MFMP: Automated experiment with Ni-LiAlH

Quote from BobHiggins

Thanks for the interesting suggestion and collected tips from ME356. While some Al is desirable for gettering the oxygen, it is not clear, as you point out that the 1:1 Li-Al ratio is preferred. Parkhomov surmised that LiAlH4 was used from the Lugano analyses, but none of those measurements indicate a 1:1 ratio of Li-Al. Measuring the Li is hard and assaying the ratio is hard. So, the Lugano reactor may well have had a different Li-Al ratio than 1:1 and the 1:1 only really comes from Parkhomov. This is test-able. Perhaps the easiest way to change the Li-Al ratio is to include LiH in addition to the LiAlH4. I can set the pressure low to basically whatever I want using my programmable back pressure regulator. Without Al, the Li will not wet to the Ni (only an observation).

For what it's worth he recommended in one post that using only pure lithium in the beginning to at least start obtaining something could be a good idea if external hydrogen admission is available, as apparently it provides the strongest reaction, at the cost of long-term reliability of reactor materials. So, that could be the starting point, which would also simplify the reaction from the point of view of kinetics.

If I am correct, elemental lithium should also be quite reactive with any oxide present. Pure lithium and other alkali metals are often sold in mineral oil for the reason that they can spontaneously combust in air. Actually, in pure form lithium metal may even be too reactive and start attacking the alumina tubes which so far have proven to act fine with LiAlH4 only. Me356 has indeed mentioned that this can be problem, and others who used larger amounts of Li in the mixture with ceramic tubes have witnessed failures as well.

It might be interesting to mention again that the at the time promising GlowStick 5.2 and GlowStick 5.3 experiments used extra Li in the fuel mixture.

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It is also pretty hard to get to high enough temperatures to have Li vapor when the heat is being supplied with a heater coil. If, instead, the heat is being supplied as a plasma discharge, the temperatures can easily reach the Li boiling point (almost guaranteed to) while remaining below the Al boiling point (2700C). Additionally, plasma discharge tubes can have a hot center plasma even while the tube itself has its envelope cooled with water, relieving the problem of the apparatus melting. This begins to sound like the case of the dusty plasma of Suhas or even (I hate to say it) Rossi's QuarkX.

In absence of a vacuum system it is indeed hard. If one is available then it's possible to decrease that point to a significantly lower temperature that won't destroy the apparatus right away. For what it's worth, me356 has suggested that "with the right equipment" it's possible to obtain excess heat even at 450°C, implying (in retrospect) if the Li is able to evaporate at that temperature. You would need a pressure of 0.1 Pa to achieve this (and a turbopump).

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I am working on a plasma apparatus now for a next round of experiments (with water cooling and flow calorimetry). In the mean time, I will see if I can acquire some LiH or other Li. I will have to check... I may have a small sample of the nano-encapsulated Li.

As far as I recall some people have had issues with that passivated nano-Li powder. Apparently, since it's passivated with CO2, it can end up being depending on batch quality, mostly lithium carbonate and not being able to absorb significant amounts of hydrogen or volatilize like pure Li. It would also free up CO2 at high temperature.

It's been suggested that using a Li wire as a lithium source is fine, indicating that at least in this form it doesn't even need to be intimately mixed with the Ni powder, although it probably depends on reactor geometry. Perhaps it could even come from small strip cut from a Li battery cathode.

Good luck with the plasma system. I guess the focus will soon move away from powder/gas systems.

can,

I have ordered some pure Li metal and have asked for a quote for LiH. One of the interesting substitutions will be the use of CsH because it will decompose and boil at a lower temperature than LiH. I have also requested a quote for CsH. I am not sure the LiH and CsH supplier will sell to me, but I have some connections to get it through another entity if that fails.

Handling Li metal can be done in a low humidity chamber, even with O2 present - the humidity is the bigger problem. I think I can get the humidity low enough in my dry glove box that I can handle the Li metal for purposes of putting pure Li in the reactor tube. Pure Li is cheap from China.

While Li can form an oxide, it quickly breaks down at high temperature. When Al2O3 forms, it is a super stable oxide that will remain up to temperatures over 2000C. Thus, Al's gettering reputation is due to the strength of its oxide molecule - basically once reacted with the aluminum, it stays out of the reaction.

I can easily operate at pressures of 25-50 Torr with my present system and the corresponding boiling point of Li will be in the 950°C - 1000°C range - these temps are in range of my experiments. I am not sure what having a percentage of Al in the Li does to its boiling temperature - probably raises it.

@Alan,

Thanks! The Li metal shouldn't be a problem. Let's see what happens with the quotes for the LiH and the CsH.

BobHiggins

It's great to know that you've already ordered the materials, but I hope you've done so because you're seeing potential in replicating what other researchers have reported and/or suggesting, and not only because I said so in this thread. I don't exactly like playing with others' money.

You're right about the Lithium oxide decomposing with temperature. Indeed one of the probable reasons why scientists like Holmlid can use some form of alkali oxide instead of the alkali metal in elemental form is that it decomposes with temperature. Alkali metals higher on the periodic table would decompose from their oxides even quicker. As a side note, according to Holmlid (if you care) alkali atoms decomposing from transition metal oxides can do it tendentially in an excited state, which supposedly helps the reaction.

In one of his patents Piantelli has an "electron donor material" composed of a substrate/support containing alkali metals (preferably Cesium); given how one of the embodiments is supposed to work (one different than what I showed last time) and that this metal melts at a very low temperature I doubt it's in the apparatus an elemental form, but rather as an oxide or mixture of oxides. At a high enough temperature and/or low enough pressure it should be able to start emitting alkali atoms in sufficient quantity to increase the reaction as reported, almost as if the alkali metal was available in the gaseous state. In this form it would be much more manageable from a materials durability standpoint and controllability, although it would probably have to be closer to the structured/prepared transition metal surface to provide the claimed benefits.

(EDIT/reworded: as for oxide gettering, that could be a an issue if you relied on it, but it also depends on how the oxides gettered this way decomposed and if they get displaced away in the process - I'm not sure how to answer here. With the possibility of manually performing as many vacuum/hydrogen cycles as wanted to clean the reaction environment at elevated pressure and temperature, is it actually required?)

This being said, this would only be one part of the system and some other things (triggering? etc) that are needed to make it work reliably are mostly unknown. Me356 (who didn't report using other alkali metals than Lithium, although there's no reason why they shouldn't work) made this intentionally cryptical statement some time back:

me356: Reactor parameters [part 2]

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there are usually at least two problems. One which nearly nobody is doing, but is done by a successfull replicators (if done, chances of getting excess heat is probably 90% higher) and second that all unsuccessfull replicators are unaware. Second one is not mentioned in any replication report and even not all successfull replicators might be aware of this. But you can still find at least a hint in one report. This mean, that everything you will need was already told in the reports. No one is replicating exactly. But doing so is really hard.

It would be useful if he could clarify what he actually meant here. I don't know if you can ask Bob Greenyer if me356 could provide a clear answer to this.

can,

Bob G has a pretty good relationship with Me356, and has arranged for MFMP to do a black box test of one of his reactors. However, Me356 does not appear to be willing to share more of the details about what he does to make his reactors work. I can understand that - he has has commercial interests. If it is real, and MFMP shows that it is real, perhaps he can get patent protection and then he may be more willing to share.

Note that oxide gettering can occur even if the LiAlH4 is segregated from the rest of the fuel, so that is an option. Put in the LiAlH4 in the end, put a zirconia felt separator, then put the Ni and Li.

can,

I have been able to write a really simple routine to read the spectrum data out of the Spectrum Techniques .spu spectrum files. Here is the simple Matlab code which would be able to re-code into almost any language:

% Function to read the Spectrum Techniques .spu binary spectrum files
%
function S = ReadSPU(fdir, fname)
%
% fdir is the directory of the files not including the final \ in a string
% fname is the name of the .spu file to open and read
%
% The return value, S, is an array of 32b integers that is of length 1 more than
% the size of the data array.  The first value is the number of channels, chan,
% and then there are chan values that follow for the counts in each channel.
% It is reasonable to presume that the channels are nominally, but not exactly 
% 1 keV per channel.  A future version of this routine will try to thread out
% this approximate value from the .spu file parameters, but for now, just presume
% approximately 1 keV per channel uncalibrated.
%
fullname = strcat(fdir,'\',fname);   % Begin by creating the full file name
%
fid = fopen(fullname);         % open the specified file in binary mode (defaults to read)
%
chan = fread(fid,1,'uint32');  % The first 32b is the number of channels
%
dummy = fread(fid,1,'uint32');  % The next 32b is read just to get the channel data aligned
%
D = fread(fid,chan,'uint32');   % Read in "chan" counts for each channel as uint32
%
S = [chan D']';  % Puts the # of channels as the first element in the array
%
fclose(fid);     % close the file 

BobHiggins

[validation plan] I remembered it different; then, back to square one.

I was thinking of the oxides on the surface of the Ni powder more than those in the internal atmosphere. I don't think there's much preventing for the latter to use cycles of vacuum and hydrogen admission at elevated temperature/pressure before the actual experiment begins; of course you wouldn't want to choose pressures/temperatures that allowed the vacuum pump to start drawing in alkali metal vapors, which could be a more significant problem once you start using cesium in elemental form.

On a related note, in the email from Parkhomov recently quoted by Alan Smith there is mention of a cleaning procedure besides the initial bakeout, performed at elevated temperature with Ni and LiAlH4 present at the same time:

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[...] Successful experiments were carried out both with a mixture of nickel with LiAlH4 and with pure nickel saturated with hydrogen gas. Pumping out air with a fore-vacuum pump, filling with hydrogen to a pressure close to atmospheric, holding at a temperature of 200-300 oC for several hours to purify nickel from the oxide, pumping out to remove the formed water, refilling with hydrogen, saturation of nickel with hydrogen at a temperature of 300-400 oC for several hours and after that a smooth increase temperature to 1200-1300 оС. After the release of excess heat, it may be necessary to reduce the power of the electric heating. The pressure in the reactor chamber is kept close to atmospheric pressure........Alexander Parkhomov

BobHiggins (#348)

Luckily, only reading channel/energy information from these binary files is simple. Many useful things can be done with this data. Extracting other information requires mainly tedious work.

BobHiggins, I am looking forward to your line of CsH experiments, if they come together.

This is the "other" embodiment from one of Piantelli's patents that I previously mentioned, which may be relevant to the recent discussions including wetting coatings and gaseous alkali. I've added some emphasis to the text and color/annotation to the relevant figure to make it a bit clearer.

Here Piantelli has two opposing surfaces, one with the transition metal nano/micro (or "right-sized") structures, and another at least partially composed of an electron-donor material (an alkali metal, preferably cesium). There is a gap between both surfaces where hydrogen can "be contained or flow", and the closer these surfaces get to each other the higher the reaction rate gets in turn, with the reaction here being the production of H-.

It's implied that both surfaces can be heated separately. The reliefs are drawn in an exaggerated manner ("are enhanced").

Given the variable distance between the opposing surfaces and the way the reliefs are drawn, isn't it more plausible that the intended interaction here between hydrogen, both gaseous in the gap and adsorbed on the transition metal surface of the active core, and the alkali metal is in the vapor phase?

If cesium can easily decompose from its oxides at elevated temperature, wouldn't it be more practical here if it wasn't in an elemental form but rather some sort of oxide? The triangular reliefs on the bottom substrate are indeed drawn exaggerated, but if the cesium was in the form of a liquid metal, how would it be able to remain contained on their surface?

Disregarding what Piantelli actually thinks of the reaction, wouldn't the usage of the alkali in the form of vapors be more consistent with what others (including also me356) have described being useful?

EDIT: given the information posted so far, I guess the bottom line is: could one possible reason why only some people have success with Ni-LAH replications while many others do not, be that you do not want a coating and that the way the powder is mixed could affect the result significantly? Following what Piantelli suggests above, one might want to have them close to each other, perhaps even very close to each other, but not actually in contact/forming a coating on the particles.

I honestly believe that the suggestion during the MFMP visit in January 2015 that according to him a LiAl coating would be a good idea was either the result of a misunderstanding/mistranslation, or he didn't give too much thought to it and actually referred to this patent instead.

Quote from Can

This is the "other" embodiment from one of Piantelli's patents that I previously mentioned,

Here a direct downloadable link: https://worldwide.espacenet.co…=2013008219A2&KC=A2&ND=1#

Advance to description and start the download. Google is just cheating you...

Alan Smith

Indeed I would be hesitant too to take an isolated null result in support of this hypothesis. Maybe there can be quicker/simpler ways to test it in "standard" experiments with Ni (hopefully treated for increased surface area) and small amounts of LAH(+Li).

Instead of homogeneously mixing the Li(+LiAlH4?) and the Ni together as it's usually done, one could have the former placed on the bottom of the tube and the latter very loosely compacted (leaving macroscopic gaps) on top of it. Refer to the diagram below for a clearer explanation of what I define "bottom". In this way the amount of liquid alkali/alkali hydride/alloy actually in contact with the porous Ni powder is reduced, while still being at a close enough distance that nascent (atomic) hydrogen decomposing from it can reach much of the powder - which may or may not be useful. At a low enough pressure and/or high enough temperature when the Li starts evaporating (if there's any free in the charge), the vapors should start permeating through the large gaps that have been initially left in the loosely compacted Ni powder, which will for the most part at least initially be coating-free.

To avoid an immediate reaction of the more concentrated alkali metal with the ceramic tube it might be an idea to use some sort of metal foil as an improvised boat to contain this part of the fuel, or use a SS fuel container.

The assumption in the past 2.5 years (almost) of mostly failed replications has been that the starting mixture has to be homogeneously mixed. What if it doesn't have to?

Note that by doing this there won't be direct gettering of oxides from the surface of the transition metal, but on the other hand this shouldn't be a problem if a vacuum pump to perform some cleaning cycles of hydrogen admission and vacuum application is available.

Gettering is commonly used to describe removal of oxygen from gas - usually residual oxygen in what should be a high vacuum. The liquid Al may very effectively strip the oxide from the Ni surface, which would not really be gettering, but rather an oxygen exchange reaction. It may be that this NiO -> Al₂O₃ oxygen exchange reaction (exothermic, thermodynamically preferred) is what allows the Li-Al-H to wet to the Ni powder surface. This wetting of the Li-Al-H has been seen in Parkhomov's SEMs and the Lugano SEMs. If you believe that either of these were active experiments, then the wetting at least does not prevent the LENR from occurring.

Perhaps wetting and Li boiling are both valuable. Could the wetted Li boiling actually cause a "precipitation" of the H- onto the Ni surface?

I have heard the molten LiAlH₄ described as being "foamy" - from the bubbling out of the H₂. We have seen that inside the reactor tube that the melted LiAlH₄ coats the reactor tube all the way around almost completely uniformly; supporting this idea of foaming of Li-Al-H liquid. In such case, it would be hard to prevent the mixing without a separator of some kind. And it also means that mixing of the powders for some kind of uniform blend is not really necessary.

In the case of Piantelli's description of an opposed alkali metal surface, it is his "afterburner" or XH enhancer. Piantelli says that the Ni-H LENR produces a lot of 6MeV protons that are ejected from the Ni. He added the Li to get extra energy from the 6MeV protons - more than would be obtained by simply thermalizing the 6MeV proton kinetic energy. In Piantelli's case, the Li is not complicit in causing the LENR in the Ni, and produces no XH by itself unless the Ni is producing the LENR generated 6MeV protons. From this Piantelli perspective of what is happening in the separated alkali metal, it is hard to decide how use of the Li will enhance the underlying Ni-H LENR.

Quote from BobHiggins

Gettering is commonly used to describe removal of oxygen from gas - usually residual oxygen in what should be a high vacuum. The liquid Al may very effectively strip the oxide from the Ni surface, which would not really be gettering, but rather an oxygen exchange reaction.

Now I get what you meant; I thought you were using the term liberally also meaning the stripping of the oxides from the surface.

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It may be that this NiO -> Al2O3 oxygen exchange reaction (exothermic, thermodynamically preferred) is what allows the Li-Al-H to wet to the Ni powder surface. This wetting of the Li-Al-H has been seen in Parkhomov's SEMs and the Lugano SEMs. If you believe that either of these were active experiments, then the wetting at least does not prevent the LENR from occurring.

Here I'm really holding onto the very specific, practical observation from me356 that the Al in LAH throttles back the reaction, and that the reaction can start once Li reaches the evaporation temperature, depending on pressure, which may be advantageously lowered. This is in contradiction with the idea that a LiAl layer/coating wetting the Ni particles is required or anyhow beneficial, or anyway that there has to be a permanent coating. Li may temporarily coat the Ni while it's in liquid form, although I suppose without wetting it. Some Ni may get dissolved into it.

I remember reading that Ni is one of the metals which dissolves the most in liquid lithium (EDIT to clarify: without forming an alloy. See the abstract in this ref.). If lithium evaporates, any dissolved Ni would precipitate from it. However this corrosive action also means that any sort of previously performed surface treatment would get quickly destroyed. Liquid metals, in particular of alkali metal compounds, tend to all be rather corrosive and difficult to handle. This is a further reason why I find rather odd that Piantelli would have agreed with this idea since he goes great lengths preserving the integrity of his carefully prepared nano/micro structures, putting aside the fact that his reaction is with hydrogen atoms adsorbed on a transition metal, and not dissolved within an alloy.

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Perhaps wetting and Li boiling are both valuable. Could the wetted Li boiling actually cause a "precipitation" of the H- onto the Ni surface?

I don't know whether the H- precipitates. I have tried to not involve researcher-specific theories when coming with possible ideas for the next experiment(s). I could cite Holmlid for examples of "H precipitation" that may occur for example with decomposing excited alkali atoms.

More broadly speaking, Piantelli and Dufour et al are saying that these alkali atoms donate electrons to the hydrogen atoms adsorbed on the transition metal. If they're in a vapor/gaseous form, they would create an electron-rich atmosphere capable of either exciting or ionizing those atoms to some extent, as well as those in the atmosphere.

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I have heard the molten LiAlH4 described as being "foamy" - from the bubbling out of the H2. We have seen that inside the reactor tube that the melted LiAlH4 coats the reactor tube all the way around almost completely uniformly; supporting this idea of foaming of Li-Al-H liquid. In such case, it would be hard to prevent the mixing without a separator of some kind. And it also means that mixing of the powders for some kind of uniform blend is not really necessary.

I don't know. If this is the case it would probably not even harm to deliberately try to not homogenously mix the usual Ni+LAH powder.

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In the case of Piantelli's description of an opposed alkali metal surface, it is his "afterburner" or XH enhancer. Piantelli says that the Ni-H LENR produces a lot of 6MeV protons that are ejected from the Ni. He added the Li to get extra energy from the 6MeV protons - more than would be obtained by simply thermalizing the 6MeV proton kinetic energy. In Piantelli's case, the Li is not complicit in causing the LENR in the Ni, and produces no XH by itself unless the Ni is producing the LENR generated 6MeV protons. From this Piantelli perspective of what is happening in the separated alkali metal, it is hard to decide how use of the Li will enhance the underlying Ni-H LENR.

I'm aware of that other embodiment, but in the very specific example that i cited, the alkali substrate (preferably comprising cesium) is operating and specifically being used as an "electron donor material", with no reference to what they call "secondary nuclear reactions" in an earlier patent. These secondary nuclear reactions would happen with any material within the range of the protons emitted by the Ni in the Piantelli process. The Lithium there was for aneutronic, useful fusion energy.

I enjoy this thread a lot. Keep up the terrific work. I understand the focus is on the reactants. But ... In these experiments, is any external signal being imposed (such as a square wave EM pulse) to stimulate oscillations or spin flipping?

Quote from Can

Here I'm really holding onto the very specific, practical observation from me356 that the Al in LAH throttles back the reaction, and that the reaction can start once Li reaches the evaporation temperature, depending on pressure, which may be advantageously lowered. This is in contradiction with the idea that a LiAl layer/coating wetting the Ni particles is required or anyhow beneficial, or anyway that there has to be a permanent coating. Li may temporarily coat the Ni while it's in liquid form, although I suppose without wetting it. Some Ni may get dissolved into it.

I remember reading that Ni is one of the metals which dissolves the most in liquid lithium (EDIT to clarify: without forming an alloy. See the abstract in this ref.). If lithium evaporates, any dissolved Ni would precipitate from it. However this corrosive action also means that any sort of previously performed surface treatment would get quickly destroyed. Liquid metals, in particular of alkali metal compounds, tend to all be rather corrosive and difficult to handle. This is a further reason why I find rather odd that Piantelli would have agreed with this idea since he goes great lengths preserving the integrity of his carefully prepared nano/micro structures, putting aside the fact that his reaction is with hydrogen atoms adsorbed on a transition metal, and not dissolved within an alloy.

Even the EDS analyses of the ash have confirmed a small dissolution of Ni in the Li-Al alloy - I believe less than 5% atomic ratio. And, it is likely that the nanoscale features of carbonyl Ni granule surface that are the first dissolved. Boiling of the Li probably also means that Ni will condense out of the Li-Al-Ni solution, perhaps as new nanoscale features on the surface of the Ni powder particles. It is an interesting conjecture.

The electron donor concept is interesting, particularly for a neutral metal gas vapor + hydrogen. I don't know if this is important or not. Me356's input can only be taken as speculation at the moment because his work has not been substantiated (yet). MFMP will be allowed to evaluate one of Me356's devices as a black box. Me356's input will be taken more seriously once it is proved that he does have something working.

Quote from hendersonmj

In these experiments, is any external signal being imposed (such as a square wave EM pulse) to stimulate oscillations or spin flipping?

Today, the only stimulation is temperature change and pressure change. I am working on 2 different coils to add around the insulated reactor: 1) a multilayer solenoid to introduce a DC magnetic field, and 2) a single-layer solenoid with fewer turns that will be resonated and driven to provide an RF magnetic field.

Quote from BobHiggins

Even the EDS analyses of the ash have confirmed a small dissolution of Ni in the Li-Al alloy - I believe less than 5% atomic ratio. And, it is likely that the nanoscale features of carbonyl Ni granule surface that are the first dissolved. Boiling of the Li probably also means that Ni will condense out of the Li-Al-Ni solution, perhaps as new nanoscale features on the surface of the Ni powder particles. It is an interesting conjecture.

Since Ni and Al do alloy together and that Ni has a limited but significant solubility in Li, it's not unexpected that it would eventually dissolve in the LiAl solution to some extent. Tests that explored the possibility of condensation of Ni particles from evaporating Li or even Li-Al in a low pressure hydrogen atmosphere would be interesting, but I suspect this would be much simpler and cleaner in execution (leaving just solid Ni particles at the temperatures/pressures of interest) with Ni-Li only or with Ni-Li and a rather limited atom fraction of Al. I imagine that the process would be more useful if it could produce various phases of solid NiAl rather than some Ni and mostly liquid Al.

Needless to say, nobody, most probably not even the reported successful ones, has performed experiments looking at this aspect in particular.

Quote from BobHiggins

The electron donor concept is interesting, particularly for a neutral metal gas vapor + hydrogen. I don't know if this is important or not. Me356's input can only be taken as speculation at the moment because his work has not been substantiated (yet). MFMP will be allowed to evaluate one of Me356's devices as a black box. Me356's input will be taken more seriously once it is proved that he does have something working.

Piantelli himself writes in one of his patent (that I previously linked) that the electron donor material is one of many possible ways to ionize the hydrogen adsorbed on the metal surface (and increase H- production. For Dufour this is a way for obtaining his own shrunken hydrogen, the pico-hydride), and lists it along things like irradiation with various kinds of radiation or radiofrequencies. It's not like I'm inventing a novel theory of operation or solely relying on the 'me356 says'.