Frank Gordon's "Lattice Energy Converter (LEC)"...replicators workshop

    http://przyrbwn.icm.edu.pl/APP/PDF/114/a114zS03.pdf


    The Response of Work Function of Thin Metal Films to Interaction with Hydrogen


    E. Nowicka and R. Nowakowski

    Institute of Physical Chemistry, Polish Academy of Sciences

    Kasprzaka 44/52, 01-224 Warszawa, Poland


    The aim of this paper is to summarize the results of experiments carried

    out at our laboratory on the response of the work function of several thin

    films of transition metals and rare earth metals to interaction with molecular

    hydrogen. The main focus concerns the description of surface phenomena

    accompanying the reaction of hydride formation as a result of the adsorbate’s incorporation into the bulk of the thin films. Work function changes

    ∆Φ caused by adsorption and reaction concern the surface, hence this experimental method is appropriate for solving the aforementioned problem.

    A differentiation is made between the work function changes ∆Φ due to creation of specific adsorption states characteristic of hydrides, and ∆Φ arising

    as a result of surface defects and protrusions induced in the course of the

    reaction. The topography of thin metal films and thin hydride films with

    defects and protrusions was illustrated by means of atomic force microscopy.

    For comparison, the paper discusses work function changes caused by H2 interaction with thin films of metals which do not form hydrides (for example

    platinum), or when this interaction is performed under conditions excluding

    hydride formation for thermodynamic reasons. Almost complete diminishing

    of ∆Φ was observed, in spite of significant hydrogen uptake on some rare

    earth metals, caused by formation of the ordered H–Y–H surface phase.

    Cydonia, can. There is considerable food for thought here. Matt made this 'voltage recovery' table using 2 brass electrodes, 1 plated and 1 un-plated (WE and CE). They were short circuited and earthed, and when the short circuit was removed mV were measured against time. What does this suggest to you?





    TIME -seconds


    		 OUTPUT mV.

    0


    100mV (instantly)



    30

    140




    60

    132




    90

    146




    120

    152




    150

    158




    180

    152




    100mV instantly it's a lot if we try a comparison with for example a Seebeck effect values several orders less.

    I remain disappointed by the plating process which could keep internal stresses.

    I could be relevant after plating to test an annealing then checking again the effect.


    About your paper, clearly hydrogen even at surface plays a role to lower the work function.

    I think too many people too quickly concluded that hydrogen inside or onto a metal lattice is simply a free H+ or an hydride.

    I expect rather more often it could remain a simple H neutral by keeping his electron ( bounded) even inside the lattice.

    In this way, we could see an interaction between the lattice with his electrons cloud and this neutral hydrogen tending to lower his work function.


    Now, if we consider that hydrogen trapped lowers the work function, this is only IRs which induce the kinetic energy to electrons escaped.

    For higher voltage we should need higher IRs frequency.

    this is the common understanding this way or hydrides formation. As i said i think that a neutral H could exists too even inside the lattice. A soup isn't never fully homogeneous it's well known there is always some pieces inside aahaha.

    Alan Smith

    What was the separation distance and in what environment? In general, I suspect that many thin spacer materials will be partially conductive through surface impurities. If there is a chemical reaction in one of the plates (e.g. desorbing H atoms causing oxide reduction) you might be observing the voltage generated by such reaction; if the materials are dissimilar, voltage due to (slow) galvanic corrosion could be observed too.


    EDIT: the plated sheet oxidizes quickly so part of the observed voltage could also be from this.


    EDIT: I just made a short-circuit recovery test using a roughly Fe-plated steel piece in diluted HCl solution (the usual grainy black layer was formed). Current upon load-testing was about 85 µA, decreasing to 60 µA. I dried the plate, but completely removing moisture is difficult within short periods, and the thin spacers I use will easily absorb it.


    Quote from can

    EDIT: the plated sheet oxidizes quickly so part of the observed voltage could also be from this.

    Not a problem (in general) if you use alkaline electrolytes and rinse and dry the electrodes immediately they come out of the tank. And indeed all or part of this voltage could be artifactual but I doubt it.

    Spacing here were 0.1 mm thick microscope slide cover slips, occluding about 20% of the area of the plates.

    Quote from Alan Smith

    Not a problem (in general) if you use alkaline electrolytes and rinse and dry the electrodes immediately they come out of the tank. And indeed all or part of this voltage could be artifactual but I doubt it.

    Spacing here were 0.1 mm thick microscope slide cover slips, occluding about 20% of the area of the plates.

    I don't have an alkaline plating solution, but I could obtain a similarly-looking rough black surface and similar voltage results by temporarily swapping electrode polarity when using a relatively diluted KOH electrolyte solution with steel electrodes, i.e. just the result of normal electrolysis. The surface does not rust as rapidly that way.


    In any case if I go great lengths avoiding moisture traces on the thin spacers and quickly rinse and dry the cathode, I get no or very little voltage (few mV) and negligible current (0.1–0.2 µA).


    Ordinary glass may adsorb H atoms, something that for instance Francesco Celani suggested being an important factor in his cells (citing Langmuir: http://www.francescocelaniener…esen_Finale-MIT2014A4.pdf). Water molecules could possibly easily migrate along glass surfaces for the same reason.



    Quote from Ahlfors

    ....

    PVD, high vacuum , quartz microbalance, etc... of course this is with much more sophisticated equipment and processes than what I am using.


    I would have never tried in the first place if I didn't read of successful results with cells in air and with Fe plating on Fe.

    Quote from can

    In any case if I go great lengths avoiding moisture traces on the thin spacers and quickly rinse and dry the cathode, I get no or very little voltage (few mV) and negligible current (0.1–0.2 µA).

    I think you should consider how long you are electrolysing the working electrodes for. Hours or days would seem to be preferable periods.

    Alan Smith

    I realize that, but when I initially saw a voltage and apparently even more easily reproduced the effect in subsequent attempts, I did not apply electrolysis for a long time at all. So, this is only a confirmation that the way I was doing it probably just causes an artifact. I don't rule out that a real LEC effect (showing a voltage with plates or sheets separated by a several millimeters distance) will become visible by following a proper electroplating protocol.

    Quote from can

    I dried the plate, but completely removing moisture is difficult within short periods, and the thin spacers I use will easily absorb it.

    A couple of suggestions:

    1) I verifyid that a little bit of moisture is not a problem (either with active electrode or dummy), no voltage arise due to moisture alone, as long as electrodes are well insulated (i.e. the spacers do their work);

    2) use plastic spacers: even electric tape (one layer) is good, its thickness is something close to 0.1 mm, and you can use multiple layers;

    3) use a wider gap: 0.1 mm can be too small and prone to isolation problems and artifacts. We tryed 0.5-0.9 mm, Frank tested even 6 mm. If you get the real effect, it should work good with these spacings;

    4) if you cannot obtain a voltage, this may be due to the duration and current used during the plating process. We all have used very small currents (mA) for very long times (many hours).

    I should try that someday. Unfortunately I haven't had yet luck with a FeCl solution, not even after plating for several hours (more than 4) at currents in the 10–20 mA range. When a voltage appeared upon subsequent testing, it seemed associated with impurities or moisture on the spacer materials (I also tried using electrical tape or scotch tape using 2 or 3 layers), and adding a new certainly clean layer removed the effect.


    I tried exploring other ways of plating Fe. A citric acid/iron citrate solution works also on Cu, in particular at high current, very quickly forming a smooth and durable thin layer. I tried doing a magnetic test and the layer was indeed magnetic. I recall reading others having problems with Fe plating on Cu using a FeCl solution, so this could possibly work.



    Brief video of magnetic test:


    However, when I tried it on Fe, following a similar procedure as done earlier using the same steel pieces (cleaned), it gave zero mV. Differently than with chloride plating, no quick oxidation occurs.


    At high current, citric acid-entrained vapor rises from the vessel and tends to make everything in the surroundings sticky, though. Also, if the cathode gets too hot, it decomposes the acid, producing an insoluble white precipitate. Your mileage may vary.

    Thanks can. I think you are still in too much of a hurry, and at some point you need to go over the Faraday limit to split water, theoretically 1.23V. Because of inefficiencies, you would need 1.8- 2V in the cell. (others may think differently).

    It's possible that I might have accidentally deposited a Fe-C alloy instead of only Fe. While looking for possible papers on citrate plating baths I found this one (open access):


    (PDF) Electrodeposition of Fe-C Alloys from Citrate Baths: Structure, Mechanical Properties, and Thermal Stability (researchgate.net)


    Some interesting excerpts:


    Quote

    Almost all studies on electrodeposition of Fe-C alloys use citric acid and/or ascorbic acid in the electrolyte in order to codeposit carbon. However, Fujiwara et al. showed that other hydroxycarboxylic and polycarboxylic acids are also suitable for the electrodeposition of Fe-C alloys [10,11]. Furthermore, they investigated the effect of other bath components [12].


    Fe-C increases hydrogen co-deposition compared to just Fe? This might be useful for LEC replications.


    Quote

    The codeposition of hydrogen is inherent to the electrodeposition of iron and its alloys in general [16], but was shown to be significantly enhanced in the case of Fe-C alloy deposition [17].


    The authors use a higher solution pH compared to other authors to avoid co-depositing too much hydrogen. It looks like if hydrogen co-deposition is what is desired for a LEC replication, pH should be low.


    Quote

    [...] The corresponding bath compositions and deposition parameters are shown in Table 1. The new electrolyte contains sodium sulfate as a conducting salt and the small amount of citric acid in the bath from [8] is replaced by a larger amount of tri-sodium citrate. Thus, the pH is increased leading to the reduction of hydrogen codeposition on the one hand, but the presence of ferric hydroxides on the other hand.


    They use however small amounts of citrates. The Fe ions come from FeSO4.7H2O (which I should get eventually). In my quick test above there were some from ferric citrate formed from steel pieces and a bit of hydrogen peroxide help.