabling patent.

I think Rossi has most certainly been intentionally obfuscating things up since he started working on the E-Cat, however this would have to be demonstrated.

If you recall, he used to say both on JONP and his first patent application that undisclosed catalysts (claim 8.) could be used (and were used) for the exothermic reaction. Later on he dropped that claim (check out the documentation in patent application 12/736,193 on the USPTO public pair) and stopped writing about them on his blog.

Now it turns out that nickel itself is apparently the catalyst. Perhaps it might be true in some circumstances (nickel dehydrogenation catalysts do exist too after all, and properly prepared ones, instead of just plain nickel powder, might turn out useful for more quickly observing LENR effects), but if some sort of alkali-promoted iron oxide catalyst is still needed for abundant excess heat, by "accidentally" using stainless steel parts in his patents he might now be able to claim that he thought Nickel alone (+ Li, LiAlH4) was sufficient, while something else is actually occurring (albeit probably only with very much luck - and that why I'm saying that in practice he'd likely use his secret catalyst in his experiments).

Granted, this is mostly conjecture, and I don't really know how things would actually work out in this case if it were true. It's also mostly built up on the initial premise of this thread where the Rossi reaction is actually similar to Leif Holmlid's, regardless of its true nature, in that it needs certain catalysts for facile molecular hydrogen dissociation.