Thanks again. Looking forward to reading and seeing the result
There was a bit of color change, but no hint of green there. These are in sequence: first the raw material before baking, then fresh out of the furnace after 6 hours at 800°C. Finally, the same material after cooling for 10 minutes in air. All photos are from an iphone6 with flash on. The color accuracy is pretty good.
Good job. Some pellets do appear on my screen like they've acquired what has been described in the literature as an olive green color, but unexpectedly this happened mostly on the surface of some of the larger ones, while the rest of the powder except for a few of the larger chunks has now an overall slightly darker red (crimson) appearance than before the treatment.
This makes me wonder if at this temperature and calcination time another phase generally associated with KFeO2 has formed instead (K2Fe22O34), except for the spots where the local concentration of Fe2O3 and K2CO3 was higher. Either way, if anything this shows that the composition can vary greatly from pellet to pellet also from the same batch.
Actually I have a photo from Alan Smith showing such a color on the pellets calcinated at 900 °C for 90 minutes immediately after being put out of the furnace, but as the lighting conditions weren't controlled and the pellets were still hot I thought this was for the most part a camera effect (artifact), not an actual change. Most of this crimson tint appeared to have been gone a few minutes later. So apparently this darker compound was unstable too:
Your "10-minute after" photo—if it has good color accuracy—appears to show too that some of this crimson coloration disappeared, while the larger pellets still retained part of their yellow-green (ochre?) color.
It will be interesting to check out again under the same lighting conditions in one hour (although at the time of posting such time probably already passed) and then after several hours (overnight).
EDIT: added composite image of the catalysts calcinated at 800°C for 6 hours.
Exactly how potassium iron oxide assists in the formation of Rydberg matter of H is not clear to me. Fom the publications I read on the subject (I have no direct expertise in surface catalysis), I can see two main hypotheses:
- breaking the H2 molecule in atomic H at the surface of the iron oxide with a simultaneous desorption of K in an excited Rydberg state K* and a rapid transfer of the excitation energy of the K* to the atomic H to produce an excited Rydberg H*, or
- absorption of atomic H within the bulk of the porous iron oxide followed by its desorption in an excited Rydberg H*, this without any apparent role of K.
Holmlid seems to favor the 1st hypothesis, going even further in suggesting that Rydberg states K* are key in the process of ethylbenzene dehydrogenation (somewhat in contradiction with the attributed role of KFeO2), but he also alluded that a direct desorption of H in H* is possible. In any case, for what it's worth, this doesn't say why KFeO2 would be the active form.
It's my understanding too that at least in the context of the K-Fe2O3 catalysts he's most often suggested the first explanation, i.e. excitation transfer of the K* energy to the atomic H. The so-called K promoter reportedly makes this transition easier than normally possible. A short explantion of the process has been described in his lapsed patent in the section Catalytic conversion: https://patents.google.com/patent/EP2680271A1/
However, this transition can also be achieved in other ways, not just from these catalysts. See for example a very general explanation in section 2.2 Formation of RM in this open access paper here: http://aa.springer.de/papers/0358001/2300276.pdf
Speaking again of the K-Fe2O3 catalysts of this thread, it could be very simplistically summarized that according to Holmlid et al. K atoms can desorb thermally directly in an excited state from the KFeO2 phase of their activated form. This probably doesn't occur only on the surface, but also in the internal macropores inherently composing their structure, but for ethylbenzene dehydrogenation the latter might not be a very significant factor.
Compounds like KAlO2 do not seem to show the same behavior. In this paper available on Researchgate the authors conclude:
These catalysts have been used for decades and other authors have studied the role of K promotion on catalytic activity in practical terms, without necessarily focusing on Rydberg emission like Holmlid and colleagues did. In this old review (1974) by Lee, the relative activity between different metal oxides, K-promoted and unpromoted, was analyzed. Al + K was not found to be catalytically active.
The Fe2O3 compound is known as a LENR H* catalyst since the early days.
The problem with the understanding of chemical papers/ their relevance for LENR is that they use H*/K* for ordinary Rydberg matter, where as Holmlid/Mills mostly use H* for the shrunken form. Mills claims that in a disproportion reaction H* (going to H 1/4) releases the exact amount of energy to split the catalyst. Holmlid assumes that H* has a different spin state. The combination of the two models would imply that the proton has a so far unknown quantization of its spin that somehow coincides with Mills quantization rules.
What could be the role of the catalyst?
One fact we know is that energy in the "some eV" range can only be added/removed from a molecule in a kinetic transaction (might be the exchange of magnetic flux quanta in the form of a temporary generated charge density). Thus a good LENR catalyst must provide a collision point that allows to efficiently transfer the energy quantum. Whether this is the same effect as in a pure chemical reactions has to be shown. But I believe this is very unlikely as the reaction frequency for catalysts is magnitudes larger than we see for LENR.
Nevertheless the origin of both effects could be the same, but the fine-tuning will be different.
The Fe2O3 compound is known as a LENR H* catalyst since the early days.
Since the start of this thread I have been showing sources explaining that the K-Fe2O3 catalysts have to undergo certain transformations in order to efficiently work and form excited atoms in desorption. Fe2O3 isn't very active on its own.
The problem with the understanding of chemical papers/ their relevance for LENR is that they use H*/K* for ordinary Rydberg matter, where as Holmlid/Mills mostly use H* for the shrunken form.
Read Holmlid's explanation from this patent (section "Catalytic conversion"). He's not using the H*/K* notation for what he calls the ultradense state.
For those interested in forming KFeO2 directly by heating in a vacuum instead of calcinating the material ex-situ at 800 °C or above, it might be worth mentioning that Ndlela and Shanks reported in Reduction behavior of potassium-promoted iron oxide under mixed steam/hydrogen atmospheres (2006) that partial reduction to Fe3O4 seems necessary for KFeO2 to form under very mild vacuum conditions (0.057 atm in the experiments described) at temperatures in the range of 600-630 °C (typical styrene process temperature).
However, excessive reduction to Fe3O4 or metallic Fe (e.g. with a too high hydrogen pressure) will prevent KFeO2 formation.
It's possible that at the deeper vacuum levels implied in the excerpts posted previously, with potassium ions diffusing from the bulk to the surface of the material (and reacting with the oxides present) more quickly, such partial reduction might not be required.
On the other hand, under prolonged heating under such conditions, it can occur that vacuum pump oils volatilize in the atmosphere and eventually crack (decompose) on the surface of the catalysts, depositing a thin carbon layer and also partially reducing the catalyst with the hydrogen produced in the process (which is however expected to be usually rather slow unless deliberately or inadvertently promoted).
Apparently Leif Holmlid—who used to perform prolonged experiments with the catalysts under high vacuum conditions—has observed such phenomenon in his experiments throughout the years and sometimes very briefly reported it in his papers.
Source: http://doi.org/10.1021/jp046288m
Source: https://doi.org/10.1007/s11051-011-0543-4
Source: https://doi.org/10.1016/j.saa.2006.09.003
Following other comments written elsewhere, it might be worth pointing out once again that this thread is not just original research for LENR replications. For the most part I looked for more detailed studies about the characteristics of these catalysts following Holmlid's references and pointers from his papers about them.
Even in his latest one, Holmlid still refers to other works in the literature describing in detail the characteristics and stability of their active state. That he's been citing specifically these two papers consistently throughout the years, should suggest that perhaps the subject they cover might be crucial.
From Meima and Menon (ref. 31):
From Muhler et al (ref. 32), right in the introduction:
I think while testing with open-air electrolysis with mild steel electrodes and a KOH solution (concentration unknown, but it was relatively diluted) I might have created the elusive green KFeO2 compound described in this thread. It looks like under narrow gap electrolytic conditions it doesn't take extremely high temperatures for its formation, although it apparently involves initially quite energetic reactions (unfortunately not caught on camera).
As described in the literature, it appears to have a short life under moist ambient air conditions. Within 30 minutes it was mostly gone, at least what was formed (accidentally) on the surface of the closely-spaced electrodes.
I've made a photo sequence of the process (inside the spoiler tag to avoid cluttering the page):
Great demo synthesising FeO2 with your electrolytic set up - nice to know this catalyst can be made without having to go up to 800 deg C. So we can just use KOH and haematite (Fe2O3) in the electrolyte to make Rydberg H and then UDH? Some KMnO2 (about half the activity of KFeO2) could be added as well to maintain catalytic activity in case the FeO2 breaks down. I'm thinking of linking these catalysts and the UDH formed to three different perovskite dialectric materials and tourmaline crystal matrices (for their pyroelectric effect) to see if I can generate excess heat in my electrolytic setup, I'll be posting the results if I have any success.
Unfortunately this KFeO2 compound (the active phase of K-Fe2O3 catalysts as reported by Muhler et al - excerpt from the paper here) is very sensitive to humid air and instantly decomposes if it comes in contact with water at low temperature, so using it in ordinary electrolytic experiments would be difficult. However this method - possibly in an improved/less crude form - could be used to synthesize small quantities to be employed in a low-temperature dry cell, preferably in a vacuum.
By the way: although potassium carbonate is generally used to synthesize it at high temperatures, KOH or other potassium sources can be used as well. In older texts/patents sometimes the Shell 105 formulation is listed as using KOH. Example:
https://patents.google.com/patent/US2813137A
In the past few weeks I have been testing a variation of the above process and it seems it was actually simpler than I thought. If a KOH aqueous solution is allowed to coat a rustable steel surface and then to evaporate under oxidizing conditions and moderate heat, the oxides formed on the steel surface as water evaporates will react with the hydroxide residues, forming an unstable olive-green compound that appears to have the same characteristics of the catalytically-active potassium ferrite (KFeO2) compound described in this thread. I'm still not entirely sure if I'm observing what I think, however.
Contrarily to what I previously thought, a current is not required and indirect heat will also work. However, it will not work if the surface is completely oxidized. Apparently this process at low temperature using KOH requires a clean or only partially oxidized steel (iron) surface. Since a current is not required, arbitrarily large surfaces could be coated and modified with the same process.
In addition to sheets I also tried steel wool, or the heating wire itself.
However, when I tried a Fe2O3–KOH solution (hematite in the form of red pigment) it didn't work well; it didn't work at all when I increased the amount of hematite.
Heamatite is pretty stable, so no surprise there. The solvo-thermal method might be something like - dissolve iron filings in hot citric acid solution, allow to cool, add KOH (carefully - gloves and goggles) to neutralise. Filter off the liquid and evaporate the water. Heat the dry solid to decompose the citrates.
But that's just a guess at a method suitable for 'kitchen chemistry'.
My thought was that the KFe complex would be solid, though I have not checked its water-solubility - and thus can be separated by filtration. If you are concerned about free KOH forming carbonates then most of the unbound material - which would be potassium citrate at this stage-could be removed by washing the solid fraction in distilled water and re-filtering. However, I do suspect that the presence of some small percentage of carbonates in the end product would not be particularly detrimental. Sometimes you have to improvise a bit when exploring the possibilities. 
